Name: 129-64-6|(3aR,4S,7R,7aS)-rel-3a,4,7,7a-Tetrahydro-4,7-methanoisobenzofuran-1,3-dione|98%
Brand: Ambeed
SKU: A198434
Price: 5.0 USD
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1
[ 67-56-1 ]
[ 129-64-6 ]
[ 39589-98-5 ]

Yield	Reaction Conditions	Operation in experiment
96%	With hydrogen cation
95%	With hydrogenchloride In water at 65℃; for 4h; Inert atmosphere;	S.2 Synthesis Example 2 Synthesis Example 2 To a 1 L reaction vessel, 5-norbornene-2,3-dicarboxylic anhydride (1,150 g, 7.01 mol, exo form:endo form=0:100) manufactured by Wako Pure Chemical Industries, Ltd., methanol (5.75 mL), and concentrated hydrochloric acid (57.5 mL) having a concentration of 37% by mass were sequentially added under an argon stream to obtain a mixture liquid. Then, the mixture liquid was stirred under reflux conditions (internal temperature: 65° C.) for 4 hours to obtain a reaction liquid. After the reaction under reflux conditions for 4 hours in this way (after completion of the reaction), GC measurement was performed on the reaction liquid to confirm the disappearance of the raw material 5-norbornene-2,3-dicarboxylic anhydride. Then, methanol was distilled off from the reaction liquid under reduced pressure using a rotary evaporator to obtain a liquid product. Next, the liquid product was dissolved in ethyl acetate (5.8 L) and transferred to a separatory funnel. The liquid product was washed twice with saturated sodium hydrogen carbonate aqueous solution (2.3 L) and then once with water (2.3 L) to obtain an organic layer. Then, ethyl acetate was distilled off from the organic layer under reduced pressure using a rotary evaporator, thereby obtaining cis-5-norbornene-endo-2,3-dimethyl dicarboxylate (1,404 g, yield: 95%, exo form: endo form=0:100). Regarding the above product, the "exo form" means that all the groups represented by the formula: -COOMe have an exo conformation with respect to the norbornene ring to be bonded, and on the other hand, the "endo form" means that all the groups represented by the formula: -COOMe have an endo conformation with respect to the norbornene ring to be bonded. Note that the structure of the product was also identified by 1H-NMR.
92%	With quinindine In tetrachloromethane; toluene at -55℃; for 60h; optical yield given as %ee;

53.2%	With toluene-4-sulfonic acid for 10h; Reflux;
	With toluene-4-sulfonic acid

Reference： [1]Gastel, F. J. C. van; Klunder, A. J. H.; Zwanenburg, B. [Recueil des Travaux Chimiques des Pays-Bas, 1991, vol. 110, # 5, p. 175 - 184]
[2]Current Patent Assignee: ENEOS HOLDINGS INC - US2021/122724, 2021, A1 Location in patent: Paragraph 0086-0087
[3]Location in patent: body text Kong, Ning-Chuan; Zhang, Yu; Gao, Suo; Lu, Yang; Zheng, Qi-Tai; Sun, Quan-Yun; Yang, Fu-Mei; Di, Ying-Tong; Hao, Xiao-Jiang [Tetrahedron Letters, 2009, vol. 50, # 8, p. 957 - 959]
[4]Mao, Jiangang; Xie, Hujun; Bao, Weiliang [Organic Letters, 2015, vol. 17, # 15, p. 3678 - 3681]
[5]Morgan et al. [Journal of the American Chemical Society, 1944, vol. 66, p. 404,406] Current Patent Assignee: SOWA - US2471790, 1945, A Bauer; Nambury [Journal of Organic Chemistry, 1961, vol. 26, p. 1106]
[6]Hung, Chi Wai; Wong, Henry N. C. [Tetrahedron Letters, 1987, vol. 28, # 21, p. 2392 - 2396]

2
[ 107-10-8 ]
[ 129-64-6 ]
[ 29633-42-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	In toluene Reflux;	General procedure for the synthesis of 3-13. General procedure: The appropriate amine ((benzylamine (3, 1 mmol), 1-aminopiperidine (5, 1 mmol), propargylamine (6, 2.6 mmol), propylamine (7, 3.9 mmol), phenylhydrazine (8, 4 mmol), ethylenediamine (9, 2.7 mmol), 1,3-diaminopropane (11, 1.4 mmol), 1,4-diaminobutane (12, 3 mmol) or N,N-dimethylethylenediamine (13, 2.5 mmol)) were reacted with compound 2 (1 mmol) in toluene (100 ml) under reflux conditions for 10-24 hours to afford compounds 3-13, respectively.
	With benzene

Reference： [1]Egunlusi, Ayodeji O.; Malan, Sarel F.; Joubert, Jacques [Arkivoc, 2020, vol. 2020, # 5, p. 17 - 27]
[2]Current Patent Assignee: DUPONT DE NEMOURS INC - US2462835, 1943, A

3
[ 1454-85-9 ]
[ 129-64-6 ]
[ 21577-88-8 ]

Reference： [1]Journal of the American Chemical Society,1952,vol. 74,p. 3955

4
[ 106-49-0 ]
[ 129-64-6 ]
[ 72657-49-9 ]

Yield	Reaction Conditions	Operation in experiment
86%	With triethylamine In N,N-dimethyl-formamide at 120℃; for 16h;
86%	With triethylamine In N,N-dimethyl-formamide at 120℃; for 16h;
86%	With triethylamine In N,N-dimethyl-formamide at 120℃; for 16h; Inert atmosphere; Sealed tube;

	With benzene
	In N,N-dimethyl-formamide at 120℃; for 16h;

Reference： [1]Mao, Jiangang; Zhang, Shuo-Qing; Shi, Bing-Feng; Bao, Weiliang [Chemical Communications, 2014, vol. 50, # 28, p. 3692 - 3694]
[2]Mao, Jiangang; Bao, Weiliang [Organic Letters, 2014, vol. 16, # 10, p. 2646 - 2649] Mao, Jiangang; Xie, Hujun; Bao, Weiliang [Organic Letters, 2015, vol. 17, # 15, p. 3678 - 3681]
[3]Mao, Jiangang; Bao, Weiliang [Chemical Communications, 2014, vol. 50, # 99, p. 15726 - 15729]
[4]Morgan et al. [Journal of the American Chemical Society, 1944, vol. 66, p. 404,406]
[5]Mao, Jiangang; Li, Huifang; Wen, Herui; Li, Min; Fan, Xiaolin; Bao, Weiliang [Advanced Synthesis and Catalysis, 2016, vol. 358, # 12, p. 1873 - 1879]

5
[ 141-43-5 ]
[ 129-64-6 ]
[ 68297-52-9 ]

Yield	Reaction Conditions	Operation in experiment
90%	With triethylamine In toluene for 12h; Dean-Stark; Reflux;
90%	With triethylamine In toluene at 120℃; for 12h; Dean-Stark;
89%	Stage #1: ethanolamine; 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride Stage #2: In toluene for 14h; Reflux;

87.3%	In toluene at 20 - 100℃; for 30h;
72%	In toluene Heating;
47%	at 175 - 180℃; for 2h;
	With benzene

Reference： [1]Rao N, Vijayakameswara; Dinda, Himadri; Venu, Parvathy; Sarma, Jayasri Das; Shunmugam, Raja [RSC Advances, 2014, vol. 4, # 85, p. 45625 - 45634]
[2]Venu, Parvathy; Le, Trong-Nghia; Kumar, Pawan; Patra, Diptendu; Kumar, Rajan; Lee, Cheng-Kang; Rao, N. Vijayakameswara; Shunmugam, Raja [Chemistry - An Asian Journal, 2021, vol. 16, # 17, p. 2552 - 2558]
[3]Location in patent: experimental part Rolfe, Alan; Probst, Donald A.; Volp, Kelly A.; Omar, Iman; Flynn, Daniel L.; Hanson, Paul R. [Journal of Organic Chemistry, 2008, vol. 73, # 22, p. 8785 - 8790]
[4]Kumar, Rajan; Ray, Subir Kumar; Mukherjee, Saikat; Saha, Sudipta; Bag, Arijit; Ghorai, Pradip Kr.; Ghosh, Nirmalya; Shunmugam, Raja [Chemistry - A European Journal, 2019, vol. 25, # 59, p. 13514 - 13522]
[5]Davies, R. Gareth; Gibson, Vernon C.; Hursthouse, Michael B.; Light, Mark E.; Marshall, Edward L.; North, Michael; Robson, David A.; Thompson, Ian; White, Andrew J. P.; Williams, David J.; Williams, Paul J. [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2001, # 24, p. 3365 - 3381]
[6]Ranise, Angelo; Spallarossa, Andrea; Cesarini, Sara; Bondavalli, Francesco; Schenone, Silvia; Bruno, Olga; Menozzi, Giulia; Fossa, Paola; Mosti, Luisa; La Colla, Massimiliano; Sanna, Giuseppina; Murreddu, Marta; Collu, Gabriella; Busonera, Bernardetta; Marongiu, Maria Elena; Pani, Alessandra; La Colla, Paolo; Loddo, Roberta [Journal of Medicinal Chemistry, 2005, vol. 48, # 11, p. 3858 - 3873]
[7]Current Patent Assignee: DUPONT DE NEMOURS INC - US2462835, 1943, A

6
[ 62-53-3 ]
[ 129-64-6 ]
N-phenylbicyclo[2.2.1]hept-5-ene-2-endo,3-endo-dicarboximide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With triethylamine In toluene at 160℃; for 2h; Sealed tube;
88%	With pyridine for 2h; Heating;
80%	Stage #1: aniline; 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride In tetrahydrofuran at 40℃; for 0.5h; Inert atmosphere; Stage #2: at 160℃; for 0.25h; Inert atmosphere;

	With benzene
	In acetic acid for 3h; Heating;
	Stage #1: aniline; 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride In ethyl acetate at 20℃; for 18h; Stage #2: With sodium acetate; acetic anhydride for 1h; Reflux;
	With benzene
	With triethylamine In toluene at 120℃; for 12h;

Reference： [1]Kotha, Sambasivarao; Aswar, Vikas R. [Organic Letters, 2016, vol. 18, # 8, p. 1808 - 1811]
[2]Abbady; Kandeel; Youssef [Phosphorus, Sulfur and Silicon and the Related Elements, 2000, vol. 163, p. 55 - 64]
[3]Takebayashi, Satoshi; John, Jeremy M.; Bergens, Steven H. [Journal of the American Chemical Society, 2010, vol. 132, # 37, p. 12832 - 12834]
[4]Morgan et al. [Journal of the American Chemical Society, 1944, vol. 66, p. 404,406]
[5]Young, Philip R.; Chang, A. C. [Journal of Heterocyclic Chemistry, 1983, vol. 20, p. 177 - 182]
[6]Current Patent Assignee: FORSCHUNGSVERBUND BERLIN EV - WO2017/186793, 2017, A1 Location in patent: Page/Page column 39
[7]Current Patent Assignee: DUPONT DE NEMOURS INC - US2462835, 1943, A
[8]Kotha, Sambasivarao; Pulletikurti, Sunil [Heterocycles, 2020, vol. 101, # 2, p. 717 - 725]

7
[ 107-11-9 ]
[ 129-64-6 ]
[ 6971-11-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	In acetic acid for 16h; Inert atmosphere; Reflux;
89%	With acetic acid at 20 - 110℃; for 6h; Reflux; Inert atmosphere;	2.1 Embodiment 2. Under nitrogen atmosphere, in 250 ml of adding three-necked bottle 10g (0.102mol) norborneol alkene Shan Gan and 150 ml glacial acetic acid, to be completely dissolved after adding dropwise under stirring 5.82g (0.102mol) ene propyl amine, the reaction at room temperature 1h, then heating to 110 °C reaction refluxing 5h. Stop reaction, to be cooled to the room temperature, is poured into 300 ml water, immediately with a white precipitate out, filtering, the cake is washed with water three times, to obtain white powder product after drying (B1) 12.45g, the yield is 89%
	With benzene

Reference： [1]Gomez-Sanjuan, Asier; Sotomayor, Nuria; Lete, Esther [European Journal of Organic Chemistry, 2013, # 29, p. 6722 - 6732]
[2]Current Patent Assignee: NANCHANG UNIVERSITY - CN105669738, 2016, A Location in patent: Paragraph 0026; 0027
[3]Current Patent Assignee: DUPONT DE NEMOURS INC - US2462835, 1943, A Current Patent Assignee: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN (MICHELIN) - US2524145, 1948, A

8
[ 74-89-5 ]
[ 129-64-6 ]
(1R,2S,6R,7S)-4-methyl-4-azatricyclo[5.2.1.0(2,6)]dec-8-ene-3,5-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With acetic acid In water for 3h; Heating;
90%	With triethylamine In toluene at 160℃; for 2h; Sealed tube;
	With water beim anschliessenden Erhitzen auf 180grad;

	With acetyl chloride In water for 20h; Heating;
	In ethanol Reflux;
	With water beim anschliessenden Erhitzen auf 180grad;

Reference： [1]Larsen, Caitlin A.; Taylor, Erin L.; Lambert, John N.; Chiefari, John A. [Australian Journal of Chemistry, 2002, vol. 55, # 4, p. 245 - 248]
[2]Kotha, Sambasivarao; Aswar, Vikas R. [Organic Letters, 2016, vol. 18, # 8, p. 1808 - 1811]
[3]Walton [Journal of Organic Chemistry, 1957, vol. 22, p. 315,317]
[4]Weinstein; Leffler; Currie [Molecular Crystals and Liquid Crystals (1969-1991), 1984, vol. 104, # 1-2, p. 95 - 109]
[5]Koehler, Valentin; Bailey, Kevin R.; Znabet, Anass; Raftery, James; Helliwell, Madeleine; Turner, Nicholas J. [Angewandte Chemie - International Edition, 2010, vol. 49, # 12, p. 2182 - 2184]
[6]Current Patent Assignee: DUPONT DE NEMOURS INC - US2462835, 1943, A

9
[ 100-46-9 ]
[ 129-64-6 ]
[ 75715-21-8 ]

Yield	Reaction Conditions	Operation in experiment
99%	In acetic acid for 5h; Inert atmosphere; Reflux;
93%	With triethylamine In toluene for 19h; Heating;
85%	In ethanol at 165 - 175℃;

	With benzene
	With triethylamine In toluene for 5h; Reflux;

Reference： [1]Gomez-Sanjuan, Asier; Sotomayor, Nuria; Lete, Esther [European Journal of Organic Chemistry, 2013, # 29, p. 6722 - 6732]
[2]Camm, Kenneth D.; Castro, Nemesio Martinez; Liu, Yuwen; Czechura, Pawel; Snelgrove, Jennifer L.; Fogg, Deryn E. [Journal of the American Chemical Society, 2007, vol. 129, # 14, p. 4168 - 4169]
[3]Yasuda; Saito; Arakawa; Yoshifuji [Chemical and Pharmaceutical Bulletin, 1995, vol. 43, # 8, p. 1318 - 1324]
[4]Current Patent Assignee: DUPONT DE NEMOURS INC - US2462835, 1943, A
[5]Fülöp, Ferenc; Haukka, Matti; Kiss, Loránd; Nonn, Melinda; Novák, Tamás T.; Remete, Attila Márió [Beilstein Journal of Organic Chemistry, 2020, vol. 16, p. 2562 - 2575]

10
[ 628-87-5 ]
[ 129-64-6 ]
[ 100394-99-8 ]

Reference： [1]Lynn [Journal of Organic Chemistry, 1958, vol. 23, p. 758]

11
[ 129-64-6 ]
[ 21715-90-2 ]

Yield	Reaction Conditions	Operation in experiment
66%	With hydroxylamine hydrochloride; sodium carbonate In water at 20℃; for 3h;	Synthesis of (3aR,4S,7R,7aS)-2-hydroxy-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione (N-hydroxy-5-endo-norbornene-2,3-dicarboximide) (3b) General procedure: The following protocolbased on a procedure of Zinner and Düerkop.19Hydroxyl amine hydrochloride (833 mg, 12 mmol)and sodium carbonate (636 mg, 6 mmol) aredissolved in water (20 mL) and allowed to stir atroom temperature. After 10 min the 5-norbornene-2,3-dicarboxylic anhydride (1.97 g, 12 mmol) isadded, and the reaction mixture is stirred foranother three hours at room temperature. Somesolid material forms, which are filtered off, washedcarefully with water (40mL) and dried underreduced pressure. The substance is used withoutfurther purification
	With methanol; hydroxylamine; sodium ethanolate
	With water; hydroxylamine

Reference： [1]Maftei, Elena; Maftei, Catalin V.; Freytag, Matthias; Franz, M. Heiko; Bannenberg, Thomas; Neda, Ion [Revue Roumaine de Chimie, 2018, vol. 63, # 3, p. 245 - 255]
[2]Stolberg et al. [Journal of the American Chemical Society, 1957, vol. 79, p. 2615]
[3]Bauer; Miarka [Journal of Organic Chemistry, 1959, vol. 24, p. 1293,1295]

12
[ 129-64-6 ]
[ 2746-19-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	at 180℃; for 24h;
94%	With triethylamine In ethanol Irradiation; 2-6 h; other endo-Diels-Alder cycloadducts;
94%	With triethylamine In ethanol Irradiation; 2-6 h;

80.1%	In toluene at 200℃; for 0.133333h; Microwave irradiation;	3 A method for preparing high-purity cis-5-norbornene-exo-2,3-dicarboxylic acid anhydride by microwave reaction is disclosed. The method comprises the following steps: using cis-5-norbornene-endo-2,3-dicarboxylic anhydride as raw material, Specific steps are as follows:(1) In a 1 L reaction flask, 200 g of cis-5-norbornene-endo-2,3-dicarboxylic anhydride and 600 mL of toluene were stirred and placed in a microwave autoclave. The temperature was raised to 200 ° C, 100-200GHz microwave for 8 minutes;(2) The reaction was completed, the reactor of step (1) was cooled to 110 ° C, stirred in an oil bath for 30 minutes to crystallize, cooled to room temperature, filtered and dried to give the product cis-5-norbornene- Dicarboxylic anhydride 160.2 g; Yield: 80.1%; Purity: 98.2%; Oxide impurity content: 0.06%.
77%	at 190 - 192℃; for 1.5h;
40%	at 190℃; for 1.5h;
40%	at 180℃; for 6h;	S.1 Synthetic Example 1 Thermal Rearrangement of Nadic Anhydride Nadic anhydride (ACROS, 225 g, 1.4 mol, pure endo isomer) was put into the 500 ml 2-neck round bottom flask, and refluxed while the temperature was increased to 180° C. Next, while it was agitated at 300 rpm, it was reacted for 6 hours, the reactants were cooled and recrystallized with benzene. The product that was rearranged by 80% exo isomers were obtained by carrying out the recrystallization twice (yield: 40%). [0082] The NMR analysis results of the pure endo isomer compound are described below. [0083] 1H-NMR (300 MHz, CDCl3): δ6.31 (2H), 3.50 (2H,) 3.59 (2H), δ1.57 to 1.80 (2H) [0084] In addition, the results of the NMR analysis that was carried out in order to confirm that the 80% exo isomer nadic anhydride compound that was manufactured through thermal rearrangement was formed are described below. [0085] 1H-NMR (300 MHz, CDCl3): δ6.30 to 6.34 (2H), 3.44 (2H) 3.01 (2H), δ1.68 (1H), 61.42 (1H)
32.8%	at 185℃;	3.1 2.3.1. Synthesis of cis-5-norbornene-exo-2,3-dicarboxylic anhydride (1) The synthetic procedure is a modification of the previously published method [16]. cis-5-norbornene-endo-2,3-dicarboxylic anhydride (250 g, 1.52 mol) was heated to 185 °C for 4-5 h. After cooling to room temperature, the endo/exo mixture was further purified by recrystallization in ethyl acetate four times to obtain pure cis-5-norbornene exo-2,3-dicarboxylic anhydride. Yield: 82 g (32.8%), purity: >98% exo isomer, mp: 141-143 °C, lit. 143 °C[16] . 1H NMR (CDCl3): δ = 6.34 (s, 2H), 3.45 (s, 2H), 3.02 (s, 2H), 1.67 (d, 1H), 1.44 (d, 1H). 13C NMR (CDCl3): δ = 172.3, 138.6, 49.4, 47.5, 44.7.
30%	In 1,2-dichloro-benzene Reflux; Inert atmosphere; Industrial scale;
25%	at 200℃;
22%	at 190℃;
16%	In 1,2-dichloro-benzene at 185℃; for 4h;
14%	at 210℃; for 2h; Inert atmosphere;	2 Example 2; Synthesis of Monomer 2: (1) Conversion of the endo to the exo isomer was adapted from previous literature procedures. (Canonne, et al., J Org Chem 1982, 47, 3953) 100 g (0.60 mol) of 5-Norbornene-2,3-dicarboxylic anhydride (endo) was placed in a 250 mL round bottom flask and heated at 210° C. under nitrogen for 2 hours. The flask was cooled to 120° C. after which toluene (100 mL) was added. This solution was allowed to cool to room temperature. The resulting mixture was filtered and the residue was recrystallized 4 times from toluene to give white crystals of 5-norbornene-2,3-dicarboxylic anhydride (exo), (14 g, 0.14 mol, 14% yield, mp=143° C.). 1H NMR (300 MHz, CDCl3) δ 1.44 (d, J=1.2 Hz, 1H), 1.66 (d, J=1.2 Hz, 1H), 3.01 (s, 2H), 3.47 (s, 2H), 6.34 (d, J=10.2 Hz, 2H). 13C NMR (300 MHz, CDCl3) δ 171.61, 137.95, 48.77, 46.87, 44.11.
	at 190℃;
	Heating;
	In Isopropyl acetate at 230℃; Microflow reactor; Thermal isomerization; optical yield given as %de;
	at 195℃; Inert atmosphere; Neat (no solvent);
	In toluene at 100 - 170℃;	1 Synthesis Example 1Synthesis of 5-norbornene-exo-2,3-dicarboxylic Anhydride Represented by Chemical Formula (2)In a 1 L four-necked flask equipped with a stirrer, condenser tube and thermometer there was charged 300 g of 5-norbornene-endo-2,3-dicarboxylic anhydride (product of Hitachi Chemical Co., Ltd., melting point: 164.5-166° C., hereunder referred to as “endo-HAC”), and it was heated and stirred at 170° C. for 5 hours. The flask was then allowed to cool, and when it reached 100° C., 300 g of toluene was added and the mixture was stirred and allowed to stand for one night. The precipitated crystals were removed by filtration. The crystal weight was 223 g. Next, 300 g of toluene was added to the crystals, recrystallization was performed, the crystals obtained by recrystallization were vacuum dried and the adhering toluene was removed. The amount of obtained crystals was 156 g and they had a melting point of 146.5-148.5° C. The NMR spectrum was analyzed, confirming that the crystals were 5-norbornene-exo-2,3-dicarboxylic anhydride (hereunder referred to as “exo-HAC”).
	at 185℃; for 4h;

Reference： [1]Kotha, Sambasivarao; Aswar, Vikas R. [Organic Letters, 2016, vol. 18, # 8, p. 1808 - 1811]
[2]Pandey, Bipin; Athawale, Asawari A.; Reddy, Ravinder S.; Dalvi, Pramod V.; Kumar, Pradeep [Chemistry Letters, 1991, # 7, p. 1173 - 1176]
[3]Pandey, Bipin; Athawale, Asawari A.; Reddy, Ravinder S.; Dalvi, Pramod V.; Kumar, Pradeep [Chemistry Letters, 1991, # 7, p. 1173 - 1176]
[4]Current Patent Assignee: JEWIM PHARMACEUTICAL SHANDONG - CN104130228, 2016, B Location in patent: Paragraph 0038-0040
[5]Cannone, Persephone; Belanger, Denis; Lemay, Gilles [Journal of Organic Chemistry, 1982, vol. 47, # 20, p. 3953 - 3959]
[6]Gastel, F. J. C. van; Klunder, A. J. H.; Zwanenburg, B. [Recueil des Travaux Chimiques des Pays-Bas, 1991, vol. 110, # 5, p. 175 - 184]
[7]Current Patent Assignee: LG CHEM CO.,LTD. - US2014/213815, 2014, A1 Location in patent: Paragraph 0081-0085
[8]Mulpuri, Syamkumar V.; Shin, Jinbok; Shin, Boo-Gyo; Yoon, Do Y.; Greiner, Andreas [Polymer, 2011, vol. 52, # 19, p. 4377 - 4386,10]
[9]Kreituss, Imants; Chen, Kuang-Yen; Eitel, Simon H.; Adam, Jean-Michel; Wuitschik, Georg; Fettes, Alec; Bode, Jeffrey W. [Angewandte Chemie - International Edition, 2016, vol. 55, # 4, p. 1553 - 1556][Angew. Chem., 2016, vol. 128, # 4, p. 1579 - 1582,4]
[10]Liu, Peng; Yasir, Mohammad; Kilbinger, Andreas F. M. [Angewandte Chemie - International Edition, 2019, vol. 58, # 43, p. 15278 - 15282][Angew. Chem., 2019, vol. 131, p. 15422 - 15426,5]
[11]To, Kenneth K.W.; Wang, Xinning; Yu, Chun Wing; Ho, Yee-Ping; Au-Yeung, Steve C.F. [Bioorganic and Medicinal Chemistry, 2004, vol. 12, # 17, p. 4565 - 4573]
[12]Matson, John B.; Grubbs, Robert H. [Journal of the American Chemical Society, 2008, vol. 130, # 21, p. 6731 - 6733]
[13]Current Patent Assignee: UNIVERSITY OF MASSACHUSETTS - US8329927, 2012, B2 Location in patent: Page/Page column 28-29
[14]Craig [Journal of the American Chemical Society, 1951, vol. 73, p. 4889,4891] Lieb, Folker; Niewoehner, Ulrich; Wendisch, Detlef [Liebigs Annalen der Chemie, 1987, p. 607 - 616] Denekamp; Weisz; Mandelbaum [Journal of Mass Spectrometry, 1996, vol. 31, # 9, p. 1028 - 1032]
[15]Location in patent: scheme or table Tarabara; Bondarenko; Kas'Yan [Russian Journal of Organic Chemistry, 2009, vol. 45, # 2, p. 234 - 241]
[16]Location in patent: experimental part Welch, Christopher J.; Gong, Xiaoyi; Cuff, James; Dolman, Sarah; Nyrop, Jason; Lin, Fiona; Rogers, Hallena [Organic Process Research and Development, 2009, vol. 13, # 5, p. 1022 - 1025]
[17]Long, Toby R.; Maity, Pradip K.; Samarakoon, Thiwanka B.; Hanson, Paul R. [Organic Letters, 2010, vol. 12, # 13, p. 2904 - 2907]
[18]Current Patent Assignee: SHOWA DENKO K K; Showa Denko Materials (in: Showa Denko) - US2011/301362, 2011, A1 Location in patent: Page/Page column 6
[19]Location in patent: experimental part Yoon, Kyung-Hwan; Kim, Kyung Oh; Wang, Chengqing; Park, Insook; Yoon, Do Y. [Journal of Polymer Science, Part A: Polymer Chemistry, 2012, vol. 50, # 18, p. 3914 - 3921]

13
[ 129-64-6 ]
[ 853658-14-7 ]

Yield	Reaction Conditions	Operation in experiment
99%	With hydrogen In tetrahydrofuran
99%	With hydrogen In tetrahydrofuran at 20℃; for 16h;	11 A solution of starting compound bicyclo[2.2.1 ]hept-5-ene-2,3-endo-dicarboxylic anhydride (0.82 g, 5 mmol) in THF (30 ml) was added Pd/C (10%, 0.53 g, 0.5 mmol). The mixture was stirred at room temperature under H2 for 16 hours. The mixture was filtered. The filtrate was concentrated under reduced pressure to give intermediate bicyclo[2.2.1 ]heptane-2,3-endo-dicarboxylic anhydride (0.82 g, 4.9 mmol, 99% yield) as white solid.Melting point: 163.8-164.6°C1HNMR (400 MHz, CDCI3): δ 3.41 (s, 2H), 2.86 (s, 2H), 1 .69-1 .73 (m, 4H), 1 .45-1.51 (m, 2H)
99%	With palladium 10% on activated carbon; hydrogen In tetrahydrofuran at 20℃; for 16h;	11 Preparation of bicyclo[2.2.1]heptane-2,3-endo-dicarboxylic anhydride (Intermediate 2) A solution of starting compound bicyclo[2.2.1]hept-5-ene-2,3-endo-dicarboxylic anhydride (0.82 g, 5 mmol) in THF (30 ml) was added Pd/C (10%, 0.53 g, 0.5 mmol). The mixture was stirred at room temperature under H2 for 16 hours. The mixture was filtered. The filtrate was concentrated under reduced pressure to give intermediate bicyclo[2.2.1]heptane-2,3-endo-dicarboxylic anhydride (0.82 g, 4.9 mmol, 99% yield) as white solid. [0246] Melting point: 163.8164.6° C. [0247] 1HNMR (400 MHz, CDCl3): δ 3.41 (s, 2H), 2.86 (s, 2H), 1.69-1.73 (m, 4H), 1.45-1.51 (m, 2H)

98%	With hydrogen In 1,4-dioxane for 6h;
98%	With cyclohexene In tetrahydrofuran Heating;
97%	With hydrogen In ethyl acetate
93%	With LaNi₅ hydride In tetrahydrofuran; methanol for 18h; Ambient temperature;
90%	With cyclohexene In tetrahydrofuran for 15h; Heating;
	With ethyl acetate; platinum Hydrogenation;
	With 1,4-dioxane; nickel Hydrogenation;
	With hydrogen In ethyl acetate
	With hydrogen In ethyl acetate
	With hydrogen In ethyl acetate
	With hydrogen
	With hydrogen
	With (bis(mesityl-benzimidazol-2-ylidene)phenyl)Co(N<SUB>2</SUB>)(PPh<SUB>3</SUB>); hydrogen In benzene-d6 at -196.16 - 59.84℃; for 17h;

Reference： [1]Cannone, Persephone; Belanger, Denis; Lemay, Gilles [Journal of Organic Chemistry, 1982, vol. 47, # 20, p. 3953 - 3959]
[2]Current Patent Assignee: CONRIG PHARMA APS - WO2012/16569, 2012, A1 Location in patent: Page/Page column 91; 92
[3]Current Patent Assignee: CONRIG PHARMA APS - US2013/303497, 2013, A1 Location in patent: Paragraph 0245
[4]Ohtani, Mitsuaki; Matsuura, Takaharu; Watanabe, Fumihiko; Narisada, Masayuki [Journal of Organic Chemistry, 1991, vol. 56, # 13, p. 4120 - 4123]
[5]Csende, Ferenc; Stajer, Geza [Organic Preparations and Procedures International, 1999, vol. 31, # 2, p. 220 - 222]
[6]Birney, David; Lim, Tang Kuan; Koh, Joanne H. P.; Pool, Brett R.; White, Jonathan M. [Journal of the American Chemical Society, 2002, vol. 124, # 18, p. 5091 - 5099]
[7]Imamoto, Tsuneo; Mita, Takeshi; Yokoyama, Masataka [Journal of Organic Chemistry, 1987, vol. 52, # 26, p. 5695 - 5699]
[8]Stajer, G.; Csende, F.; Bernath, G.; Sohar, P.; Szunyog, J. [Monatshefte fur Chemie, 1994, vol. 125, # 8/9, p. 933 - 944]
[9]Craig [Journal of the American Chemical Society, 1951, vol. 73, p. 4889,4891]
[10]Morgan et al. [Journal of the American Chemical Society, 1944, vol. 66, p. 404,406]
[11]Jaeschke, Georg; Seebach, Dieter [Journal of Organic Chemistry, 1998, vol. 63, # 4, p. 1190 - 1197]
[12]O'Brien, Erin M.; Bercot, Eric A.; Rovis, Tomislav [Journal of the American Chemical Society, 2003, vol. 125, # 35, p. 10498 - 10499] Bercot, Eric A.; Rovis, Tomislav [Journal of the American Chemical Society, 2005, vol. 127, # 1, p. 247 - 254]
[13]Bolm, Carsten; Schiffers, Ingo; Dinter, Christian L.; Gerlach, Arne [Journal of Organic Chemistry, 2000, vol. 65, # 21, p. 6984 - 6991]
[14]Youk, Sung Hun; Oh, Sang Ho; Rho, Ho Sik; Lee, Je Eun; Lee, Ji Woong; Song, Choong Eui [Chemical Communications, 2009, # 16, p. 2220 - 2222]
[15]Van Zee, Nathan J.; Sanford, Maria J.; Coates, Geoffrey W. [Journal of the American Chemical Society, 2016, vol. 138, # 8, p. 2755 - 2761]
[16]Tokmic, Kenan; Markus, Charles R.; Zhu, Lingyang; Fout, Alison R. [Journal of the American Chemical Society, 2016, vol. 138, # 36, p. 11907 - 11913]

14
[ 129-64-6 ]
[ 6265-30-1 ]

Yield	Reaction Conditions	Operation in experiment
100%	With ammonium acetate; acetic acid at 140℃; for 96h; Inert atmosphere;
100%	With ammonium acetate; acetic acid at 140℃; for 16h;
98.8%	With ammonium acetate at 135℃; Industrial scale;	5 industrial synthesis of 7 A mixture of anhydride 6 (70.0 kg, 426.4 mol) and ammonium acetate (98.6 kg, 1279.2 mol) is heated to 135°C. The resulting liquid is then stirred at 135°C until the reaction is complete. The liquid is cooled and water (360 1) is added in about half an hour. The resulting suspension is then cooled, and the whitesolid is centrifuged and washed with 180 1 of water to obtain imide 7 as a white solid (dry weight 68.8 kg, yield 98.8%, purity [GCJ 99.84%).

91%	Stage #1: 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride With urea at 145℃; for 4h; Stage #2: With water Heating;
87%	With sodium acetate; ammonium chloride In acetic acid for 72h; Heating;
77%	With ammonium hydroxide for 48h; Reflux;	4.1 2.4.1 Synthesis of the exo-norbornene-2,3-dicarboximide (2) 5-Norbornene-2,3-dicarboxylic anhydride (15.03 g, 91.4 mmol, 1 equiv) and aqueous ammonia (25%, v/v, 100 mL) were added in a round-bottom flask equipped with reflux condenser and drying tube, and then heated to reflux for 48 h. Crystallization occurred over night, and the colorless crystal was filtered and washed with hexane. Yield: 11.52 g (70.6 mmol), 77%. 1H NMR (400 MHz, CDCl3), δ (ppm): 8.37 (brs, 1H, NH); 6.18 (s, 2H, C=CH); 3.36 (s, 2H, =CH-CH); 3.29 (s, 2H, CO-CH); 1.72 (d, 1H, J = 8.0 Hz, CH2-bridge); 1.51 (d, 1H, J = 12.0 Hz, CH2-bridge).
71%	With urea at 170 - 180℃; for 1h;
	With ammonia at 170℃;
	With ammonia; water Erhitzen des erhaltenen Ammonium-Salzes mit Acetanhydrid;
	With ammonium hydroxide; acetic anhydride 2.) reflux, 2 h; Yield given. Multistep reaction;
	With ammonia at 170 - 220℃;
	With ammonium hydroxide In water for 5h; Heating;
	Stage #1: 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride With ammonium hydroxide In water Stage #2: In acetic acid Heating;

Reference： [1]Breuning, Matthias; Haeuser, Tobias; Mehler, Christian; Daeschlein, Christian; Strohmann, Carsten; Oechsner, Andreas; Braunschweig, Holger [Beilstein Journal of Organic Chemistry, 2009, vol. 5]
[2]Combe, Craig M. S.; Biniek, Laure; Schroeder, Bob C.; McCulloch, Iain [Journal of Materials Chemistry C, 2014, vol. 2, # 3, p. 538 - 541]
[3]Current Patent Assignee: PROCOS SPA - WO2015/56205, 2015, A1 Location in patent: Page/Page column 13
[4]Location in patent: experimental part Mansfeld, Friederike M.; Feng, Guoqiang; Otto, Sijbren [Organic and Biomolecular Chemistry, 2009, vol. 7, # 20, p. 4289 - 4295]
[5]Ramon, Diego J.; Guillena, Gabriela; Seebach, Dieter [Helvetica Chimica Acta, 1996, vol. 79, # 3, p. 875 - 894]
[6]Yao, Pei-Shui; Cao, Qian-Yong; Peng, Rong-Peng; Liu, Jing-Hua [Journal of Photochemistry and Photobiology A: Chemistry, 2015, vol. 305, p. 11 - 18]
[7]Levchenko, N. K.; Segal', G. M.; Torgov, I. V. [Chemistry of Heterocyclic Compounds, 1981, vol. 17, # 3, p. 251 - 256][Khimiya Geterotsiklicheskikh Soedinenii, 1981, vol. 17, # 3, p. 347 - 351]
[8]Morgan et al. [Journal of the American Chemical Society, 1944, vol. 66, p. 404,406]
[9]Blomquist; Winslow [Journal of Organic Chemistry, 1945, vol. 10, p. 149,157]
[10]Chow, Yuan L.; Colon, Carlos J.; Chang, Dawid W. L.; Pillay, K. Somasekharen; Lochart Robert D.; Tezuka, Takahiro [Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1982, vol. 36, # 9, p. 622 - 634]
[11]Schier, Ernst-Juergen; Sacher, Wolfgang; Beck, Wolfgang [Zeitschrift fur Naturforschung, B: Chemical Sciences, 1987, vol. 42, # 11, p. 1424 - 1434]
[12]Weinstein; Leffler; Currie [Molecular Crystals and Liquid Crystals (1969-1991), 1984, vol. 104, # 1-2, p. 95 - 109]
[13]Location in patent: body text Makan; Tsymbal; Soboleva; Tarabara; Kas'Yan; Andronati [Russian Journal of General Chemistry, 2009, vol. 79, # 2, p. 292 - 296]

15
[ 129-64-6 ]
exo-2-hydroxy-5-oxo-4-oxatricyclo-[4.2.1.0^3,7]nonane-endo-9-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With formic acid; dihydrogen peroxide In water at 0℃;
	With peracetic acid; acetic acid
	Multi-step reaction with 2 steps 1: 90 percent / benzene; H₂O / 48 h / 20 °C 2: 70 percent / HCl / H₂O

	Multi-step reaction with 2 steps 1: 86 percent / benzene / 336000 h / 20 °C 2: 50 percent / formic acid; H₂O₂ / H₂O / 0 °C
	Multi-step reaction with 2 steps 1: 74 percent / benzene / 48 h / 20 °C 2: 85 percent / formic acid; H₂O₂ / H₂O / 0 °C
	Multi-step reaction with 2 steps 1: 78 percent / benzene; H₂O / 20 °C 2: 85 percent / formic acid; aq. hydrogen peroxide / 0 °C
	Multi-step reaction with 2 steps 1: chloroform; peroxyacetic acid 2: water
	Multi-step reaction with 2 steps 1: dichloromethane; chloroform; trifluoro-peroxyacetic acid / Reagens 4: Natriumsulfat 2: water

Reference： [1]Pal'chikov; Tarabara; Shishkina; Shishkin; Kol'tsov; Kas'yan [Russian Journal of Organic Chemistry, 2007, vol. 43, # 5, p. 660 - 673]
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[3]Pal'chikov; Tarabara; Shishkina; Shishkin; Kol'tsov; Kas'yan [Russian Journal of Organic Chemistry, 2007, vol. 43, # 5, p. 660 - 673]
[4]Pal'chikov; Tarabara; Shishkina; Shishkin; Kol'tsov; Kas'yan [Russian Journal of Organic Chemistry, 2007, vol. 43, # 5, p. 660 - 673]
[5]Pal'chikov; Tarabara; Shishkina; Shishkin; Kol'tsov; Kas'yan [Russian Journal of Organic Chemistry, 2007, vol. 43, # 5, p. 660 - 673]
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[7]Nasarow; Kutscherow; Bucharow [Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1958, p. 192,196][Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1958, p. 179,182]
[8]Berson; Suzuki [Journal of the American Chemical Society, 1958, vol. 80, p. 4341,4344]

16
[ 129-64-6 ]
[ 3853-88-1 ]

Yield	Reaction Conditions	Operation in experiment
	With water;Heating;	Carbic anhydride was synthesized by the reaction of maleic anhydride with cyclo peantadiene in a tri-flask at 160-190C until no back heat flow. The reaction was a cyclo addition to abide by the Diels-Alder rule, along with the performing of the reaction, there was a transient state intermediate product firstly, then transforming into carbic anhydride [26]. It was going to a get a white precipitation after putting the mixture into diethyl ether for dissolving at room temperature. The powder without diethyl ether was volatilized and hydrolyzed into Endc in the boiling water for continuous heating.

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[11]Applied Organometallic Chemistry,2017,vol. 31

17
[ 108-31-6 ]
[ 542-92-7 ]
[ 129-64-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	With 3-(n-butoxycarbonyl)-1-methylpyridinium bis(trifluoromethanesulfonyl)imide at 20℃; for 0.166667h; diastereoselective reaction;
99%	With 1-hexyl-3-methylimidazolium tetrafluoroborate at 20℃; for 0.0833333h;
98%	In dichloromethane at 0 - 20℃; for 10h; Inert atmosphere;

97%	With tin-tungsten mixed oxide, Sn/W molar ratio = 2, calcined at 800 °C In dichloromethane at 20℃; for 3h; Inert atmosphere;
94%	at 20℃; for 0.5h; Neat (no solvent); chemoselective reaction;
94%	In dichloromethane for 24h; Inert atmosphere; stereoselective reaction;	4.1.2. endo-Norbornene-5,6-cis-dicarboxylic anhydride (4) Maleic anhydride (30.0 g, 306 mmol) briquettes were ground in mortar and dried 2-3 h in vacuo and then dissolved in anhydrous dichloromethane (60 mL). Cyclopentadiene (freshly distilled) (22.2 g, 337 mmol) in dichloromethane (10 mL) was added dropwise to the solution of maleic anhydride at 0 °C under argon. After 24 h the white precipitate was collected and washed with diethyl ether (2×20 mL) and dried in vacuo to give known 4refPreviewPlaceHolder25 as a white crystalline solid (47.0 g, 94%). 1H NMR (300 MHz, CDCl3): δ 6.30 (2H, m), 3.58-3.55 (2H, m), 3.52-3.47 (2H, m), 1.77 (1H, dd, J=1.8, 9.3 Hz); 1.57 (1H, dd, J=1.8, 9.3 Hz). GC-MS: [M]+, m/z 164.
92%	In dichloromethane at -78℃; for 3h;	4.h EXAMPLE 4; Use of Different Dienophiles and bis(imine) Ligands; The general method of Example 2 was repeated using cyclopentadiene as the diene with a range of different dienophiles as depicted in Table 2 below. The reaction times were varied as shown. In each case the copper-exchanged zeolite Y (CuHY) was treated with one of four different bis(oxazoline) compounds as follows
91%	In benzene at 6℃; for 12h;
85%	With molecular sieve; scandium nonafluorobutanesulfonate In dichloromethane at -20℃;
85%	In benzene at -5 - 20℃;
84%	In ethyl acetate at 0℃;
84%	In chloroform at 0℃;
83%	In ethyl acetate; Petroleum ether
81.1%	In ethyl acetate; Petroleum ether for 0.5h; cooling;
81%	In chloroform at 0 - 20℃; for 5h; Darkness;
80%	In dichloromethane at 20℃; for 5h;
77%	In ethyl acetate at 0 - 20℃; for 1h;
74%	at 0℃; for 1h;
63%	In ethyl acetate; Petroleum ether at 20℃; for 4h;
56%	In ethyl acetate at 0 - 20℃;
55%	In ethyl acetate; Petroleum ether at 20℃; for 4h;
49%	In toluene for 1.5h; Reflux;	(1R,2S,6R,7S)-4-Oxatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione (2). To a solution of maleic anhydride (10 g, 100 mmol) in toluene (100 ml), monomerised cyclopentadiene (7 g, 105.90 mmol) was slowly added and refluxed. After 1.5 hours, the mixture was allowed to cool to room temperature and concentrated in vacuo to form a crude white product. The product was purified by re-crystallisation in methanol to afford a white crystalline material (8.04 g, 49%). The NMR data and melting point of compound 2 correspond to those reported in the literature.43,44,46 Physical characteristics: mp 163-165 °C (Lit. 164 °C).44 FT-IR (ATR): max (cm-1) = 1840, 1766, 1229, 1088, 901, 733. 1H-NMR (400 MHz, CDCl3): δ 6.31 (t, J 1.6 Hz, 2H), 3.58-3.57 (dd, J 3.0, 1.7 Hz, 2H), 3.51-3.50 (dd, J 2.9, 1.6 Hz, 2H), 1.80-1.77 (dt, J 9.0, 1.5 Hz. 1H), 1.58-1.56 (d, J 9.0 Hz, 1H). 13C-NMR (100 MHz, CDCl3) and DEPT-135: δ 171.29 (C=O), 135.55 (C=C), 52.76 (CH2), 47.08 (CH), 46.13 (CH).
	Yield given. Multistep reaction;
	With difluoro-phenyl-borane In tetrahydrofuran at 0℃; for 1h; Yield given;
	In benzene room t., 10 min, 353 K, 10 min;
	In toluene for 5h;
	Inert atmosphere;
	Heating;
	In toluene at 20℃;
	at 160 - 190℃;	2.2.1 Syntheses of endo-norbornene-cis-5,6-dicarboxylicacid Carbic anhydride was synthesized by the reaction of maleic anhydride with cyclo peantadiene in a tri-flask at 160-190°C until no back heat flow. The reaction was a cyclo addition to abide by the Diels-Alder rule, along with the performing of the reaction, there was a transient state intermediate product firstly, then transforming into carbic anhydride [26]. It was going to a get a white precipitation after putting the mixture into diethyl ether for dissolving at room temperature. The powder without diethyl ether was volatilized and hydrolyzed into Endc in the boiling water for continuous heating.
	In hexane; ethyl acetate at 0 - 20℃; for 1h; Darkness;
	In hexane; ethyl acetate at 0 - 20℃;
	at 160 - 190℃;
	In ethyl acetate at 0℃;
	In ethyl acetate at 0℃;
	In toluene at 20℃;

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[37]Gao, Enjun; Ding, Yuqing; Sun, Na; Zhang, Shaozhong; Qiu, Xue; Zhan, Yang; Zhu, Mingchang [Applied Organometallic Chemistry, 2017, vol. 31, # 3]
[38]Albayrak, Fatma; Gunkara, Omer Tahir; Ersoy, Elif Basak; Ocal, Nuket; Kaufmann, Dieter E. [Arkivoc, 2017, vol. 2017, # 5, p. 244 - 256] Ersoy, Elif Basak; Gunkara, Omer Tahir; Ocal, Nuket [Phosphorus, Sulfur and Silicon and the Related Elements, 2019, vol. 194, # 3, p. 257 - 268]
[39]Tahir Gunkara, Omer [Phosphorus, Sulfur and Silicon and the Related Elements, 2019, vol. 194, # 9, p. 909 - 916]
[40]Bagdatli, Emine; Cil, Elif [Journal of Heterocyclic Chemistry, 2022, vol. 59, # 2, p. 264 - 274]

18
[ 129-64-6 ]
[ 3853-88-1 ]

Reference： [1]Helvetica Chimica Acta,1982,vol. 65,p. 538 - 545

19
[ 13209-15-9 ]
[ 129-64-6 ]
2,11:3,10-di(o-benzeno)-5,8:13,16-dimethanotricyclo<10.4.0.0^4,9>hexadecane-4,7:14,15-tetracarboxylic dianhydride [ No CAS ]

Reference： [1]Journal of Crystallographic and Spectroscopic Research,1993,vol. 23,p. 55 - 60

20
[ 129-64-6 ]
[ 941567-71-1 ]

Yield	Reaction Conditions	Operation in experiment
100%	With lithium aluminium tetrahydride In tetrahydrofuran; diethyl ether at 0℃; Reflux;
97%	With lithium aluminium tetrahydride In diethyl ether at 20℃;
95%	With lithium aluminium tetrahydride In tetrahydrofuran Heating;

95%	With lithium aluminium tetrahydride In tetrahydrofuran at 20℃; for 5.5h;
95%	With lithium aluminium tetrahydride In tetrahydrofuran at 0 - 20℃; for 6.5h;
82%	With lithium aluminium tetrahydride
79%	With lithium aluminium tetrahydride In tetrahydrofuran at -78 - 20℃;
74%	With lithium aluminium tetrahydride In tetrahydrofuran at 65℃; for 3h;
39.4%	With lithium aluminium tetrahydride In tetrahydrofuran for 48h; Heating;
	With lithium aluminium tetrahydride In tetrahydrofuran
	With lithium aluminium tetrahydride
	Multi-step reaction with 2 steps 1: 185 °C 2: lithium aluminium tetrahydride / tetrahydrofuran / 19 h / 0 °C / Inert atmosphere
	With lithium aluminium tetrahydride In tetrahydrofuran at 0 - 20℃;
	With lithium aluminium tetrahydride In tetrahydrofuran at 60℃; Glovebox;
	With lithium aluminium tetrahydride In tetrahydrofuran at 0 - 20℃; Inert atmosphere;

Reference： [1]Location in patent: experimental part Polo, Eleonora; Forlini, Fabrizio; Bertolasi, Valerio; Boccia, Antonella Caterina; Sacchi, Maria Carmela [Advanced Synthesis and Catalysis, 2008, vol. 350, # 10, p. 1544 - 1556]
[2]Liu, Peng; Yasir, Mohammad; Kilbinger, Andreas F. M. [Angewandte Chemie - International Edition, 2019, vol. 58, # 43, p. 15278 - 15282][Angew. Chem., 2019, vol. 131, p. 15422 - 15426,5]
[3]Mihovilovic, Marko D.; Snajdrova, Radka; Winninger, Alexander; Rudroff, Florian [Synlett, 2005, # 18, p. 2751 - 2754]
[4]Zhang, Mianji; Flynn, Daniel L.; Hanson, Paul R. [Journal of Organic Chemistry, 2007, vol. 72, # 9, p. 3194 - 3198]
[5]Kotha, Sambasivarao; Gunta, Rama [Beilstein Journal of Organic Chemistry, 2015, vol. 11, p. 1373 - 1378]
[6]Lok, Kar P.; Jakovac, Ignac J.; Jones, J.Bryan [Journal of the American Chemical Society, 1985, vol. 107, # 8, p. 2521 - 2526]
[7]Border, Sarah E.; Pavlović, Radoslav Z.; Zhiquan, Lei; Badjić, Jovica D. [Journal of the American Chemical Society, 2017, vol. 139, # 51, p. 18496 - 18499]
[8]Laurenti; Feuerstein; Pepe; Doucet; Santelli [Journal of Organic Chemistry, 2001, vol. 66, # 5, p. 1633 - 1637]
[9]Setzer, William N.; Brown, Milton L.; Arif, Atta; Vanderveer, Donald G. [Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 54, # 1/4, p. 187 - 196] Setzer, William N.; Brown, Milton L.; Yang, Xiao-jing; Thompson, Melody A.; Whitaker, Kylen W. [Journal of Organic Chemistry, 1992, vol. 57, # 10, p. 2812 - 2818]
[10]Lin, Hui-Chang; Wu, Chung-Yi; Wu, Hsien-Jen [Journal of the Chinese Chemical Society, 1997, vol. 44, # 6, p. 609 - 616]
[11]Ye, Ji-Myoung; Maheswara, Muchchintala; Do, Jung Yun [Bulletin of the Korean Chemical Society, 2012, vol. 33, # 8, p. 2494 - 2498]
[12]Mulpuri, Syamkumar V.; Shin, Jinbok; Shin, Boo-Gyo; Yoon, Do Y.; Greiner, Andreas [Polymer, 2011, vol. 52, # 19, p. 4377 - 4386,10]
[13]Pavlović, Radoslav Z.; Border, Sarah E.; Gallucci, Judith; Badjić, Jovica D. [Tetrahedron Letters, 2016, vol. 57, # 50, p. 5584 - 5587]
[14]Stößer, Tim; Williams, Charlotte K. [Angewandte Chemie - International Edition, 2018, vol. 57, # 21, p. 6337 - 6341][Angew. Chem., 2018, vol. 130, # 21, p. 6445 - 6450,6]
[15]Hyatt, Michael G.; Walsh, Dylan J.; Lord, Richard L.; Andino Martinez, José G.; Guironnet, Damien [Journal of the American Chemical Society, 2019, vol. 141, # 44, p. 17918 - 17925]

21
[ 129-64-6 ]
(3aS*,4R*,7S*,7aR*)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86.9%	With sodium tetrahydroborate In N,N-dimethyl-formamide Ambient temperature;
68%	With LTBA In tetrahydrofuran at 5℃; for 7h;
52%	With sodium tetrahydroborate In tetrahydrofuran at 0 - 20℃; for 1h;

	With sodium tetrahydroborate In tetrahydrofuran
	With sodium tetrahydroborate; sulfuric acid 1) DMF, temperature below 20 deg C; 2) room temperature, 3 h; Yield given. Multistep reaction;
	With sodium tetrahydroborate; NAD; Flavin mononucleotide at 20℃; at pH 9; Yield given;
	Multi-step reaction with 2 steps 1: LiAlH₄ / tetrahydrofuran 2: 80 percent / pyridinium chlorochromate, Celite / CH₂Cl₂ / 8 h / Ambient temperature
	Multi-step reaction with 3 steps 1: 90 percent / NaOMe / 12 h / 0 °C 2: 81 percent / I₂, KI / tetrahydrofuran; H₂O / 18 h / 25 °C 3: 45 percent / NaBH₄ / methanol / 2 h / 0 °C

Reference： [1]Suzuki, Toshio; Tomino, Akiko; Matsuda, Yasuyuki; Unno, Katsuo; Kametani Tetsuji [Heterocycles, 1980, vol. 14, # 11, p. 1735 - 1738]
[2]Neidlein; Deigner [Arzneimittel-Forschung/Drug Research, 1988, vol. 38, # 2, p. 260 - 266]
[3]Citron, Christian A.; Wickel, Susanne M.; Schulz, Barbara; Draeger, Siegfried; Dickschat, Jeroen S. [European Journal of Organic Chemistry, 2012, # 33, p. 6636 - 6646]
[4]Janssen; Klunder; Zwanenburg [Tetrahedron Letters, 1990, vol. 31, # 49, p. 7219 - 7222]
[5]Kametani, Tetsuji; Suzuki, Toshio; Kamada, Shinko; Unno, Katsuo [Journal of the Chemical Society. Perkin transactions I, 1981, p. 3101 - 3105]
[6]Lok, Kar P.; Jakovac, Ignac J.; Jones, J.Bryan [Journal of the American Chemical Society, 1985, vol. 107, # 8, p. 2521 - 2526]
[7]Lin, Hui-Chang; Wu, Chung-Yi; Wu, Hsien-Jen [Journal of the Chinese Chemical Society, 1997, vol. 44, # 6, p. 609 - 616]
[8]Tsai, Shih-Hwa; Wu, Hsien-Jen; Chung, Wen-Sheng [Journal of the Chinese Chemical Society, 1996, vol. 43, # 5, p. 445 - 449]

22
[ 32854-09-4 ]
[ 129-64-6 ]
N-(endo-himoyl)-didehydroalanine methyl ester [ No CAS ]
N-(endo-himoyl)-(R)-cystine methyl ester [ No CAS ]

Reference： [1]Tetrahedron,1995,vol. 51,p. 7247 - 7262

23
[ 32854-09-4 ]
[ 121-44-8 ]
[ 129-64-6 ]
C₂₆H₃₂N₂O₁₀S₂*2C₆H₁₅N [ No CAS ]

Reference： [1]Tetrahedron,1995,vol. 51,p. 7247 - 7262

24
[ 56-40-6 ]
[ 129-64-6 ]
[ 165035-09-6 ]

Yield	Reaction Conditions	Operation in experiment
83%	With acetic acid for 4h; Reflux;	The general method of the synthesis of N-substitutedimides of alicyclic dicarboxylic acids (III)-(X). General procedure: Acyclicanhydride (I) or (II) (0.05 mol), an amino acid(55 mmol), and acetic acid (15 mL) were placed in around-bottomed flask equipped with a reflux condenserand refluxed for 4 h. Then, the reaction mixturewas poured into water (100 mL), and the sedimentwas filtered, washed with water, and dried at 40°.
81%	at 160 - 165℃; for 0.166667h;
80.1%	With acetic acid at 80℃; for 6h;	50 Example 50 (3aR,4S,7R,7aS)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione (326 mg, 2.0 mmol) and glycine (150 mg, 2.0 mmol)Dissolved in 10 mL of glacial acetic acid, heated to 80 ° C for 6 h. The reaction was quenched with water (10 mL) and NaOH solution (0.1 mol/L) was adjusted to pH 6-8.Dichloromethane extraction (10 mL × 3), washed with saturated NaHCO3 solution,Washed, combined organic phase, dried over anhydrous sodium sulfate, separated and purified on silica gel column.Made a yellow oil 354mg,LC-MS and 1H-NMR confirmed the expected intermediate compound in a yield of 80.1%.

63%	at 150℃; for 1h;	Compounds 3a-3e and 5a-5d (general procedure). General procedure: A mixture of 10 mmol of endic anhydride (1) and 10 mmol of amino acid 2a-2e or 4a-4d was thoroughly ground in a porcelain mortar and was then heated for 1 h at 150°C on an oil bath. After cooling to room temperature, the mixture was dissolved in pure acetone, and the product was isolated by silica gel column chromatography using anhydrous acetone as eluent. 2-(1,3-Dioxo-1,3,3a,4,7,7a-hexahydro-2H-4,7-methanoisoindol-2-yl)acetic acid (3a). Yield 1.39 g (63%), white crystals, mp 139-141°C. IR spectrum, ν, cm-1: 1233, 1377, 1461, 1709, 1746, 3180. 1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.57 d and 1.74 d (1H each, 8-H, J = 8.6), 3.39 s (4H, 3a-H, 4-H, 7-H, 7a-H), 4.12 s (2H, 2-H), 6.08 s (2H, 5-H, 6-H), 8.73 s (1H, OH). 13C NMR spectrum, δC, ppm: 38.98 (C2′), 44.99 (C3a, C7a), 46.11 (C4, C7), 52.25 (C8), 134.67 (C5, C6), 170.15 (C1′), 177.94 (C1, C3). Found, %: C 59.72; H 5.00; N 6.35. C11H11NO4. Calculated, %: C 59.73; H 5.01; N 6.33. M 221.21.
61%	In N,N-dimethyl-formamide for 24h; Reflux;	Synthesis of N-endo-5-norbornene-2,3-dicarboxyloylglycine 1 To endo-5-norbornene-2,3-dicarboxylic anhydride (16.41 g, 100.0 mmol) dissolved in DMF (30 mL) was added glycine (7.50 g, 100.0 mmol). The reaction mixture was refluxed for 24 h, cooled to room temperature, diluted with ethyl acetate (70 mL) and washed with saturated aqueous ammonium chloride solution (5 x 50 mL). The organic phase was dried on anhydrous Na2SO4, filtered and evaporated in vacuo. The residue was recrystallized (five times) from ethyl acetate giving N-5-norbornene-2,3-dicarboxyloylglycine as a white crystalline solid (yield 61 %, 13.5 g); mp: 149-151 °C.
49%	In N,N-dimethyl-formamide for 18h; Heating;
	With acetic acid Reflux;
	In toluene Reflux;
	With triethylamine In toluene for 12h; Reflux;

Reference： [1]Firstova; Kofanov; Zakshevskaya; Kovaleva [Russian Journal of Bioorganic Chemistry, 2019, vol. 45, # 3, p. 204 - 213][Bioorg. Khim., 2019, vol. 45, # 3, p. 430 - 440,11]
[2]Location in patent: experimental part Jarrahpour, Aliasghar; Zarei, Maaroof [Tetrahedron, 2009, vol. 65, # 15, p. 2927 - 2934]
[3]Current Patent Assignee: CHINESE ACADEMY OF MEDICAL SCIENCES; CHINESE ACADEMY OF SCIENCES - CN109867661, 2019, A Location in patent: Paragraph 0345; 0347
[4]Sakhautdinov; Mukhametyanova [Russian Journal of Organic Chemistry, 2019, vol. 55, # 9, p. 1280 - 1286][Zh. Org. Khim., 2019, vol. 55, # 9, p. 1359 - 1366,8]
[5]Jarrahpour, Aliasghar; Shirvani, Pouria; Sinou, Véronique; Latour, Christine; Brunel, Jean M. [Medicinal Chemistry Research, 2016, vol. 25, # 1, p. 149 - 162]
[6]Biagini, Stefano C. G.; Bush, Stephen M.; Gibson, Vernon C.; Mazzariol, Luisa; North, Michael; Teasdale, William G.; Williams, Carol M.; Zagotto, Guiseppe; Zamuner, Dora [Tetrahedron, 1995, vol. 51, # 26, p. 7247 - 7262]
[7]Location in patent: scheme or table Tarabara; Bondarenko; Kas'Yan [Russian Journal of Organic Chemistry, 2009, vol. 45, # 2, p. 234 - 241]
[8]Bai, Yugang; Lu, Hua; Ponnusamy, Ettigounder; Cheng, Jianjun [Chemical Communications, 2011, vol. 47, # 38, p. 10830 - 10832]
[9]Sarkar, Santu; Mondal, Arobendo; Tiwari, Ashwani Kumar; Shunmugam, Raja [Chemical Communications, 2012, vol. 48, # 35, p. 4223 - 4225]

25
[ 302-72-7 ]
[ 129-64-6 ]
2-(1,3-dioxo-1,3,3a,4,7,7a-hexahydro-2H-4,7-methanoisoindol-2-yl)propanoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79.5%	With acetic acid at 80℃; for 6h;	51 Example 51 (3aR, 4S, 7R, 7aS)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-Dione (328 mg, 2.0 mmol) and alanine (180 mg, 2.0 mmol)Dissolved in 10 mL of glacial acetic acid, heated to 80 ° C for 6 h. The reaction was quenched with water (10 mL) and NaOH solution (0.1 mol/L) was adjusted to pH 6-8.Dichloromethane extraction (10 mL × 3), washed with saturated NaHCO3 solution,Washed, combined organic phase, dried over anhydrous sodium sulfate, separated and purified on silica gel column.Made a yellow oil 375mg,LC-MS and 1 H-NMR confirmed the expected intermediate compound in a yield of 79.5%.
73%	at 150℃; for 1h;	Compounds 3a-3e and 5a-5d (general procedure). General procedure: A mixture of 10 mmol of endic anhydride (1) and 10 mmol of amino acid 2a-2e or 4a-4d was thoroughly ground in a porcelain mortar and was then heated for 1 h at 150°C on an oil bath. After cooling to room temperature, the mixture was dissolved in pure acetone, and the product was isolated by silica gel column chromatography using anhydrous acetone as eluent.
43%	In N,N-dimethyl-formamide for 14h; Heating;

Reflux;

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF MEDICAL SCIENCES; CHINESE ACADEMY OF SCIENCES - CN109867661, 2019, A Location in patent: Paragraph 0349; 0351
[2]Sakhautdinov; Mukhametyanova [Russian Journal of Organic Chemistry, 2019, vol. 55, # 9, p. 1280 - 1286][Zh. Org. Khim., 2019, vol. 55, # 9, p. 1359 - 1366,8]
[3]Biagini, Stefano C. G.; Bush, Stephen M.; Gibson, Vernon C.; Mazzariol, Luisa; North, Michael; Teasdale, William G.; Williams, Carol M.; Zagotto, Guiseppe; Zamuner, Dora [Tetrahedron, 1995, vol. 51, # 26, p. 7247 - 7262]
[4]Ersoy, Elif Basak; Gunkara, Omer Tahir; Ocal, Nuket [Phosphorus, Sulfur and Silicon and the Related Elements, 2019, vol. 194, # 3, p. 257 - 268]

26
[ 3853-88-1 ]
[ 129-64-6 ]

Reference： [1]Journal of Heterocyclic Chemistry,1995,vol. 32,p. 971 - 978

27
[ 13257-67-5 ]
[ 129-64-6 ]
(1R,2S,3R,4S)-3-(1-Methoxycarbonyl-1-methyl-ethylcarbamoyl)-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	In dichloromethane for 12h; Ambient temperature;

Reference： [1]Ranganathan, Darshan; Haridas; Kurur, Sunita; Thomas, Achamma; Madhusudanan; Nagaraj; Kunwar; Sarma; Karle, Isabella L. [Journal of the American Chemical Society, 1998, vol. 120, # 33, p. 8448 - 8460]

28
[ 67-56-1 ]
[ 129-64-6 ]
[ 96243-73-1 ]

Yield	Reaction Conditions	Operation in experiment
99%	With (S)-1-(3,5-bis(trifluoromethyl)phenyl)-3-(1-(dimethylamino)-3-methylbutan-2-yl)thiourea In tert-butyl methyl ether at 20℃; for 32h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
98%	Stage #1: 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride With quinine In tetrachloromethane; toluene Inert atmosphere; Stage #2: methanol In tetrachloromethane; toluene at -55 - 25℃; Stage #3: With hydrogenchloride In water; ethyl acetate	4.a a) (lR,2S,3R,4S)-3-(Methoxycarbonyl)bicyclo[2.2.1]hept-5-ene-2-carboxylic acid[00246] The starting material (a) was prepared as described in J. Org. Chem. 2000, 65, 6984-6991. czs-S-Norbornene-ewfifc^S-dicarboxylic anhydride (4.104 g, 25 mmol) was suspended in a 1 : 1 mixture of toluene and carbon tetrachloride (500 mL). The mixture was stirred for 20 min. Quinine (8.92 g, 27.5 mmol) was added and the flask was degassed and backfilled with nitrogen. The solution was cooled to -55 0C. While stirring, methanol (3.04 mL, 75 mmol) was added. The mixture was stirred at - 55 0C for 20 h. Upon warming to 25 0C, the mixture was concentrated in vacuo to a thick oil. The oil was dissolved in ethyl acetate (400 mL), washed with 1.0 M aqueous hydrochloric acid solution (2 x 400 mL), saturated aqueous brine solution (100 mL), dried over magnesium sulfate, filtered, and concentrated in vacuo to afford the desired product, (lR,2S,3R,4S>3-(methoxycarbonyl)bicyclo[2.2.1]hept-5-ene-2- carboxylic acid (4.8 g, 24.5 mmol, 98%), as a clear waxy solid. 1H NMR (400 MHz, DMSO-(Z6) δ: 1.26 (IH, d, J= 8.5 Hz), 1.33 (IH, d, J= 8.8 Hz), 3.00 (IH, s), 3.03 (IH, s), 3.21 - 3.30 (2H, m), 3.45 (3H, s), 6.02 - 6.04 (IH, m), 6.14 - 6.16 (IH, m), 11.86 (IH, s).
94%	With textile immobilized (9S)-9-(3,5-di(trifluoromethyl)phenyl)sulfonamido-9-deoxyquinidine In tert-butyl methyl ether at 20℃; for 14h; enantioselective reaction;

93%	In various solvent(s) at 20℃; for 100h;
93%	With polymer-supported Cinchona-based sulfonamide In mBTE at 20℃; for 8h; optical yield given as %ee; enantioselective reaction;
92%	With Quinine In tetrachloromethane; toluene at -55℃; for 60h;
92%	With Quinine In tetrachloromethane; toluene at -55℃; for 60h;
90%	With N-((1S)-(6-methoxyquinolin-4-yl)((2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)-3,5-bis(trifluoromethyl)benzenesulfonamide In diethyl ether at 20℃; for 5h; optical yield given as %ee;
90%	With 1-(3,5-bis(trifluoromethyl)phenyl)-3-((1S,2R)-3-(tert-butyldimethylsilyloxy)-2-(dimethylamino)-1-(4-nitrophenyl)propyl)thiourea In tert-butyl methyl ether at 20℃; for 72h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
90%	Stage #1: methanol; 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride In di-isopropyl ether at 20℃; for 5h; Stage #2: With hydrogenchloride In di-isopropyl ether; water	27 ; 0.5 mmol of an anhydride (Id) was dissolved in 10 mL of diisopropyl ether at 20 °C, 5 mol% of an organocatalyst (Q-BTBSA) was added thereto, 10 equivalents of methanol was added once thereto, and the mixture was stirred at normal temperature for 5 hours. This reaction was quenched using an aqueous solution of dilute hydrochloric acid (IN, 3 mL). The aqueous layer was extracted with ethyl acetate (2x10 mL), and the combined organic layer was dried with MgSO4 and concentrated. The residue was purified by flash chromatography (25% ethyl acetate in normal-hexane) to obtain a hemiester (2d, 90% yield). According to the known method (H. Han, Tetrahedron Lett. 2004, 45, 3301-3304), it was determined to obtain an enantiomeric excess of 97.5% by reacting the hemiester and R-l-(l-naphthyl)ethyl amine to be converted to an ester amide corresponding to the hemiester. The enantioselectivity was measured using high performance liquid chromatography (Hypersil, 40:1, hexane: isopropyl alcohol, 1 mL/min., t (side product) = 18.90 min., t (main product) = 24.93 min.).
90%	Stage #1: methanol; 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride In di-isopropyl ether at 20℃; for 5h; Stage #2: With hydrogenchloride In di-isopropyl ether; water	31 Example 310.5 mmol of an anhydride (1d) was dissolved in 10 mL of diisopropyl ether at 20° C., 5 mol % of an organocatalyst (Q-BTBSA) was added thereto, 10 equivalents of methanol was added once thereto, and the mixture was stirred at normal temperature for 5 hours. This reaction was quenched using an aqueous solution of dilute hydrochloric acid (1N, 3 mL). The aqueous layer was extracted with ethyl acetate (2×10 mL), and the combined organic layer was dried with MgSO4 and concentrated. The residue was purified by flash chromatography (25% ethyl acetate in normal-hexane) to obtain a hemiester (2d, 90% yield). According to the known method (H. Han, Tetrahedron Lett. 2004, 45, 3301-3304), it was determined to obtain an enantiomeric excess of 97.5% by reacting the hemiester and R-1-(1-naphthyl)ethyl amine to be converted to an ester amide corresponding to the hemiester. The enantioselectivity was measured using high performance liquid chromatography (Hypersil, 40:1, hexane:isopropyl alcohol, 1 mL/min., t (side product)=18.90 min., t (main product)=24.93 min).
88%	With C₄₁H₂₁F₁₂N₂O₂PS In toluene at -10℃; for 144h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
85%	With Quinine In tetrachloromethane; toluene at -50℃; for 36h;
80%	With C₂₆H₃₄F₆N₄O₃SSi In tert-butyl methyl ether at 20℃; for 120h; Inert atmosphere; enantioselective reaction;

Reference： [1]Manzano, Ruben; Andres, Jose M.; Muruzabal, Maria-Dolores; Pedrosa, Rafael [Journal of Organic Chemistry, 2010, vol. 75, # 15, p. 5417 - 5420]
[2]Current Patent Assignee: ROCHE HOLDING AG - WO2008/124450, 2008, A1 Location in patent: Page/Page column 81
[3]Lee, Ji-Woong; Mayer-Gall, Thomas; Opwis, Klaus; Song, Choong Eui; Gutmann, Jochen Stefan; List, Benjamin [Science, 2013, vol. 341, # 6151, p. 1225 - 1229]
[4]Peschiulli, Aldo; Gun'ko, Yurii; Connon, Stephen J. [Journal of Organic Chemistry, 2008, vol. 73, # 6, p. 2454 - 2457]
[5]Youk, Sung Hun; Oh, Sang Ho; Rho, Ho Sik; Lee, Je Eun; Lee, Ji Woong; Song, Choong Eui [Chemical Communications, 2009, # 16, p. 2220 - 2222]
[6]Tanyeli, Cihangir; Suenbuel, Murat [Tetrahedron Asymmetry, 2005, vol. 16, # 11, p. 2039 - 2043]
[7]Bolm, Carsten; Schiffers, Ingo; Dinter, Christian L.; Gerlach, Arne [Journal of Organic Chemistry, 2000, vol. 65, # 21, p. 6984 - 6991]
[8]Oh, Sang Ho; Rho, Ho Sik; Lee, Ji Woong; Lee, Je Eun; Youk, Sung Hoon; Chin, Jik; Song, Choong Eui [Angewandte Chemie - International Edition, 2008, vol. 47, # 41, p. 7872 - 7875]
[9]Wang, Su-Xi; Chen, Fen-Er [Advanced Synthesis and Catalysis, 2009, vol. 351, # 4, p. 547 - 552]
[10]Current Patent Assignee: SUNGKYUNKWAN UNIVERSITY - WO2010/8117, 2010, A1 Location in patent: Page/Page column 38; 45
[11]Current Patent Assignee: SUNGKYUNKWAN UNIVERSITY - US2011/213151, 2011, A1 Location in patent: Page/Page column 16-17
[12]Wakchaure, Vijay N.; List, Benjamin [Angewandte Chemie - International Edition, 2010, vol. 49, # 24, p. 4136 - 4139]
[13]Bolm, Carsten; Gerlach, Arne; Dinter, Christian L. [Synlett, 1999, # 2, p. 195 - 196]
[14]Yan, Lin-Jie; Wang, Hai-Feng; Chen, Wen-Xue; Tao, Yuan; Jin, Kai-Jun; Chen, Fen-Er [ChemCatChem, 2016, vol. 8, # 13, p. 2249 - 2253]

29
[ 67-56-1 ]
[ 129-64-6 ]
[ 96243-74-2 ]

Yield	Reaction Conditions	Operation in experiment
99%	With quinidine In tetrachloromethane; toluene
99%	With 1-((1R,2R)-2-(dimethylamino)cyclohexyl)-3-phenylthiourea In diethyl ether at 20℃; for 24h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
98%	With quinidine In tetrachloromethane; toluene at -55℃; for 60h;

98%	With quinidine at -55℃;
98%	With C₁₆H₂₁F₆N₃S In tert-butyl methyl ether at 20℃; for 32h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
94%	Stage #1: 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride With quinindine In tetrachloromethane; toluene Inert atmosphere; Stage #2: methanol In tetrachloromethane; toluene at -55 - 25℃; Stage #3: With hydrogenchloride In water; ethyl acetate	5.a a) (15',2R,35r,4R)-3-(Methoxycarbonyl)bicyclo[2.2.1]hept-5-ene-2-carboxylic acid[00252] The starting material (a) was prepared as described in J Org. Chem. 2000, 65, 6984-6991. cw-S-Norbornene-eMt/o^^-dicarboxylic anhydride (8.21 g, 50 mmol) was suspended in a 1 :1 mixture of toluene and carbon tetrachloride (250 mL). The mixture was stirred for 10 min. Quinidine (17.84 g, 55 mmol) was added and the flask was degassed and backfilled with nitrogen. The solution was cooled to -55 0C. While stirring, methanol (6.08 mL, 150 mmol) was added. The mixture was stirred at -55 0C for 18 h. Upon warming to 25 0C, the mixture was concentrated in vacuo to a thick oil. The oil was dissolved in a mixture of ethyl acetate (400 mL) and 1.0 M aqueous hydrochloric acid solution (300 mL). After shaking, the layers were separated and the organic layer was further washed with 1.0 M aqueous hydrochloric acid solution (2 x 100 mL), saturated aqueous brine solution (100 mL), dried over magnesium sulfate, filtered, and concentrated in vacuo to afford the desired product, (15r,2R,35',4R)-3-(methoxycarbonyl)bicyclo[2.2.1]hept-5-ene-2-carboxylic acid (9.15 g, 46.6 mmol, 94%), as a clear oil. 1H NMR (400 MHz, DMSCM6) δ: 1.26 (IH, d, J = 8.4 Hz), 1.33 (IH, d, J= 8.4 Hz), 3.00 (IH, s), 3.03 (IH, s), 3.21 - 3.29 (2H, m), 3.45 (3H, s), 6.02 - 6.04 (IH, m), 6.14 - 6.16 (IH, m), 11.86 (IH, s).
87%	With quinidine In tetrachloromethane; toluene at -55℃; for 60h;
83%	With quinidine In tetrachloromethane; toluene at -50℃; for 36h;
96 % ee	With quinindine regioselective reaction;

Reference： [1]Bolm; Dinter; Schiffers; Defrère [Synlett, 2001, # 12, p. 1875 - 1877]
[2]Location in patent: experimental part Schmitt, Ellen; Schiffers, Ingo; Bolm, Carsten [Tetrahedron, 2010, vol. 66, # 33, p. 6349 - 6357]
[3]Bolm, Carsten; Schiffers, Ingo; Dinter, Christian L.; Gerlach, Arne [Journal of Organic Chemistry, 2000, vol. 65, # 21, p. 6984 - 6991]
[4]Bolm, Carsten; Schiffers, Ingo; Atodiresei, Iuliana; Ozcubukcu, Salih; Raabe, Gerhard [New Journal of Chemistry, 2003, vol. 27, # 1, p. 14 - 17]
[5]Manzano, Ruben; Andres, Jose M.; Muruzabal, Maria-Dolores; Pedrosa, Rafael [Journal of Organic Chemistry, 2010, vol. 75, # 15, p. 5417 - 5420]
[6]Current Patent Assignee: ROCHE HOLDING AG - WO2008/124450, 2008, A1 Location in patent: Page/Page column 85-86
[7]Tanyeli, Cihangir; Oezcubukcu, Salih [Tetrahedron Asymmetry, 2003, vol. 14, # 9, p. 1167 - 1170]
[8]Bolm, Carsten; Gerlach, Arne; Dinter, Christian L. [Synlett, 1999, # 2, p. 195 - 196]
[9]Zhang, Fan; Wen, Xiaoan; Xu, Qing-Long; Sun, Hongbin [European Journal of Organic Chemistry, 2014, vol. 2014, # 36, p. 8101 - 8109]

30
[ 3717-38-2 ]
[ 129-64-6 ]
(1R,2S,3R,4S)-3-(Adamantan-1-yl-methyl-carbamoyl)-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid [ No CAS ]

Reference： [1]Russian Journal of Organic Chemistry,1998,vol. 34,p. 1731 - 1735

31
[ 516-06-3 ]
[ 129-64-6 ]
2-(1,3-dioxo-1,3,3a,4,7,7a-hexahydro-2H-4,7-methanoisoindol-2-yl)-3-methylbutanoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	at 150℃; for 1h;	Compounds 3a-3e and 5a-5d (general procedure). General procedure: A mixture of 10 mmol of endic anhydride (1) and 10 mmol of amino acid 2a-2e or 4a-4d was thoroughly ground in a porcelain mortar and was then heated for 1 h at 150°C on an oil bath. After cooling to room temperature, the mixture was dissolved in pure acetone, and the product was isolated by silica gel column chromatography using anhydrous acetone as eluent.
	Heating;

Reference： [1]Sakhautdinov; Mukhametyanova [Russian Journal of Organic Chemistry, 2019, vol. 55, # 9, p. 1280 - 1286][Zh. Org. Khim., 2019, vol. 55, # 9, p. 1359 - 1366,8]
[2]Singh, Kalpana; Srivastava, Nishi; Verma, Shiva M. [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1997, vol. 36, # 2, p. 142 - 145]

32
[ 557-20-0 ]
[ 129-64-6 ]
(+/-)-(2,3-endo)-3-(1-oxopropyl)bicyclo<2.2.1>hept-5-ene-2-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With [2,2]bipyridinyl; bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; 1-trifluoromethyl-4-vinyl-benzene In tetrahydrofuran; hexane at 0℃; for 4h;
96%	With [2,2]bipyridinyl; bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; 1-trifluoromethyl-4-vinyl-benzene In tetrahydrofuran; hexane at 0℃; for 4.5h;

Reference： [1]Bercot, Eric A.; Rovis, Tomislav [Journal of the American Chemical Society, 2005, vol. 127, # 1, p. 247 - 254]
[2]Bercot, Eric A.; Rovis, Tomislav [Journal of the American Chemical Society, 2002, vol. 124, # 2, p. 174 - 175]

33
[ 100-42-5 ]
[ 129-64-6 ]
(3aR,4S,6R,6aS,E)-4-styryl-6-vinyl-tetrahydro-cyclopenta[c]furan-1,3-dione [ No CAS ]
(3aS,4R,6S,6aR,E)-4-styryl-6-vinyl-tetrahydro-cyclopenta[c]furan-1,3-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With [ruthenium(dichloride)(CHC₆H₄OiPr)(C₃H₃N₂(C₆H₃(CH₃)3)(C₆H₄Ph)iPr)] In dichloromethane at 25℃; for 15h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
	With chiral Ru catalyst In tetrahydrofuran at 22℃; for 25h; Title compound not separated from byproducts;
	In tetrahydrofuran at 50℃; for 1.5h; Title compound not separated from byproducts.;

41 % ee	With C₂₉H₄₀Cl₂N₂ORu In tetrahydrofuran at 20℃; for 0.166667h; Schlenk technique; Inert atmosphere; enantioselective reaction;	AROCM with 16; General Procedure Anhydride 16 (0.054 g, 0.3308 mmol, 1 equiv), styrene (0.27 mL,2.316 mmol, 7 equiv), THF (0.66 mL) and catalyst (3.308 μmol, 0.01equiv) were mixed in a Schlenk tube. The reaction was quenched withethylvinyl ether (1 mL) after the consumption of the educt (moni-tored by thin-layer chromatography) after 10 min. The product waspurified by column chromatography (Et2O/n-pentane = 1:1). Determi-nation of the ee values for the (E)-isomer 17: Daicel Chiralcel OJ-H(4.6 mm 250 mm; 5 μm particle size), 50% 2-propanol + 50% n-hex-ane, 0.7 mL/min, 254 nm, t1 = 23.7 min (b), t2 = 46.2 min (a). The abso-lute configuration could be determined by comparison with reportedHPLC runs.17b,15,40
11 % ee	With C₃₁H₄₄Cl₂N₂ORu In tetrahydrofuran at 20℃; for 0.166667h; Schlenk technique; Inert atmosphere; enantioselective reaction;	AROCM with 16; General Procedure Anhydride 16 (0.054 g, 0.3308 mmol, 1 equiv), styrene (0.27 mL,2.316 mmol, 7 equiv), THF (0.66 mL) and catalyst (3.308 μmol, 0.01equiv) were mixed in a Schlenk tube. The reaction was quenched withethylvinyl ether (1 mL) after the consumption of the educt (moni-tored by thin-layer chromatography) after 10 min. The product waspurified by column chromatography (Et2O/n-pentane = 1:1). Determi-nation of the ee values for the (E)-isomer 17: Daicel Chiralcel OJ-H(4.6 mm 250 mm; 5 μm particle size), 50% 2-propanol + 50% n-hex-ane, 0.7 mL/min, 254 nm, t1 = 23.7 min (b), t2 = 46.2 min (a). The abso-lute configuration could be determined by comparison with reportedHPLC runs.17b,15,40
79 % ee	With C₃₅H₅₀Cl₂N₂O₃Ru In tetrahydrofuran at 35℃; for 120h; Inert atmosphere; Schlenk technique; Overall yield = 45 percent; enantioselective reaction;

Reference： [1]Tiede, Sascha; Berger, Anke; Schlesiger, David; Rost, Daniel; Luehl, Anja; Blechert, Siegfried [Angewandte Chemie - International Edition, 2010, vol. 49, # 23, p. 3972 - 3975]
[2]Van Veldhuizen, Joshua J.; Gillingham, Dennis G.; Garber, Steven B.; Kataoka, Osamu; Hoveyda, Amir H. [Journal of the American Chemical Society, 2003, vol. 125, # 41, p. 12502 - 12508]
[3]Van Veldhuizen, Joshua J.; Garber, Steven B.; Kingsbury, Jason S.; Hoveyda, Amir H. [Journal of the American Chemical Society, 2002, vol. 124, # 18, p. 4954 - 4955]
[4]Rais, Eduard; Flörke, Ulrich; Wilhelm, René [Synthesis, 2017, vol. 49, # 13, p. 2852 - 2864]
[5]Rais, Eduard; Flörke, Ulrich; Wilhelm, René [Synthesis, 2017, vol. 49, # 13, p. 2852 - 2864]
[6]Bertrand, Guy; Cavallo, Luigi; Crévisy, Christophe; Dorcet, Vincent; Falivene, Laura; Jazzar, Rodolphe; Mauduit, Marc; Morvan, Jennifer; Roisnel, Thierry; Vanthuyne, Nicolas; Vermersch, François; Vives, Thomas; Zhang, Ziyun [Journal of the American Chemical Society, 2020, vol. 142, # 47, p. 19895 - 19901]

34
[ 592-76-7 ]
[ 129-64-6 ]
4-hept-1-enyl-6-vinyl-tetrahydro-cyclopenta[c]furan-1,3-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57%	In tetrahydrofuran at 50℃; for 1.5h;

Reference： [1]Van Veldhuizen, Joshua J.; Garber, Steven B.; Kingsbury, Jason S.; Hoveyda, Amir H. [Journal of the American Chemical Society, 2002, vol. 124, # 18, p. 4954 - 4955]

35
[ 695-12-5 ]
[ 129-64-6 ]
4-(2-cyclohexyl-vinyl)-6-vinyl-tetrahydro-cyclopenta[c]furan-1,3-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	In tetrahydrofuran at 50℃; for 1.5h;

Reference： [1]Van Veldhuizen, Joshua J.; Garber, Steven B.; Kingsbury, Jason S.; Hoveyda, Amir H. [Journal of the American Chemical Society, 2002, vol. 124, # 18, p. 4954 - 4955]

36
[ 1078-58-6 ]
[ 129-64-6 ]
7-phenyl-tricyclo[2.2.1.0]heptane-3-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	Stage #1: 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; 2.9-dimethyl-1,10-phenanthroline; bis(diphenylphosphino)butane In tetrahydrofuran at 45℃; for 3h; Stage #2: diphenylzinc In tetrahydrofuran at 66℃; for 5h;

Reference： [1]O'Brien, Erin M.; Bercot, Eric A.; Rovis, Tomislav [Journal of the American Chemical Society, 2003, vol. 125, # 35, p. 10498 - 10499]

37
[ 105-13-5 ]
[ 129-64-6 ]
[ 581100-34-7 ]

Yield	Reaction Conditions	Operation in experiment
93%	With quinidine In tetrachloromethane; toluene at -55℃; for 60h;
	With quinidine In tetrachloromethane; toluene at -55℃; for 96.25h;	36 endo-Bicyclo[2.2.1]hept-5-ene-2-(4-methoxy)benzylcarboxylate-3-carboxylic acid (S6-48) Compound S3-19 and quinidine are suspended in equal amounts of toluene and carbon tetrachloride and cooled to -55[deg.] C. p-Methoxybenzyl alcohol is added over 15 minutes and the solution stirred at -55[deg.] C. for 96 hours. After removal of the solvents, the residue is partitioned between ethyl acetate and 2 M hydrochloric acid. The organic layer is washed with water and saturated aqueous sodium chloride. Drying over magnesium sulfate and removal of the solvent gives S6-48.
	With (S)-[(2R)-5-ethenyl-1-azabicyclo[2.2.2]oct-2-yl](6-methoxyquinolin-4-yl)methanol In tetrachloromethane; toluene at -55℃; for 96.25h;	49 Example 49 endo-Bicyclo [2.2. LLHEPT-5-ENE-2- (4-METHOXY) BENZYLCARBOXYLATE-3-CARBOXYLIC ACID (S26-48) [0342] Compound S23-19 and quinidine are suspended in equal amounts of toluene and carbon tetrachloride and cooled to-55° C. p-Methoxybenzyl alcohol is added over 15 minutes and the solution stirred at-55° C for 96 hours. After removal of the solvents, the residue is partitioned between ethyl acetate and 2 M hydrochloric acid. The organic layer is washed with water and saturated aqueous sodium chloride. Drying over magnesium sulfate and removal of the solvent gives S26-48.

Reference： [1]Zhang, Mingbao; Zhu, Lei; Ma, Xin [Tetrahedron Asymmetry, 2003, vol. 14, # 22, p. 3455 - 3468]
[2]Current Patent Assignee: COVALENT PARTNERS - US2003/199688, 2003, A1 Location in patent: Page/Page column 34
[3]Current Patent Assignee: COVALENT PARTNERS - WO2005/30711, 2005, A2 Location in patent: Page/Page column 127-128

38
[ 129-64-6 ]
[ 100-51-6 ]
[ 581100-26-7 ]

Yield	Reaction Conditions	Operation in experiment
95%	With quinindine In toluene at -55℃; for 96h; Inert atmosphere; enantioselective reaction;
92%	With quinidine In tetrachloromethane; toluene at -55℃; for 60h;
63%	With quinidine In tetrachloromethane; toluene at -55℃; for 99.25h;	26 endo-Bicyclo[2.2.1]hept-5-ene-2-benzylcarboxylate-3-carboxylic acid (S5-37) Compound S3-19 (4.00 g, 0.0244 mol) and quinidine (8.63 g, 0.0266 mol) were suspended in equal amounts of toluene (50 mL) and carbon tetrachloride (50 mL). The suspension was cooled to -55[deg.] C. after which benzyl alcohol (7.90 g, 0.0732 mol) was added over 15 minutes. The reaction mixture became homogenous after 3 hours and was stirred at -55[deg.] C. for an additional 96 hours. After removal of the solvents, the residue was partitioned between ethyl acetate (300 mL) and 2M hydrochloric acid (100 mL). The organic layer was washed with water (250 mL) and saturated aqueous sodium chloride (150 mL). Drying over magnesium sulfate and evaporation of the solvent gave S5-37 (4.17 g, 0.0153 mol, 63% yield).

63%	With (S)-[(2R)-5-ethenyl-1-azabicyclo[2.2.2]oct-2-yl](6-methoxyquinolin-4-yl)methanol In tetrachloromethane; toluene at -55℃; for 99.25h;	39 Example 39 endo-Bicyclo [2.2. 1] hept-5-ene-2-benzylcarboxylate-3-carboxylic acid (S25-37) [0330] Compound S23-19 (4.00 g, 0.0244 mol) and quinidine (8.63 g, 0.0266 mol) were suspended in equal amounts of toluene (50 mL) and carbon tetrachloride (50 mL). The suspension was cooled to-55° C after which benzyl alcohol (7.90 g, 0.0732 mol) was added over 15 minutes. The reaction mixture became homogenous after 3 hours and was stirred at-55° C for an additional 96 hours. After removal of the solvents, the residue was partitioned between ethyl acetate (300 mL) and 2M hydrochloric acid (100 mL). The organic layer was washed with water (2 x 50 mL) and saturated aqueous sodium chloride (1 x 50 mL). Drying over magnesium sulfate and evaporation of the solvent gave S25-37 . (4. 17 g, 0.0153 mol, 63% yield).
	With (1R,2R)-N,N-dimethyl-N'-[3,5-bis(trifluoromethyl)benzenesulfonyl]-1,2-diphenyl-1,2-ethanediamine In diethyl ether at 20℃; for 20h; optical yield given as %ee; enantioselective reaction;

Reference： [1]Bolm, Carsten; Atodiresei, Iuliana; Schiffers, Ingo; Kanai, Motomu; Shibasaki, Masakatsu [Organic Syntheses, 2005, vol. 82, p. 120 - 125]
[2]Zhang, Mingbao; Zhu, Lei; Ma, Xin [Tetrahedron Asymmetry, 2003, vol. 14, # 22, p. 3455 - 3468]
[3]Current Patent Assignee: COVALENT PARTNERS - US2003/199688, 2003, A1 Location in patent: Page/Page column 33
[4]Current Patent Assignee: COVALENT PARTNERS - WO2005/30711, 2005, A2 Location in patent: Page/Page column 124-125
[5]Location in patent: experimental part Honjo, Takashi; Tsumura, Takeshi; Sano, Shigeki; Nagao, Yoshimitsu; Yamaguchi, Kentaro; Sei, Yoshihisa [Synlett, 2009, # 20, p. 3279 - 3282]

39
[ 100-42-5 ]
[ 129-64-6 ]
(3aR,4S,6R,6aS)-4-((E)-Styryl)-6-vinyl-tetrahydro-cyclopenta[c]furan-1,3-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With chiral ruthenium N-heterocyclic carbene In tetrahydrofuran at 22℃; for 4h;

Reference： [1]Van Veldhuizen, Joshua J.; Campbell, John E.; Giudici, Russell E.; Hoveyda, Amir H. [Journal of the American Chemical Society, 2005, vol. 127, # 18, p. 6877 - 6882]

40
[ 108-00-9 ]
[ 129-64-6 ]
[ 744151-96-0 ]

Yield	Reaction Conditions	Operation in experiment
97%	In toluene Reflux;	General procedure for the synthesis of 3-13. General procedure: The appropriate amine ((benzylamine (3, 1 mmol), 1-aminopiperidine (5, 1 mmol), propargylamine (6, 2.6 mmol), propylamine (7, 3.9 mmol), phenylhydrazine (8, 4 mmol), ethylenediamine (9, 2.7 mmol), 1,3-diaminopropane (11, 1.4 mmol), 1,4-diaminobutane (12, 3 mmol) or N,N-dimethylethylenediamine (13, 2.5 mmol)) were reacted with compound 2 (1 mmol) in toluene (100 ml) under reflux conditions for 10-24 hours to afford compounds 3-13, respectively.
86%	In toluene at 80℃;
44%	In benzene at 110℃; for 18h;

Reference： [1]Egunlusi, Ayodeji O.; Malan, Sarel F.; Joubert, Jacques [Arkivoc, 2020, vol. 2020, # 5, p. 17 - 27]
[2]Fernandez, Fernando; Cordero, Beatriz; Durand, Jerome; Muller, Guillermo; Malbosc, Franois; Kihn, Yolande; Teuma, Emmanuelle; Gomez, Montserrat [Dalton Transactions, 2007, # 47, p. 5572 - 5581]
[3]Gallivan, Justin P.; Jordan, Jason P.; Grubbs, Robert H. [Tetrahedron Letters, 2005, vol. 46, # 15, p. 2577 - 2580]

41
[ 6298-37-9 ]
[ 129-64-6 ]
endo-3-(6-quinoxalylcarbamoyl)bicyclo[2.2.1]hept-5-ene-endo-2-carboxylic acid [ No CAS ]

Reference： [1]Russian Journal of Organic Chemistry,2005,vol. 41,p. 1530 - 1538

42
[ 129-64-6 ]
[ 38253-40-6 ]

Yield	Reaction Conditions	Operation in experiment
92.5%	With hydrazine hydrate In water; benzene
91.4%	With hydrazine hydrate In water
87%	With hydrazine hydrate In benzene at 20℃; Inert atmosphere;

73%	With hydrazine hydrate In isopropyl alcohol for 3h; Heating;
	With hydrazine hydrate In ethanol for 4h;
	With hydrazine hydrochloride In benzene at 20℃;
	With hydrazine hydrate In benzene at 20℃; for 4h; Inert atmosphere;
	With hydrazine hydrochloride In toluene at 20℃;

Reference： [1]Kas'yan; Tarabara; Bondarenko; Shishkina; Shishkin; Musatov [Russian Journal of Organic Chemistry, 2005, vol. 41, # 8, p. 1122 - 1131]
[2]Kas'yan; Tarabara; Bondarenko; Svyatenko; Bondarenko [Russian Journal of Organic Chemistry, 2007, vol. 43, # 7, p. 1014 - 1026]
[3]Location in patent: scheme or table Gul, Melek; Ocal, Nuket [Canadian Journal of Chemistry, 2010, vol. 88, # 4, p. 323 - 330]
[4]Zibinsky, Mikhail; Butkevich, Alexey N.; Kuznetsov, Mikhail A. [Tetrahedron Letters, 2008, vol. 49, # 38, p. 5505 - 5507]
[5]Bagdatli, Emine; Oecal, Nueket; Kaufmann, Dieter E. [Helvetica Chimica Acta, 2007, vol. 90, # 12, p. 2380 - 2385]
[6]Gul, Melek; Kulu, Irem; Gunkara, Omer Tahir; Ocal, Nuket [Acta Chimica Slovenica, 2013, vol. 60, # 1, p. 87 - 94]
[7]Gul, Melek; Kulu, Irem; Ocal, Nuket [Journal of Chemical Research, 2013, vol. 37, # 6, p. 345 - 350]
[8]Albayrak, Fatma; Gunkara, Omer Tahir; Ersoy, Elif Basak; Ocal, Nuket; Kaufmann, Dieter E. [Arkivoc, 2017, vol. 2017, # 5, p. 244 - 256]

43
[ 129-64-6 ]
[ 95340-88-8 ]

Yield	Reaction Conditions	Operation in experiment
64.76%	Stage #1: 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride With sodium tetrahydroborate In tetrahydrofuran; methanol at 30 - 35℃; for 4h; Stage #2: With sulfuric acid In tetrahydrofuran; methanol; water at 20℃;	2.1 [0090] Under nitrogen atmosphere, 176 g (4.649 mol) of sodium borohydride was put into a flask and 2000 g of THF and 9.8 g of methanol were added thereto. A solution of 954 g (5.812 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 2800 g of THF was added thereto dropwise while cooling them by an ice bath to keep the reaction temperature at 35° C. or lower. After completion of the dropping, the mixture was stirred at 30° C. for 4 hours, then poured into 3000 g of 10% aqueous sulfuric acid solution at 20° C. or lower and stirred for a while. Under reduced pressure, THF was recovered, and 1800 g of MIBK was added thereto for extraction. Further 900 g of MIBK was added to the separated aqueous layer for extraction and combined with the organic layer. 63.6 g of sodium carbonate and 200 g of water were added to the organic layer and stirred for a while. The separated organic layer was washed with diluted sulfuric acid and water, then concentrated, thereby 565.3 g of a white solid desired product of a lactone compound was obtained (64.76% yield).
	Multi-step reaction with 2 steps 1: diethyl ether / 144 h / -22 °C 2: 1.) LiBEt₃H, 2.) HCl / 1.) THF, rt, 2.) THF, H₂O
	Multi-step reaction with 2 steps 1: tetrahydrofuran / 144 h / -30 °C 2: 1.) LiBEt₃H, 2.) HCl / 1.) THF, rt, 2.) THF, H₂O

	Multi-step reaction with 2 steps 1: tetrahydrofuran / 168 h / -30 °C 2: 1.) LiBEt₃H, 2.) HCl / 1.) THF, rt, 2.) THF, H₂O
	Multi-step reaction with 3 steps 1: BuLi, HMPA / tetrahydrofuran / 2 h / -78 °C 2: lithium pyrrolidinoborohydride / tetrahydrofuran / 1.5 h / Ambient temperature 3: 3 N HCl
	Multi-step reaction with 2 steps 1: 82 percent / LiAlH₄ 2: 64 percent / NAD⁽¹⁺⁾, FMN / HLADH / 144 h / Ambient temperature; 0.1 M NaOH-glycine buffer (pH=9)
	Multi-step reaction with 4 steps 1: NaBH₄ / tetrahydrofuran 2: 94 percent / 1) aq. NaOH, 2) KI*I₂ 3: 42 percent / Porcine Pancreatic Lipase (PPL) / 384 h / 40 °C 4: 87 percent / Zn / acetic acid
	Multi-step reaction with 2 steps 1: lithium aluminium tetrahydride / diethyl ether; tetrahydrofuran / 16 h / Reflux 2: Micrococcus sp. DSM 30771 / 264 h / 28 °C
	Multi-step reaction with 2 steps 1.1: quinine / toluene / 96 h / -55 °C / Inert atmosphere 2.1: lithium triethylborohydride / tetrahydrofuran / 1 h / 0 - 20 °C / Schlenk technique; Inert atmosphere 2.2: 2 h / 20 °C / Schlenk technique; Inert atmosphere

Reference： [1]Current Patent Assignee: TAKASAGO INTERNATIONAL CORPORATION - US2005/32887, 2005, A1 Location in patent: Page/Page column 8
[2]Jaeschke, Georg; Seebach, Dieter [Journal of Organic Chemistry, 1998, vol. 63, # 4, p. 1190 - 1197]
[3]Jaeschke, Georg; Seebach, Dieter [Journal of Organic Chemistry, 1998, vol. 63, # 4, p. 1190 - 1197]
[4]Jaeschke, Georg; Seebach, Dieter [Journal of Organic Chemistry, 1998, vol. 63, # 4, p. 1190 - 1197]
[5]Imado, Hideo; Ishizuka, Tadao; Kunieda, Takehisa [Tetrahedron Letters, 1995, vol. 36, # 6, p. 931 - 934]
[6]Lok, Kar P.; Jakovac, Ignac J.; Jones, J.Bryan [Journal of the American Chemical Society, 1985, vol. 107, # 8, p. 2521 - 2526]
[7]Janssen; Klunder; Zwanenburg [Tetrahedron Letters, 1990, vol. 31, # 49, p. 7219 - 7222]
[8]Boratyński; Pannek; Walczak; Janik-Polanowicz; Huszcza; Szczepańska; Martinez-Rojas; Olejniczak [Process Biochemistry, 2014, vol. 49, # 10, p. 1637 - 1646]
[9]Bolm, Carsten; Atodiresei, Iuliana; Schiffers, Ingo; Kanai, Motomu; Shibasaki, Masakatsu [Organic Syntheses, 2005, vol. 82, p. 120 - 125]

44
[ 129-64-6 ]
[ 2746-19-2 ]
[ 17812-27-0 ]
[ 14166-28-0 ]

Yield	Reaction Conditions	Operation in experiment
50%	With hydrogen;5%-palladium/activated carbon; In tetrahydrofuran;Product distribution / selectivity;	5-norbornene-endo-2,3-dicarboxylic anhydride and 5-norbornene-exo-2,3-dicarboxylic anhydride were mixed together, tetrahydrofuran was added to the resulting mixture, and a hydrogenation was conducted under a hydrogen atmosphere using 5% palladium-carbon as a catalyst. The hydrogenation rate was 100%. Following completion of the hydrogenation reaction, the product was filtered and dried. The resulting powdered mixture of norbornane-endo-2,3-dicarboxylic anhydride and norbornane-exo-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (2) type = 50%) was used as the test material

Reference： [1]Patent: EP1669342,2006,A1 .Location in patent: Page/Page column 18-19

45
bicyclo<2.2.1>-5-hepten-2endo,3endo-dicarboxylic anhydride [ No CAS ]
[ 129-64-6 ]
[ 2746-19-2 ]

Yield	Reaction Conditions	Operation in experiment
87%	With sodium hydroxide In water at 70℃; for 0.166667h;	31 To 5.0 g of stereoisomerized methyl-5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48%) and 5.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48%) were added 18.5 g of water and 16.5 g of a 30 wt% aqueous solution of sodium hydroxide (1.1 equivalents relative to 5-norbornene-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 7.4 g (exo stereoisomeric ratio for the general formula (1) type = 87%).
1: 83% 2: 26%	With sodium hydroxide In water at 70℃; for 0.166667h;	1; 2; 3; 4; 5; 6; 7; 8; 9; 10; 11; 12; 13 (Example 1) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 26%) were added 33.6 g of water and 16.3 g of a 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 1.4 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 1.17 g (exo stereoisomeric ratio for the general formula (1) type = 88%).; (Example 2) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75%) were added 11.1 g of water and 16.3 g of a 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 4.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 10.33 g (exo stereoisomeric ratio for the general formula (1) type = 84%).; (Example 3) With the exception of using 33.7 g of water, preparation was conducted in the same manner as the example 2. The obtained solid was 7.21 g (exo stereoisomeric ratio for the general formula (1) type = 92%).; (Example 4) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48%) were added 33.6 g of water and 16.3 g of a 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 1.9 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 4.48 g (exo stereoisomeric ratio for the general formula (1) type = 88%).; (Example 5) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75%) were added 39.3 g of water and 8.2 g of a 30 wt% aqueous solution of sodium hydroxide (0.5 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 2.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 6.62 g (exo stereoisomeric ratio for the general formula (1) type = 86%).; (Example 6) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75%) were added 27.9 g of water and 24.5 g of a 30 wt% aqueous solution of sodium hydroxide (1.5 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 6.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 9.90 g (exo stereoisomeric ratio for the general formula (1) type = 91%).; (Example 7) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75%) were added 16.8 g of water and 8.2 g of a 30 wt% aqueous solution of sodium hydroxide (0.5 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 2.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 9.42 g (exo stereoisomeric ratio for the general formula (1) type = 79%).; (Example 8) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48%) were added 42.4 g of water and 4.1 g of a 30 wt% aqueous solution of sodium hydroxide (0.25 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 0.5 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 2.81 g (exo stereoisomeric ratio for the general formula (1) type = 89%).; (Example 9) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75%) were added 21.0 g of water and 2.1 g of a 30 wt% aqueous solution of sodium hydroxide (0.13 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 0.5 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 5.82 g (exo stereoisomeric ratio for the general formula (1) type = 96%).; (Example 10) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (endo stereoisomeric ratio for the general formula (1) type = 78%) were added 13.6 g of water and 16.4 g of a 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 1.3 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration. The endo stereoisomeric ratio for the 5-norbornene-2,3-dicarboxylic acid contained within the resulting filtrate was 95%. Furthermore, the filtration residue was 4.21 g (exo stereoisomeric ratio for the general formula (1) type = 46%).; (Example 11) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (endo stereoisomeric ratio for the general formula (1) type = 25%) were added 13.6 g of water and 16.3 g of a 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 4.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration. The endo stereoisomeric ratio for the 5-norbornene-2,3-dicarboxylic acid contained within the resulting filtrate was 87%. Furthermore, the filtration residue was 11.15 g (exo stereoisomeric ratio for the general formula (1) type = 89%).; (Example 12) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (endo stereoisomeric ratio for the general formula (1) type = 78%) were added 1.1 g of water and 16.3 g of a 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 1.3 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration. The endo stereoisomeric ratio for the 5-norbornene-2,3-dicarboxylic acid contained within the resulting filtrate was 96%. Furthermore, the filtration residue was 12.11 g (exo stereoisomeric ratio for the general formula (1) type = 26%).
50%	With sodium hydroxide In water at 70℃; for 0.166667h;	26; 27; 28; 29 (Example 26) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48%) were added 48.9 g of water and 1.6 g of a 30 wt% aqueous solution of sodium hydroxide (0.1 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride, 0.19 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 4.47 g (exo stereoisomeric ratio for the general formula (1) type = 50%).; (Example 27) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48%) were added 3.3 g of water and 87 g of a 45 wt% aqueous solution of sodium hydroxide (8.1 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride, 15.6 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 15.0 g (exo stereoisomeric ratio for the general formula (1) type = 51 %).; (Example 28) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48%) was added 8.6 g of a 30 wt% aqueous solution of sodium hydroxide (0.5 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride, 1.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 11.8 g (exo stereoisomeric ratio for the general formula (1) type = 52%).; (Example 29) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48%) were added 3.8 g of water and 66 g of a 30 wt% aqueous solution of sodium hydroxide (4.1 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride, 7.9 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 14.8 g (exo stereoisomeric ratio for the general formula (1) type = 55%).

Reference： [1]Current Patent Assignee: Showa Denko Materials (in: Showa Denko); SHOWA DENKO K K - EP1669342, 2006, A1 Location in patent: Page/Page column 21
[2]Current Patent Assignee: Showa Denko Materials (in: Showa Denko); SHOWA DENKO K K - EP1669342, 2006, A1 Location in patent: Page/Page column 16-18
[3]Current Patent Assignee: Showa Denko Materials (in: Showa Denko); SHOWA DENKO K K - EP1669342, 2006, A1 Location in patent: Page/Page column 20

46
[ 129-64-6 ]
[ 17812-27-0 ]
[ 14166-28-0 ]

Yield	Reaction Conditions	Operation in experiment
76 - 90%; 76 - 91%	With sodium hydroxide; In water; at 70℃; for 0.166667h;Product distribution / selectivity;	(Example 16) To 10.0 g of norbornane-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (2) type = 50%) were added 33.8 g of water and 16.0 g of a 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), and the mixture was stirred at 70C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 4.62 g (exo stereoisomeric ratio for the general formula (2) type = 88%).; (Example 17) With the exception of adding 48.9 g of water, preparation was conducted in the same manner as the example 16. The obtained solid was 2.42 g (exo stereoisomeric ratio for the general formula (2) type = 91 %).; (Example 18) With the exceptions of using 41.6 g of water and 12.0 g of the 30 wt% aqueous solution of sodium hydroxide (0.75 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 1.84 g (exo stereoisomeric ratio for the general formula (2) type = 88%).; (Example 19) With the exceptions of using 38.8 g of water and 16.0 g of the 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 4.01 g (exo stereoisomeric ratio for the general formula (2) type = 88%).; (Example 20) With the exceptions of using 33.2 g of water and 24.1 g of the 30 wt% aqueous solution of sodium hydroxide (1.5 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 6.91 g (exo stereoisomeric ratio for the general formula (2) type = 83%). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 83%.; (Example 21) With the exceptions of using 27.6 g of water and 32.2 g of the 30 wt% aqueous solution of sodium hydroxide (2.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 9.24 g (exo stereoisomeric ratio for the general formula (2) type = 76%). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 90%.; (Example 22) With the exceptions of using 21.6 g of water and 12.0 g of the 30 wt% aqueous solution of sodium hydroxide (0.75 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 5.39 g (exo stereoisomeric ratio for the general formula (2) type = 85%). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 76%.; (Example 23) With the exceptions of using 18.8 g of water and 16.1 g of the 30 wt% aqueous solution of sodium hydroxide (1.0 equivalents relative to the norbornane-2,3-dicarboxylic anhydride mixture), preparation was conducted in the same manner as the example 16. The obtained solid was 7.61 g (exo stereoisomeric ratio for the general formula (2) type = 81 %). Furthermore, the filtrate exhibited an endo stereoisomeric ratio for the general formula (2) type = 83%.

Reference： [1]Patent: EP1669342,2006,A1 .Location in patent: Page/Page column 19

47
[ 673-32-5 ]
[ 129-64-6 ]
9-methyl-10-phenyl-4-oxatetracyclo[5.4.1.0(2,6).0(8,11)]dodec-9-en-3,5-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With Br₂Co*C₂₇H₂₆P₂; zinc(II) iodide; zinc In dichloromethane at 25℃;

Reference： [1]Treutwein, Jonas; Hilt, Gerhard [Angewandte Chemie - International Edition, 2008, vol. 47, # 36, p. 6811 - 6813]

48
[ 501-65-5 ]
[ 129-64-6 ]
[ 1072142-93-8 ]

Yield	Reaction Conditions	Operation in experiment
95%	With Br₂Co*C₂₇H₂₆P₂; zinc(II) iodide; zinc In dichloromethane at 25℃;

Reference： [1]Treutwein, Jonas; Hilt, Gerhard [Angewandte Chemie - International Edition, 2008, vol. 47, # 36, p. 6811 - 6813]

49
[ 31872-98-7 ]
[ 129-64-6 ]
4-methyl-2-(3,5-dioxo-4-azatricyclo[5.2.1.0^{2-endo,6-endo}]dec-8-en-4-yl)pentanoic acid [ No CAS ]

Reference： [1]Russian Journal of Organic Chemistry,2009,vol. 45,p. 234 - 241

50
[ 129-64-6 ]
[ 107-95-9 ]
[ 200111-36-0 ]

Yield	Reaction Conditions	Operation in experiment
80.2%	With acetic acid at 80℃; for 6h;	52 Example 52 (3aR, 4S, 7R, 7aS)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-Dione (328 mg, 2.0 mmol) and aminopropionic acid (180 mg, 2.0 mmol) dissolved in 10 mLIn glacial acetic acid, the mixture was heated to 80 ° C for 6 h. The reaction was quenched with water (10 mL).The pH of the solution was adjusted to 6-8 by NaOH solution (0.1 mol/L). Dichloromethane extraction (10mL × 3),Wash with saturated NaHCO3 solution, wash with water, and combine organic phases.Dry over anhydrous sodium sulfate, separate and purify on silica gel column.Made a yellow oil 385mg,LC-MS and 1 H-NMR confirmed the expected intermediate compound in a yield of 80.2%.
79%	at 150℃; for 1h;	Compounds 3a-3e and 5a-5d (general procedure). General procedure: A mixture of 10 mmol of endic anhydride (1) and 10 mmol of amino acid 2a-2e or 4a-4d was thoroughly ground in a porcelain mortar and was then heated for 1 h at 150°C on an oil bath. After cooling to room temperature, the mixture was dissolved in pure acetone, and the product was isolated by silica gel column chromatography using anhydrous acetone as eluent.
	With acetic acid Reflux;

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF MEDICAL SCIENCES; CHINESE ACADEMY OF SCIENCES - CN109867661, 2019, A Location in patent: Paragraph 0353; 0355
[2]Sakhautdinov; Mukhametyanova [Russian Journal of Organic Chemistry, 2019, vol. 55, # 9, p. 1280 - 1286][Zh. Org. Khim., 2019, vol. 55, # 9, p. 1359 - 1366,8]
[3]Location in patent: scheme or table Tarabara; Bondarenko; Kas'Yan [Russian Journal of Organic Chemistry, 2009, vol. 45, # 2, p. 234 - 241]

51
[ 129-64-6 ]
[ 60-32-2 ]
[ 537656-33-0 ]

Yield	Reaction Conditions	Operation in experiment
81%	With acetic acid Reflux;
75%	at 150℃; for 1h;	Compounds 3a-3e and 5a-5d (general procedure). General procedure: A mixture of 10 mmol of endic anhydride (1) and 10 mmol of amino acid 2a-2e or 4a-4d was thoroughly ground in a porcelain mortar and was then heated for 1 h at 150°C on an oil bath. After cooling to room temperature, the mixture was dissolved in pure acetone, and the product was isolated by silica gel column chromatography using anhydrous acetone as eluent.
	With triethylamine In toluene for 14h; Reflux;

Reference： [1]Location in patent: scheme or table Tarabara; Bondarenko; Kas'Yan [Russian Journal of Organic Chemistry, 2009, vol. 45, # 2, p. 234 - 241]
[2]Sakhautdinov; Mukhametyanova [Russian Journal of Organic Chemistry, 2019, vol. 55, # 9, p. 1280 - 1286][Zh. Org. Khim., 2019, vol. 55, # 9, p. 1359 - 1366,8]
[3]Arkinstall, Lucy A.; Husband, Jonathan T.; Wilks, Thomas R.; Foster, Jeffrey C.; O'Reilly, Rachel K. [Chemical Communications, 2021, vol. 57, # 44, p. 5466 - 5469]

52
[ 129-64-6 ]
exo-NB-DiSXDA [ No CAS ]
5,5'-exo-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bisbicyclo[2.2.1] heptane-exo-2,3-dicarboxylic anhydride [ No CAS ]
[ 14166-28-0 ]

Reference： [1]Patent: US2011/301362,2011,A1

53
[ 129-64-6 ]
[ 1357517-65-7 ]

Yield	Reaction Conditions	Operation in experiment
	With deuterium In tetrahydrofuran; water at 20℃;	4 A mixture of 4-oxatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione (0.1 mol) and 50% water- containing 10% palladium on charcoal (0.8 g) in tetrahydrofuran (THF) is treated with D2 gas at room temperature. Upon filtration the mixture was concentrated in vacou to give (8, 9-2H2)-4-oxatricyclo[5.2.1.02'6]decane-3,5-dione.
	With palladium 10% on activated carbon; deuterium In tetrahydrofuran; water at 20℃;	4 A mixture of 4-oxatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione (0.1 mol) and 50% water-containing 10% palladium on charcoal (0.8 g) in tetrahydrofuran (THF) is treated with D2 gas at room temperature. Upon filtration the mixture was concentrated in vacou to give (8,9-2H2)-4-oxatricyclo[5.2.1.02,6]decane-3,5-dione.

Reference： [1]Current Patent Assignee: CONRIG PHARMA APS - WO2012/16569, 2012, A1 Location in patent: Page/Page column 77
[2]Current Patent Assignee: CONRIG PHARMA APS - US2013/303497, 2013, A1 Location in patent: Paragraph 0192

54
4-(4-(pyrimidin-2-yl)piperazin-1-yl)-(4,4-<SUP>2</SUP>H<SUB>2</SUB>)butan-1-amine trihydrochloride [ No CAS ]
[ 129-64-6 ]
[ 1357388-53-4 ]

Yield	Reaction Conditions	Operation in experiment
60.8%	With pyridine at 100℃; for 3h;	13 A solution of 4-(4-(pyrimidin-2-yl) piperazin-1 -yl)-(4,4-2H2)butan-1 -amine (200 mg, 1.22 mmol) and bicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxylic acid anhydride (420 mg, 1.22 mmol) in pyridine (5 ml) was heated to 100 °C for 3 hrs. The reaction mixture was cooled to room temperature, and then diluted with EtOAc (150 ml), washed with water. The organic phase was dried over Na2S04, and concentrated in vacuo to give N-[4-[4- (pyrimidin-2-yl)piperazin-1 -yl]-(4,4-2H2)butyl]-2,3-endo-bicyclo[2.2.1 ]hept-5-ene- dicarboximide (284 mg, 60.8 % yield) as a colorless oil.LCMS: RT =0.872 min, m/z =384.1 (M+1 ).
60.8%	With pyridine at 100℃; for 3h;	13 Preparation of N-[4-[4-(pyrimidin-2-yl)piperazin-1-yl]-(4,4-²H₂)-butyl]-2,3-endo-bicyclo[2.2.1]hept-5-ene-dicarboximide A solution of 4-(4-(pyrimidin-2-yl)piperazin-1-yl)-(4,4-2H2)butan-1-amine (200 mg, 1.22 mmol) and bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride (420 mg, 1.22 mmol) in pyridine (5 ml) was heated to 100° C. for 3 hrs. The reaction mixture was cooled to room temperature, and then diluted with EtOAc (150 ml), washed with water. The organic phase was dried over Na2SO4, and concentrated in vacuo to give N-[4-[4-(pyrimidin-2-yl)piperazin-1-yl]-(4,4-2H2)butyl]-2,3-endo-bicyclo[2.2.1]hept-5-ene-dicarboximide (284 mg, 60.8% yield) as a colorless oil. [0322] LCMS: RT=0.872 min, m/z=384.1 (M+1)

Reference： [1]Current Patent Assignee: CONRIG PHARMA APS - WO2012/16569, 2012, A1 Location in patent: Page/Page column 102
[2]Current Patent Assignee: CONRIG PHARMA APS - US2013/303497, 2013, A1 Location in patent: Paragraph 0321-0322

55
[ 15118-60-2 ]
[ 129-64-6 ]
[ 1365657-65-3 ]

Reference： [1]Journal of Polymer Science, Part A: Polymer Chemistry,2012,vol. 50,p. 1333 - 1341

56
[ 2469-55-8 ]
[ 129-64-6 ]
nadic anhydride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97.2%	In N,N-dimethyl acetamide at 20℃; for 6h; Inert atmosphere;

Reference： [1]Singh, Ajit Shankar; Shukla, Shailendra Kumar; Alam, Sarfaraz [Journal of Thermal Analysis and Calorimetry, 2012, vol. 107, # 2, p. 509 - 517]

57
[ 186581-53-3 ]
[ 184346-45-0 ]
[ 129-64-6 ]
methyl (1R,2S,3R,4S)-3-[(S)-4-isopropyl-2-oxo-5,5-diphenyloxazolidin-3-yl]carbonyl}bicyclo[2.2.1]hept-5-ene-2-carboxylate [ No CAS ]
methyl (1S,2R,3S,4R)-3-[(S)-4-isopropyl-2-oxo-5,5-diphenyloxazolidin-3-yl]carbonyl}bicyclo[2.2.1]hept-5-ene-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		n-Butyl lithium (350 muL, 1.6 M in hexane, 0.55 mmol) was slowly added to a suspension of oxazolidin-2-one 4 (141 mg, 0.5 mmol) in dry THF (1.3 mL) at 0 C to -10 C under an argon atmosphere. After 10 min, the reaction mixture was cooled to -78 C. Dry DMPU (0.6 mL) was then added to the reaction mixture followed by a solution of anhydride 10 (99 mg, 0.6 mmol) in dry THF (1.2 mL). After 15 min at -78 C, the reaction mixture was acidified with 5% citric acid solution, brought to room temperature, and extracted with ethyl acetate. The extract was washed with water, dried (MgSO4), and concentrated under reduced pressure. The residue was esterified with ethereal diazomethane, concentrated under reduced pressure, and purified by column chromatography to give a mixture of methyl esters 20 and 21 (20:21 = 90/10) (201 mg, 88%) as a colorless solid. Pure 20 (160 mg, 70%) was obtained as a colorless solid by a single crystallization from hexane-ethyl acetate. Mp 162-165 C; Rf = 0.65 (85:15 hexane/ethyl acetate); (c 1, MeOH); IR (CHCl3 film): 3063, 3021, 2971, 2876, 1776, 1737, 1706, 1450 cm-1; 1H NMR (200 MHz, CDCl3): delta 0.75 (d, J = 6.7 Hz, 3H, CH3CHCH3), 0.86 (d, J = 7.0 Hz, 3H, CH3CHCH3), 1.38-1.51 (m, 2H, CH2), 1.91-1.95 (m, 1H, CH3CHCH3), 3.12 (s, broad, 1H, CHCHCON), 3.18 (s, 3H, CO2CH3), 3.25 (s, broad, 1H, CHCHCO2Me), 3.33 (dd, J = 3.5, 9.8 Hz, 1H, CHCON), 4.20 (dd, J = 3.1, 9.7 Hz, 1H, CHCO2Me), 5.34 (d, J = 3.2 Hz, 1H, CHN), 6.22-6.28 (m, 2H, CH=CH), 7.25-7.49 (m, 10H, Ar); 13C NMR (50 MHz, CDCl3): delta 16.2, 21.7, 29.7, 45.9, 47.2, 47.9, 48.6, 49.0, 50.7, 64.1, 88.9, 125.6 (2C), 125.7 (2C), 127.6, 128.0 (3C), 128.4 (2C), 134.6, 135.1, 138.3, 142.3, 152.8, 172.0, 172.2; Anal. Calcd for C28H29NO5: C, 73.18; H, 6.36; N, 3.05. Found: C, 73.29; H, 6.35; N, 3.26.
		n-Butyl lithium (720 muL, 1.6 M in hexane, 1.15 mmol) was slowly added to a suspension of oxazolidin-2-one 4 (281 mg, 1 mmol) in dry THF (2.5 mL) at 0 C to -10 C under an argon atmosphere. After 10 min, the reaction mixture was brought to 28 C. Dry DMPU (1.2 mL) was then added to the reaction mixture followed by a solution of anhydride 10 (197 mg, 1.2 mmol) in dry THF (2.5 mL). After 15 min at 28 C, the reaction mixture was acidified with 5% citric acid solution and extracted with ethyl acetate. The extract was washed with water, dried (MgSO4), and concentrated under reduced pressure. The residue was esterified with ethereal diazomethane, concentrated under reduced pressure, and purified by column chromatography to give a mixture of methyl esters 20 and 21 (20:21 = 20/80) (410 mg, 90%) as a colorless solid. Pure 21 (312 mg, 68%) was obtained as a colorless solid by a single crystallization from hexane-ethyl acetate. Mp 176-178 C. Rf = 0.65 (85:15 hexane/ethyl acetate); (c 1, MeOH); IR (CHCl3 film): 3021, 2971, 2876, 1778, 1735, 1704, 1450, 1437 cm-1; 1H NMR (200 MHz, CDCl3): delta 0.76 (d, J = 6.7 Hz, 3H, CH3CHCH3), 0.88 (d, J = 7.0 Hz, 3H, CH3CHCH3), 1.28-1.33 (m, 2H, CH2), 1.92-2.03 (m, 1H, CH3CHCH3), 2.72 (s, broad, 1H, CHCHCON), 3.10 (s, broad, 1H, CHCHCO2Me), 3.31 (dd, J = 3.3, 9.8 Hz, 1H, CHCON), 3.56 (s, 3H, CO2CH3), 4.21 (dd, J = 3.3, 9.8 Hz, 1H, CHCO2Me), 5.27 (d, J = 2.9 Hz, 1H, CHN), 5.48 (dd, J = 2.9, 5.2 Hz, 1H, CH=CH), 6.31 (dd, J = 2.9, 5.3 Hz, 1H, CH=CH), 7.26-7.52 (m, 10H, Ar); 13C NMR (50 MHz, CDCl3): delta 15.8, 21.0, 29.5, 45.6, 46.8, 47.5, 48.2, 48.7, 51.0, 65.2, 89.1, 125.1 (2C), 125.5 (2C), 127.6, 128.1 (2C), 128.3, 128.6 (2C), 133.4, 135.6, 137.6, 142.4, 153.0, 171.2, 173.0.

Reference： [1]Tetrahedron Asymmetry,2013,vol. 24,p. 1212 - 1217
[2]Tetrahedron Asymmetry,2013,vol. 24,p. 1212 - 1217

58
[ 100-42-5 ]
[ 129-64-6 ]
[ 1379803-98-1 ]

Yield	Reaction Conditions	Operation in experiment
75%	With C₄₀H₅₃Cl₂F₅N₃OPRu In tetrahydrofuran at 24℃; for 24h; Inert atmosphere; Schlenk technique;	VI Example VI The use of complex 1 as (pre)catalysts for asymmetric ring opening metathesis with a cross metathesis (AROM/CM) of compound SI SI PI Using a protective atmosphere of argon, a Schlenk vessel was loaded with the substrate SI (32.8 mg, 0.2 mmol), styrene (41.7 mg, 0.4 mmol, 2 eq.) and dry deoxygenated tetrahydrofuran (1 mL). Next, solid carbene complex of ruthenium defined by Formula If (0.004 mmol, 2 mol%) was added. The mixture was stirred at a temperature of 24 °C for 24 hours. After this time ethyl-vinyl ether (0.5 mL) was added and after 30 minutes mixture was evaporated. The product PI was isolated using column chromatography on a silica gel (ethyl acetate/cyclohexane = 1:4 v/v). The product was analyzed using high performance liquid chromatography with a chiral column (Chiralcel OJ, n-hexane/isopropanol = 1:1 v/v; 0.7 ml/min; 254 nm). Colourless solid (40 mg, 75%), ee = 67%.

Reference： [1]Current Patent Assignee: POLISH ACADEMY OF SCIENCES - WO2014/102622, 2014, A1 Location in patent: Page/Page column 19-20

59
[ 129-64-6 ]
[ 941567-71-1 ]
(3aS*,4R*,7S*,7aR*)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 55.8% 2: 25.5%	With lithium aluminium tetrahydride In tetrahydrofuran; diethyl ether for 16h; Reflux;	Reduction of anhydrides 1a-e General procedure: A solution of anhydride 1a-e (6mmol) in a mixture of diethyl ether (20mL) and tetrahydrofuran (10mL) was added dropwise to LiAlH4 (8mmol) in diethyl ether (20mL). The mixture was stirred for 16h under reflux. When the reaction was completed (controlled by GC, TLC), water was added to decompose the excess of LiAlH4. The mixture was then acidified with 0.1M HCl and the products were extracted with chloroform. Then the extract was washed with saturated NaCl and dried over anhydrous MgSO4. The crude products were purified by column chromatography (silica gel, methylene chloride-methanol, 95:5). The yields and spectral data of diols 3c-e and lactones 2a-e obtained are given below. The spectral data of diols 3a and 3b have been describe previously [13].

Reference： [1]Boratyński; Pannek; Walczak; Janik-Polanowicz; Huszcza; Szczepańska; Martinez-Rojas; Olejniczak [Process Biochemistry, 2014, vol. 49, # 10, p. 1637 - 1646]

60
[ 129-64-6 ]
[ 14805-29-9 ]

Reference： [1]Patent: WO2015/56205,2015,A1

61
[ 73259-81-1 ]
[ 129-64-6 ]
(2′S)(1α,2β,6β,7α)-N-[2′-(tertbutoxycarbonylamino)carboxyethyl] 4-azatricyclo[5.2.1.02,6]dec-8-en-3,6 dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
146 mg	at 120℃; for 0.75h;Irradiation;	A microwave vessel was charged with norbornene anhydride (82 mg, 0.5 mmol) and N?(tertbutoxycarbonyl) di-1,2-aminopropinoic acid (Boc-Dap-OH) (102 mg, 0.5 mmol) and EtOAc (0.5 mL). The resulting mixture was heated to 120 C under microwave irradiation for 45 min. The solution was cooled, diluted with EtOAc (20 mL), washed with 1 M HCl (3 × 15 mL), dried with MgSO4, filtered and concentrated in vacuo to afford the title compound (146 mg, 83%) as a white solid Mp 165-170 C; deltaH (270 MHz, CDCl3) 1.43 (9H, s, t-Bu), 1.54 (1H, d, J 8.6, H10b), 1.73 (1H, d, J 8.9, H10a), 3.31 (2H, m, H1, H7), 3.38(2H, bs, H2, H6), 3.77 (2H, m, H1?), 4.39 (1H, m, H2?), 5.26 (1H, d, J 5.8, NH), 6.12 (2H, m, H8, H9); deltaC (75 MHz, CDCl3) 178.2, 177.6, 172.8, 155.7, 134.8, 134.2, 80.7, 77.2, 52.2, 52.0, 45.9, 45.0, 44.9, 38.8, 28.3; HRMS m/z (-ESI) 349.1442 ([C17H22N2O6-H]- requires 349.1400).

Reference： [1]Supramolecular Chemistry,2015,vol. 27,p. 847 - 853

62
[ 13734-28-6 ]
[ 129-64-6 ]
C₂₀H₂₈N₂O₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	In ethyl acetate at 120℃; for 0.75h; Microwave irradiation;	(2′S) (1α, 2β, 6β, 7α)-N-[2′-(phenylthioureido) N′-(5′methoxycarbonyl)methyl ethylamide] 4-azatricyclo[5.2.1.0^2,6]dec-8-en-3,6 dione (7) A microwave vessel was charged with norbornene anhydride 10 (82 mg, 0.5 mmol) and α-Boc-Lys-OH (123 mg, 0.5 mmol) and EtOAc (0.25 mL). The resulting mixture was heated to 120 °C under microwave irradiation for 45 min. The solution was cooled, diluted with EtOAc (20 mL), washed with 1 M HCl (3 × 15 mL), dried with MgSO4, filtered and concentrated in vacuo to afford imide 11a (146 mg, 77%) as a pale yellow viscous oil. δH (270 MHz, CDCl3) 1.16-1.91 (6H, m, H2′,3′,4′), 1.43 (9H, s, t-Bu), 1.52 (1H, d, J 8.7, H10a), 1.71 (1H, d, J 10.2, H10b), 3.24 (2H, m, H1,7), 3.36 (4H, m, H2,6 and H1′), 4.23 (1H, m, H5′), 5.10 (1H, bd, J 7.9, NH Boc), 6.08 (2H, s, H8,9); δC (100 MHz, CDCl3) 178.06, 176.44, 155.70, 134.52, 80.14, 53.23, 52.34, 45.80, 44.97, 37.98, 31.71, 28.38, 27.32, 22.50.

Reference： [1]Long, Benjamin M.; Pfeffer, Frederick M. [Supramolecular Chemistry, 2015, vol. 27, # 11-12, p. 847 - 853]

63
[ 91-01-0 ]
[ 129-64-6 ]
(1R,2S,5R,6S)-6-benzhydryloxycarbonyl-2,5-methylene-3-cyclohexenecarboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With (R)-3,3’-bis(2,4,6-triisopropylphenyl)-6,6’-dinitro-1,1’-binaphthylphosphate In chloroform at 20℃; for 72h; enantioselective reaction;	General Procedure for Desymmetrization of Acid Anhydrides: General procedure: To a mixture of 2 (0.10 mmol), catalyst 1 (5mol%), and alcohol 3 (0.11 mmol), was added CHCl3 (0.25 mL) at rt. The mixture was stirred at rt for indicated time in the tables and diluted with Et2O (5 mL). The organic layer was extracted with saturated aq. Na2CO3 (3 mL),and the aqueous layer was acidified with 6 N HCl. The aqueous layer was extracted with Et2O (5 mL), and the organic layer was dried over MgSO4 and concentrated in vacuo. The resulting residue was purified by column chromatography to afford the desired product 4.

Reference： [1]Yamada, Ken-ichi; Oonishi, Akinori; Kuroda, Yusuke; Harada, Shingo; Kiyama, Hiroki; Yamaoka, Yousuke; Takasu, Kiyosei [Tetrahedron Letters, 2016, vol. 57, # 36, p. 4098 - 4100]

64
[ 84282-78-0 ]
[ 129-64-6 ]
(3aR,4S,7R,7aS)-rel-2-[(3-chloro-4-fluorophenyl)amino]-3a,4,7,7a-tetrahydro-4,7-methano-1H-isoindole-1,3(2H)-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	In acetonitrile at 20℃; for 4h; Inert atmosphere;	The synthesis of (3aR,4S,7R,7aS)-rel-2-[(3-Chloro-4-fluorophenyl)amino]-3a,4,7,7a-tetrahydro-4,7-methano-1H-isoindole-1,3(2H)-dione (3) A mixture of 1 (164 mg, 1 mmol) and 2 (160.5 mg, 1 mmol) in CH3CN (5 mL) was stirred at r.t. for 4 h. The solid was filtered and recrystallized from 2-propanol to afford 3 in 80 % yield. The characterization data for 3 are given in the Supplementary material to this paper.

Reference： [1]Atbakar, Muge; Topbastekin, Onur; Ocal, Nuket [Journal of the Serbian Chemical Society, 2016, vol. 81, # 10, p. 1121 - 1125]

65
[ 83558-37-6 ]
[ 129-64-6 ]
(3aR,4S,7R,7aS)-2-(4-(3-methoxyphenyl)thiazol-2-yl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With triethylamine In toluene for 36h; Reflux;

Reference： [1]Kocyigit, Umit M.; Aslan, Osman Nuri; Gulcin, Ilhami; Temel, Yusuf; Ceylan, Mustafa [Archiv der Pharmazie, 2016, vol. 349, # 12, p. 955 - 963]

66
[ 6318-74-7 ]
[ 129-64-6 ]
(3aR,4S,7R,7aS)-2-(4,5-diphenylthiazol-2-yl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione [ No CAS ]

Reference： [1]Archiv der Pharmazie,2016,vol. 349,p. 955 - 963

67
[ 112-35-6 ]
[ 129-64-6 ]
C₁₆H₂₄O₇ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With triethylamine In dichloromethane at 20℃; for 72h;	1.A 10103] To a mixture of cis-5-norbornen-endo-2,3-dicar- boxylic anhydride (1, 16 g, 97.5 mmol) and 2-(2-(2- methoxyethoxy)ethoxy)ethanol (16 g, 97.5 mmol) in dichloromethane (250 mE) at room temp was added slowly triethylamine (14.8 g, 146.2 mmol). The reaction mixture was stirred at room temperature for 3 days. Upon completion of reaction, the mixture was acidified with 6N HC1 (150mE). The organic layer was separated, dried and conc. to getthe product (2) in 90% yield (28.8 g) which was used as suchwithout any further purification. ‘H NMR ((CD3)2C0, 300 MHz): ö 1.35 (m, 2H), 2.03 (m, 1H), 3.08 (s, 2H), 3.27 (s, 3H), 3.31 (m, 2H), 3.46 (m, 2H), 3.56 (m, 8H), 4.03 (m, 2H),6.08 (m, 1H), 6.18 (m, 1H). To a solution of compound (2) (15.43 g, 47 mmol) in dichloromethane (200 mE) was added as meta-chloroperoxybenzioc acid (mCPI3A) (17.3 g, 100 mmol). The reaction mixture was stirred at room tempera-ture for 16 h. After the reaction completion, ethyl acetate (50mE) and water (5 mE) was added to the mixture. The organic layer was separated, washed with dilute NaHCO3 followed by water (50 mE). The organic layer was evaporated to provide white solids. Redissolved the white solids in dichloromethane and passed through silica plug eluting with dichloromethane. The organic part was evaporated to yield the product (3) in 89% yield (14 g). ‘H NMR (CDC13, 300 MHz): ö 1.61 (d, 1H), 2.20 (d, 1H), 2.77 (m, 2H), 3.06 (m, 1H), 3.26 (t, 1H), 3.39 (s, 3H), 3.57 (m, 2H), 3.64 (m, 9H),4.18 (m, 1H), 4.3 (s, 1H), 4.42 (m, 1H), 4.5 (d, 1H). To the solution of compound (3) (20 g, 60 mmol) in acetonitrile (100 mE) was added pyridine (5.24 g, 66 mmol) followed by slow addition of 2-bromo-2,2-difluoroacetyl chloride (11.82 g, 61 mmol). The resulting reaction mixture was stirred overnight at room temp. Upon completion of reaction, solvent was evaporated, the residue was redissolved in dichloromethane (300 mE), washed with iN HC1 (100 mE) followed by Millipore deionized water (100 ml). The organic part was evaporated to yield crude product (4) in 85% yield (25 g) which was used as such without further purification. ‘H NMR (CDC13, 300 MHz): ö 1.39 (d, 1H), 1.72 (d, 1H), 2.53 (m, 2H), 2.79 (m, 1H), 3.0 (m, 4H), 3.26 (m, 2H), 3.28 (m, 8H), 3.94 (m, 2H), 4.31 (d, 1H), 5.14 (s, 1H). ‘9F NMR: ö -61.77.

Reference： [1]Current Patent Assignee: DOW INC - US2016/347709, 2016, A1 Location in patent: Paragraph 0064; 0103

68
[ 4415-82-1 ]
[ 129-64-6 ]
bis(cyclobutylmethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68.0%	With toluene-4-sulfonic acid; In tetrahydrofuran; benzine; at 60℃; for 12h;	.82 g (4.95 mmole) of 5-norbornene-2,3-dicarboxylic anhydride was dissolved in 5 mL of tetrahydrofuran and 25 mL of benzene After dissolving in the solvent, 4.30 g (49.45 mmole) of <strong>[4415-82-1]cyclobutyl methanol</strong> and 0.29 g (1.50 mmole) of para-toluenesulfonic acid were added And reacted at 60 DEG C for 12 hours. To the mixed solution, 10 mL of an aqueous solution was added, and then 50 mL of ethyl ether Respectively. The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to column separation (nucleic acid: / RTI & gt; (5-norbornene-2,3-dicarboxylic anhydride = 50: 1) to give 1.07 g Yield: 68.0%) of NOR-3 was obtained.

Reference： [1]Patent: KR101600896,2016,B1 .Location in patent: Paragraph 0079-0081

69
[ 452-84-6 ]
[ 129-64-6 ]
(3aR,4S,7R,7aS)-2-(2-fluoro-5-methylphenyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2017,vol. 56,p. 7209 - 7212
Angew. Chem.,2017,vol. 129,p. 7315 - 7318,4

70
[ 95-55-6 ]
[ 129-64-6 ]
C₁₅H₁₃NO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With acetic acid at 120℃; for 6h;	1.1 10.9 g (0.1 mol) of 2-aminophenol and 16.4 g (0.1 mol) of norbornanedione were added to the reaction flask, and 30 ml of glacial acetic acid was added to the flask, and the reaction was raised from room temperature to 120 ,Stir with a magnetic stirrer for 6 h,The reaction mixture was poured into deionized ice water to precipitate,The precipitate was collected and dried in a vacuum oven for 10 to 12 hours to obtain 23.4 g of the white product norbornene phenol in a yield of 92%.
92%	With acetic acid at 120℃; for 6h;	1.1 Example 1 The specific steps are: (1) 1 g of norbornene dianhydride and 0.665 g of o-aminophenol,40 mL of glacial acetic acid (AcOH) was separately added to a reaction vessel equipped with a stirring magnet and a condenser, and the reaction apparatus was transferred to an oil bath and reacted at 120 ° C for 6 hours.After the reaction was completed, the reaction solution was poured into 150 mL of deionized water.A large amount of precipitate was obtained. After suction filtration, it was washed three times with a large amount of deionized water.Into a vacuum oven at 60 ° C, the product ortho-norbornene-functionalized phenol 1.435 g,The yield was 92%. The reaction equation is as follows:
	Heating;

Reference： [1]Current Patent Assignee: JIANGSU UNIVERSITY - CN106699748, 2017, A Location in patent: Paragraph 0039; 0040
[2]Current Patent Assignee: JIANGSU UNIVERSITY - CN109293648, 2019, A Location in patent: Paragraph 0034-0037
[3]Li, Ping; Madukwe, Daniel O.; Maier, Josef M.; Masson, Eric; Pellechia, Perry J.; Rassolov, Vitaly A.; Shimizu, Ken D.; Vik, Erik C. [Chemical Science, 2020, vol. 11, # 28, p. 7487 - 7494]

71
[ 14044-63-4 ]
[ 129-64-6 ]
C₁₃H₁₅NO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	In acetonitrile at 20℃; for 0.333333h; Inert atmosphere;	4.10 Synthesis of alkyne 19 (Fig.8A) 1-amino-3-butyne (59.2μL, 0.723mmol) was added to a stirred solution of cis-5-norbornene-endo-2,3-dicarboxylic anhydride (239mg, 1.46mmol) in acetonitrile (1mL) and stirred at room temperature for 20min, over which time a white precipitate formed. The resulting mixture was transferred into a centrifuge tube and pelleted by centrifugation for 10min. The supernatant was decanted and the remaining pellet washed with EtOAc. The final product was isolated by filtration without further purification to give the product 19 as a white solid (154mg, 91% yield): m.p. 129°C; IR (νmax, ATR): 3359, 2987, 1716, 1622, 1550, 1321, 1267, 1229, 1074, 846, 759, 679, 625; 1H NMR (600MHz, DMSO-d6): δ=11.54 (1H, br-s, COOH), 7.86 (1H, t, J=5.9Hz, NH), 6.15 (1H, dd, J=5.5, 2.9Hz, HC=CH), 5.95 (1H, dd, J=5.4, HC=CH), 3.14 (1H, dd, J=10.3, 3.3Hz, CH=CHCHCHCOOH or CH=CHCHCHCONH), 3.08 (3H, contains CONHCH2CH2 and CH=CHCHCHCOOH or CH=CHCHCHCONH), 2.93 (2H, m, CHCH=CHCH), 2.80 (1H, t, J=2.6, C≡CH), 2.28-2.14 (2H, m, CH2C≡CH), 1.25 (1H, d, J=8.1Hz, CHCHAHBCH), 1.21 (1H, d, J=8.2Hz, CHCHAHBCH); 13C NMR (150MHz, DMSO-d6): 173.5, 171.2, 134.9, 133.7, 82.4, 71.9, 48.4, 48.1, 48.1, 46.7, 45.3, 37.8, 18.7; LRMS (ESI): [M-H]-: found 232.0, C13H14NO2 requires 232.1.

Reference： [1]Alcock, Lisa J.; Farrell, Kyle D.; Akol, Mawey T.; Jones, Gregory H.; Tierney, Matthew M.; Kramer, Holger B.; Pukala, Tara L.; Bernardes, Gonçalo J.L.; Perkins, Michael V.; Chalker, Justin M. [Tetrahedron, 2018, vol. 74, # 12, p. 1220 - 1228]

72
[ 507-09-5 ]
[ 129-64-6 ]
5-(thioacetoxy)-endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With dimethyl 2,2'-azobis(isobutyrate) at 65℃; for 5h; Inert atmosphere;	A.1 1. Thio-acetoxylation of endo-cis-bicyclo[ 2.2.1 ]hept-5-ene-2, 3-dicarboxylic anhydride The thio-acetoxylation ofendo-c/5-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride is depicted in Equation (la): (0160) ation (la) (0161) (0162) Structure (la) Structure (2a) (0163) [0089] In a 250 milliliter (mL) 2-neck round bottomed flask fitted with a condenser and a rubber septum are placed (i) 20 grams (0.122 mol) of endo-czs-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride (Structure (la)), (ii) 37.1 grams (35 mL, 0.49 mol) thioacetic acid, and (iii) 0.5 grams V- 601 initiator. The components are mixed and the mixture is purged with N2 for 5 minutes. The flask is then placed in an oil bath set at 65°C. The mixture is heated to 65°C for 5 hours. The flask is then removed from the oil bath and the mixture is cooled to room temperature (23°C). After cooling, 5- (thioacetoxy)endo-c/5-bicyclo[2.2. l]hept-5-ene-2,3-dicarboxylic anhydride is purified by including hexane in the mixture and stirring the mixture, which forms 28 grams of a white precipitate. The white precipitate is washed with hexane and dried under a vacuum. The product formed is 5- (thioacetoxy)endo-c/5-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, depicted as Structure (2a) in Equation (la) above. The reaction achieves a 96% yield of 5-(thioacetoxy)endo-czs- bicyclo[2.2. l]hept-5-ene-2,3-dicarboxylic anhydride. (0164) [0090] 1H MR (400 MHz, CDCl3, 30°C): 53.54 (dd,J= 10.2, 5.4 Hz, 1H), 3.47 (dd, J= 5.3, 1.9 Hz, 1H), 3.45-3.40 (m, 1H), , 2.88-2.80 (m, 1H), 2.76-2.68 (m, 1H), 2.24 (s, 3H), 2.00 (ddd, J = 15.0, 8.6, 2.5 Hz, 1H), 1.80 (dt, J= 10.8, 1.5 Hz, 1H), 1.73-1.64 (m, 1H), 1.58 (dtd, , J= 14.9, 4.7, 1.9 Hz, 1H). (0165) [0091] 13C NMR (101 MHz, CDC13, 30°C): δ 194.70, 171.75, 170.94, 49.56, 48.98, 46.55, 40.63, 40.44, 40.10, 33.49, 30.27.

Reference： [1]Current Patent Assignee: DOW INC - WO2017/223164, 2017, A1 Location in patent: Paragraph 0088-0091

73
[ 63-91-2 ]
[ 129-64-6 ]
endo-(S)-2-(3,5-dioxo-4-azatricyclo[5.2.1.0^2,6]dec-8-en-4-yl)-3-phenylpropionic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With triethylamine In toluene at 110℃; for 16h; Dean-Stark;
74%	With acetic acid for 4h; Reflux;	The general method of the synthesis of N-substitutedimides of alicyclic dicarboxylic acids (III)-(X). General procedure: Acyclicanhydride (I) or (II) (0.05 mol), an amino acid(55 mmol), and acetic acid (15 mL) were placed in around-bottomed flask equipped with a reflux condenserand refluxed for 4 h. Then, the reaction mixturewas poured into water (100 mL), and the sedimentwas filtered, washed with water, and dried at 40°.
	Reflux;

Reference： [1]Engstrom, Jordan R.; Savyasachi, Aramballi J.; Parhizkar, Marzieh; Sutti, Alessandra; Hawes, Chris S.; White, Jonathan M.; Gunnlaugsson, Thorfinnur; Pfeffer, Frederick M. [Chemical Science, 2018, vol. 9, # 23, p. 5233 - 5241]
[2]Firstova; Kofanov; Zakshevskaya; Kovaleva [Russian Journal of Bioorganic Chemistry, 2019, vol. 45, # 3, p. 204 - 213][Bioorg. Khim., 2019, vol. 45, # 3, p. 430 - 440,11]
[3]Tahir Gunkara, Omer [Phosphorus, Sulfur and Silicon and the Related Elements, 2019, vol. 194, # 9, p. 909 - 916]

74
[ 51688-75-6 ]
[ 129-64-6 ]
C₄₂H₂₉NO₅ [ No CAS ]

Reference： [1]Chemical Communications,2018,vol. 54,p. 8502 - 8505

75
[ 129-64-6 ]
[ 56-12-2 ]
4-(1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindol-2(3H)-yl)butanoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84.6%	With acetic acid at 80℃; for 6h;	53 Example 53 (3aR,4S,7R,7aS)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione (328 mg, 2.0 mmol) and 4-aminobutyric acid (210 mg, 2.0 mmol) Dissolved in 10 mL of glacial acetic acid, heated to 80 ° C for 6 h.The reaction was quenched with water (10 mL) and NaOH solution (0.1 mol/L) was adjusted to pH 6-8.Dichloromethane extraction (10mL × 3), washed with saturated NaHCO3 solution, washed with water,The organic phase is combined, dried over anhydrous sodium sulfate, and purified by silica gel column.Made a yellow oil 420mg,LC-MS and 1 H-NMR confirmed the expected intermediate compound in a yield of 84.6%.
75%	at 150℃; for 1h;	Compounds 3a-3e and 5a-5d (general procedure). General procedure: A mixture of 10 mmol of endic anhydride (1) and 10 mmol of amino acid 2a-2e or 4a-4d was thoroughly ground in a porcelain mortar and was then heated for 1 h at 150°C on an oil bath. After cooling to room temperature, the mixture was dissolved in pure acetone, and the product was isolated by silica gel column chromatography using anhydrous acetone as eluent.
61%	With triethylamine In toluene for 14h; Inert atmosphere; Schlenk technique; Reflux;

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF MEDICAL SCIENCES; CHINESE ACADEMY OF SCIENCES - CN109867661, 2019, A Location in patent: Paragraph 0357; 0359
[2]Sakhautdinov; Mukhametyanova [Russian Journal of Organic Chemistry, 2019, vol. 55, # 9, p. 1280 - 1286][Zh. Org. Khim., 2019, vol. 55, # 9, p. 1359 - 1366,8]
[3]Dato, Florian M.; Sheikh, Miriam; Uhl, Rocky Z.; Schüller, Alexandra W.; Steinkrüger, Michaela; Koch, Peter; Neudörfl, Jörg-Martin; Gütschow, Michael; Goldfuss, Bernd; Pietsch, Markus [ChemMedChem, 2018, vol. 13, # 17, p. 1833 - 1847]

76
[ 155130-15-7 ]
[ 129-64-6 ]
exo,exo-bis(2-(2′-(2″-(2’’’-(2’’’’-tosyloxyethoxy)ethoxy)ethoxy)ethoxy)ethyl) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate [ No CAS ]

Reference： [1]Macromolecules,2019,vol. 52,p. 1371 - 1388

77
[ 373-88-6 ]
[ 129-64-6 ]
C₁₁H₁₄F₃N [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2018,vol. 83,p. 12683 - 12693

78
[ 35613-84-4 ]
[ 129-64-6 ]
trans-3-(3-isopropyl-1,2,4-oxadiazol-5-yl)bicyclo[2.2.1]hept-5-ene-2-carboxylic acid [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2019,vol. 2019,p. 5685 - 5693

79
[ 22179-78-8 ]
[ 129-64-6 ]
trans-3-(3-(4-fluorophenyl)-1,2,4-oxadiazol-5-yl)bicyclo[2.2.1]hept-5-ene-2-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With sodium hydroxide In dimethyl sulfoxide at 20℃; for 20h; diastereoselective reaction;

Reference： [1]Baykov, Sergey; Tarasenko, Marina; Zelenkov, Lev E.; Kasatkina, Svetlana; Savko, Polina; Shetnev, Anton [European Journal of Organic Chemistry, 2019, vol. 2019, # 33, p. 5685 - 5693]

80
[ 129-64-6 ]
[ 13414-56-7 ]
(3aR,4S,7R,7aS)-2-(2,3-dihydrobenzofuran-7-yl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2019,vol. 141,p. 12513 - 12517

81
[ 33631-01-5 ]
[ 129-64-6 ]
(3aR,4S,7R,7aS)-2-(1-methyl-2-oxo-1,2-dihydropyridin-3-yl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2019,vol. 141,p. 12513 - 12517

82
[ 1978-33-2 ]
[ 129-64-6 ]
(3aR,4S,7R,7aS)-2-(2-fluoro-3-methylphenyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2019,vol. 141,p. 12513 - 12517

83
[ 29027-17-6 ]
[ 129-64-6 ]
(3aR,4S,7R,7aS)-2-(2-chloro-3-methylphenyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2019,vol. 141,p. 12513 - 12517

84
[ 1462-96-0 ]
[ 129-64-6 ]
C₁₆H₂₂O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: 1-ethylcyclopentanol With sodium hydride In tetrahydrofuran at 60℃; for 2h; Inert atmosphere; Reflux; Stage #2: 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride In tetrahydrofuran at 40 - 50℃; for 12h; Inert atmosphere;	1-1.1-1-1 [Example 1-1-1] Synthesis of Intermediate 1 Under a nitrogen atmosphere, sodium hydride (178g) was suspended in THF (2,192g),Heat to an internal temperature of 60°C. After that, raw material 2 (460g) was added dropwise,Heating and refluxing were performed for 2 hours to prepare alkoxide. After cooling to an internal temperature of 40,A solution prepared by dissolving raw material 1 (644 g) in THF (1,930 mL) was added dropwise while maintaining an internal temperature of 40 to 50°C.After dripping, it was aged for 12 hours at an internal temperature of 45°C. After aging, the reaction system is cooled,A 20% by mass formic acid aqueous solution (1,040 g) was added dropwise to stop the reaction.After that, it was extracted with toluene (1,500 mL),Carry out usual water treatment (aqueous work-up),The solvent is distilled off and recrystallized with hexane,In this way, a white crystal intermediate 1 (yield 926 g, yield 85%) was obtained.

Reference： [1]Current Patent Assignee: SHIN-ETSU CHEMICAL CO., LTD. - CN111440104, 2020, A Location in patent: Paragraph 0573-0577

85
[ 593-51-1 ]
[ 129-64-6 ]
(1R,2S,6R,7S)-4-methyl-4-azatricyclo[5.2.1.0(2,6)]dec-8-ene-3,5-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50%	With sodium hydrogencarbonate; triethylamine In toluene at 20℃; for 33h; Reflux;	Preparation of the N-methyl imide 24 Compound 24 was synthesized by a slightly modified version of the method used to obtain theimide 19. 3.00 g (18.27 mmol) of the tricyclic anhydride 23 was dissolved in 80 mL toluene.Then, 1 equiv MeNH3Cl, 1.2 equiv Et3N, and 1 equiv NaHCO3 were added. Since MeNH2 is volatile, the mixture was stirred at rt for 18 h to allow the half-amide intermediate to form.Then, the mixture was treated at reflux temperature for 15 h to facilitate ring-closing. Aftercooling, it was washed with 3×40 mL 10% aqueous HCl solution, and then with 3×30 mLsaturated aqueous NaCl solution. The organic layer was dried (Na2SO4), slightly concentrated,and titurated with hexane to obtain the product 24 as a white solid (yield of 50%)

Reference： [1]Fülöp, Ferenc; Haukka, Matti; Kiss, Loránd; Nonn, Melinda; Novák, Tamás T.; Remete, Attila Márió [Beilstein Journal of Organic Chemistry, 2020, vol. 16, p. 2562 - 2575]

86
[ 115-69-5 ]
[ 129-64-6 ]
C₁₃H₁₇NO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	In toluene at 120℃; for 0.266667h; Inert atmosphere;	1.1 (1) Preparation of compound 1 Take 5-norbornene-2,3-dicarboxylic anhydride (5.00g, 30.46mmol) and 2-amino-2-methyl-1,3-propanediol (3.80g, 36.14mmol) into a 250ml dry reaction flask In the medium, nitrogen was introduced for 10 minutes, and then 150 ml of anhydrous toluene was added, refluxed at 120° C. for 16 hours and installed with a water trap. After the completion of the reaction was confirmed by thin-layer chromatography, the solvent was removed by rotary evaporation, and the product was separated by silica gel column chromatography to obtain 5.21 g of a white solid with a yield of 68%.

Reference： [1]Current Patent Assignee: SHANGHAI INSTITUE OF TECHNOLOGY - CN112592376, 2021, A Location in patent: Paragraph 0050; 0058-0061

87
[ 67-56-1 ]
[ 129-64-6 ]
dimethyl 5-cis-norbornene-2,3-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With hydrogenchloride In water at 65℃; for 4h; Inert atmosphere;	1 Synthesis Example 1 To a 1 L reaction vessel, cis-5s-norbornene-exo-2,3-dicarboxylic anhydride (100 g, 0.609 mol, exo form:endo form=98:2) manufactured by Mancherster Organics, methanol (500 mL), and concentrated hydrochloric acid (5.0 mL) having a concentration of 37% by mass were sequentially added under an argon stream to obtain a mixture liquid. Then, the mixture liquid was stirred under reflux conditions (internal temperature: 65° C.) for 4 hours to obtain a reaction liquid. After the reaction under reflux conditions for 4 hours in this way (after completion of the reaction), GC measurement was performed on the reaction liquid to confirm the disappearance of the raw material cis-5s-norbornene-exo-2,3-dicarboxylic anhydride. Then, methanol was distilled off from the reaction liquid under reduced pressure using a rotary evaporator to obtain a liquid product. Next, the liquid product was dissolved in ethyl acetate (500 mL) and transferred to a separatory funnel. The liquid product was washed twice with saturated sodium hydrogen carbonate aqueous solution (200 mL) and then once with water (200 mL) to obtain an organic layer. Then, ethyl acetate was distilled off from the organic layer under reduced pressure using a rotary evaporator, thereby obtaining cis-5-norbornene-exo-2,3-dimethyl dicarboxylate (120 g, yield: 94%, exo form:endo form=100:0). The structure of the product was identified by 1H-NMR and 13C-NMR. Note that, regarding the above product, the "exo form" means that all the groups represented by the formula: -COOMe have an exo conformation with respect to the norbornene ring to be bonded, and on the other hand, the "endo form" means that all the groups represented by the formula: -COOMe have an endo conformation with respect to the norbornene ring to be bonded. The reaction formula of the reaction used in the production of such a product is presented below.

Reference： [1]Current Patent Assignee: ENEOS HOLDINGS INC - US2021/122724, 2021, A1 Location in patent: Paragraph 0077-0078

88
[ 150-13-0 ]
[ 129-64-6 ]
4-((1R,2S,6R,7S)-3,5-Dioxo-4-aza-tricyclo[5.2.1.0^2,6]dec-8-en-4-yl)-benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78.2%	With dmap; acetic acid at 0 - 110℃; for 24h; Schlenk technique;	2.4. Synthesis of N-4-carboxylphenyl-Norbornene-Dicarboximide (Compound, 2) 5-Norbornene-2,3-dicarboxylicanhydride (8.85 g, 54 mmol), 4- dimethylaminopyridine (DMAP) (0.66 g, 5.4 mmol) and acetic acid (120 mL) were charged into a 500 mL Schlenk flask. A solution of 4-aminobenzoic acid (6.18 g, 45 mmol) in 100 mL of acetic acid was then added dropwise to the above mixture at 0 C. The reaction mixture was allowed to warm to room temperature and stirred at 110 C for 24 h. The reaction mixture was poured into excess water, the precipitate was isolated and further purified through recrystallization from ethanol: CH2Cl2 = 4: 1 to afford a white crystal, 2 (11.76 g, 78.2% yield). 1 H NMR (CDCl3), δ (ppm): 8.15-8.08 (d, 2H, m-NArHCOOH), 7.26-7.07 (d, 2H, o-NArHCOOH), 6.20-6.15 (d, 2H, CH- -CH), 3.25-3.13 (m, 4H, CHCHOCN + CH- -CHCHCH), 1.45-1.31, (d, 2H, CH2). EI/MS: Calcd. for C16H13NO4: 283.08; found: 283.21. Anal. calcd for C: 67.84, H: 4.63, O: 22.59, N: 4.94; found C: 67.89, H: 4.64, O: 22.56, N: 4.91.

Reference： [1]Li, Yadi; Song, Wei; Li, Juan; Wang, Chengshuang; Ding, Liang [Polymer, 2021, vol. 232]

Type	HazMat fee for 500 gram (Estimated)
Excepted Quantity	USD 0.00
Limited Quantity	USD 15-60
Inaccessible (Haz class 6.1), Domestic	USD 80+
Inaccessible (Haz class 6.1), International	USD 150+
Accessible (Haz class 3, 4, 5 or 8), Domestic	USD 100+
Accessible (Haz class 3, 4, 5 or 8), International	USD 200+

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
{[ item.p_purity ]}	{[ item.pr_size ]}	{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]}	{[ getRatePrice(item.pr_usd, 1,1) ]}	Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]}	{[ item.pr_usastock ]}	Inquiry -	{[ item.pr_chinastock ]}	Inquiry -

CAS No. :	129-64-6	MDL No. :	MFCD00151106
Formula :	C₉H₈O₃	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	-
M.W :	164.16	Pubchem ID :	-
Synonyms :		Chemical Name :	(3aR,4S,7R,7aS)-rel-3a,4,7,7a-Tetrahydro-4,7-methanoisobenzofuran-1,3-dione

Num. heavy atoms :	12
Num. arom. heavy atoms :	0
Fraction Csp3 :	0.56
Num. rotatable bonds :	0
Num. H-bond acceptors :	3.0
Num. H-bond donors :	0.0
Molar Refractivity :	40.05
TPSA :	43.37 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.83 cm/s

[ CAS No. 129-64-6 ] {[proInfo.proName]}

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Medicinal Chemistry

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[ 129-64-6 ] Synthesis Path-Upstream 1~10

[ 129-64-6 ] Synthesis Path-Downstream 1~88

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Log Po/w (iLOGP) :	1.33
Log Po/w (XLOGP3) :	0.66
Log Po/w (WLOGP) :	0.51
Log Po/w (MLOGP) :	1.61
Log Po/w (SILICOS-IT) :	0.97
Consensus Log Po/w :	1.02

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.55

Log S (ESOL) :	-1.27
Solubility :	8.74 mg/ml ; 0.0533 mol/l
Class :	Very soluble
Log S (Ali) :	-1.15
Solubility :	11.7 mg/ml ; 0.0713 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-0.49
Solubility :	53.2 mg/ml ; 0.324 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	3.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	3.71

Signal Word:	Danger	Class:	N/A
Precautionary Statements:	P261-P272-P280-P284-P302+P352-P304+P340-P305+P351+P338+P310-P333+P313-P342+P311-P501	UN#:	N/A
Hazard Statements:	H317-H318-H334	Packing Group:	N/A
GHS Pictogram:

Yield	Reaction Conditions	Operation in experiment
80.1%	at 200℃; for 0.133333 h; Microwave irradiation	A method for preparing high-purity cis-5-norbornene-exo-2,3-dicarboxylic acid anhydride by microwave reaction is disclosed. The method comprises the following steps: using cis-5-norbornene-endo-2,3-dicarboxylic anhydride as raw material, Specific steps are as follows:(1) In a 1 L reaction flask, 200 g of cis-5-norbornene-endo-2,3-dicarboxylic anhydride and 600 mL of toluene were stirred and placed in a microwave autoclave. The temperature was raised to 200 ° C, 100-200GHz microwave for 8 minutes;(2) The reaction was completed, the reactor of step (1) was cooled to 110 ° C, stirred in an oil bath for 30 minutes to crystallize, cooled to room temperature, filtered and dried to give the product cis-5-norbornene- Dicarboxylic anhydride 160.2 g; Yield: 80.1percent; Purity: 98.2percent; Oxide impurity content: 0.06percent.
40%	at 180℃; for 6 h;	Nadic anhydride (ACROS, 225 g, 1.4 mol, pure endo isomer) was put into the 500 ml 2-neck round bottom flask, and refluxed while the temperature was increased to 180° C. Next, while it was agitated at 300 rpm, it was reacted for 6 hours, the reactants were cooled and recrystallized with benzene. The product that was rearranged by 80percent exo isomers were obtained by carrying out the recrystallization twice (yield: 40percent). [0082] The NMR analysis results of the pure endo isomer compound are described below. [0083] ¹H-NMR (300 MHz, CDCl₃): δ6.31 (2H), 3.50 (2H,) 3.59 (2H), δ1.57 to 1.80 (2H) [0084] In addition, the results of the NMR analysis that was carried out in order to confirm that the 80percent exo isomer nadic anhydride compound that was manufactured through thermal rearrangement was formed are described below. [0085] ¹H-NMR (300 MHz, CDCl₃): δ6.30 to 6.34 (2H), 3.44 (2H) 3.01 (2H), δ1.68 (1H), 61.42 (1H)
32.8%	at 185℃;	The synthetic procedure is a modification of the previously published method [16]. cis-5-norbornene-endo-2,3-dicarboxylic anhydride (250 g, 1.52 mol) was heated to 185 °C for 4-5 h. After cooling to room temperature, the endo/exo mixture was further purified by recrystallization in ethyl acetate four times to obtain pure cis-5-norbornene exo-2,3-dicarboxylic anhydride. Yield: 82 g (32.8percent), purity: >98percent exo isomer, mp: 141-143 °C, lit. 143 °C[16] . ¹H NMR (CDCl₃): δ = 6.34 (s, 2H), 3.45 (s, 2H), 3.02 (s, 2H), 1.67 (d, 1H), 1.44 (d, 1H). ¹³C NMR (CDCl₃): δ = 172.3, 138.6, 49.4, 47.5, 44.7.

Yield	Reaction Conditions	Operation in experiment
87%	With sodium hydroxide In water at 70℃; for 0.166667 h;	To 5.0 g of stereoisomerized methyl-5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) and 5.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 18.5 g of water and 16.5 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.1 equivalents relative to 5-norbornene-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 7.4 g (exo stereoisomeric ratio for the general formula (1) type = 87percent).
83%	With sodium hydroxide In water at 70℃; for 0.166667 h;	(Example 1) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 26percent) were added 33.6 g of water and 16.3 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 1.4 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 1.17 g (exo stereoisomeric ratio for the general formula (1) type = 88percent).; (Example 2) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75percent) were added 11.1 g of water and 16.3 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 4.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 10.33 g (exo stereoisomeric ratio for the general formula (1) type = 84percent).; (Example 3) With the exception of using 33.7 g of water, preparation was conducted in the same manner as the example 2. The obtained solid was 7.21 g (exo stereoisomeric ratio for the general formula (1) type = 92percent).; (Example 4) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 33.6 g of water and 16.3 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 1.9 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 4.48 g (exo stereoisomeric ratio for the general formula (1) type = 88percent).; (Example 5) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75percent) were added 39.3 g of water and 8.2 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.5 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 2.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 6.62 g (exo stereoisomeric ratio for the general formula (1) type = 86percent).; (Example 6) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75percent) were added 27.9 g of water and 24.5 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.5 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 6.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 9.90 g (exo stereoisomeric ratio for the general formula (1) type = 91percent).; (Example 7) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75percent) were added 16.8 g of water and 8.2 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.5 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 2.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 9.42 g (exo stereoisomeric ratio for the general formula (1) type = 79percent).; (Example 8) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 42.4 g of water and 4.1 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.25 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 0.5 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 2.81 g (exo stereoisomeric ratio for the general formula (1) type = 89percent).; (Example 9) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 75percent) were added 21.0 g of water and 2.1 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.13 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 0.5 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 5.82 g (exo stereoisomeric ratio for the general formula (1) type = 96percent).; (Example 10) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (endo stereoisomeric ratio for the general formula (1) type = 78percent) were added 13.6 g of water and 16.4 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 1.3 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration. The endo stereoisomeric ratio for the 5-norbornene-2,3-dicarboxylic acid contained within the resulting filtrate was 95percent. Furthermore, the filtration residue was 4.21 g (exo stereoisomeric ratio for the general formula (1) type = 46percent).; (Example 11) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (endo stereoisomeric ratio for the general formula (1) type = 25percent) were added 13.6 g of water and 16.3 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 4.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration. The endo stereoisomeric ratio for the 5-norbornene-2,3-dicarboxylic acid contained within the resulting filtrate was 87percent. Furthermore, the filtration residue was 11.15 g (exo stereoisomeric ratio for the general formula (1) type = 89percent).; (Example 12) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (endo stereoisomeric ratio for the general formula (1) type = 78percent) were added 1.1 g of water and 16.3 g of a 30 wtpercent aqueous solution of sodium hydroxide (1.0 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride mixture, 1.3 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration. The endo stereoisomeric ratio for the 5-norbornene-2,3-dicarboxylic acid contained within the resulting filtrate was 96percent. Furthermore, the filtration residue was 12.11 g (exo stereoisomeric ratio for the general formula (1) type = 26percent).
50%	With sodium hydroxide In water at 70℃; for 0.166667 h;	(Example 26) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 48.9 g of water and 1.6 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.1 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride, 0.19 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 4.47 g (exo stereoisomeric ratio for the general formula (1) type = 50percent).; (Example 27) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 3.3 g of water and 87 g of a 45 wtpercent aqueous solution of sodium hydroxide (8.1 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride, 15.6 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 15.0 g (exo stereoisomeric ratio for the general formula (1) type = 51 percent).; (Example 28) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) was added 8.6 g of a 30 wtpercent aqueous solution of sodium hydroxide (0.5 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride, 1.0 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 11.8 g (exo stereoisomeric ratio for the general formula (1) type = 52percent).; (Example 29) To 10.0 g of 5-norbornene-2,3-dicarboxylic anhydride (exo stereoisomeric ratio for the general formula (1) type = 48percent) were added 3.8 g of water and 66 g of a 30 wtpercent aqueous solution of sodium hydroxide (4.1 equivalents relative to the 5-norbornene-2,3-dicarboxylic anhydride, 7.9 equivalents relative to 5-norbornene-endo-2,3-dicarboxylic anhydride), and the mixture was stirred at 70°C for 10 minutes. The solid was then separated by filtration and dried. The obtained solid was 14.8 g (exo stereoisomeric ratio for the general formula (1) type = 55percent).

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling