Name: 4463-33-6|2,3-Dimethoxytoluene|95%
Brand: Ambeed
SKU: A573655
Price: 8.0 USD
Availability: InStock
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1
[ 4463-33-6 ]
[ 78312-28-4 ]

Yield	Reaction Conditions	Operation in experiment
82%	With nitric acid at -10℃; for 0.166667h;
	With nitric acid; acetic acid

Reference： [1]Sanchez, Ignacio H.; Larraza, Maria Isabel; Basurto, Fernando; Yanez, Ricardo; Avila, Salvador; et al. [Tetrahedron, 1985, vol. 41, # 12, p. 2355 - 2359]
[2]Cain; Simonsen [Journal of the Chemical Society, 1914, vol. 105, p. 163] Majima; Okazaki [Chemische Berichte, 1916, vol. 49, p. 1490]

2
[ 4463-33-6 ]
[ 107-30-2 ]
[ 5417-19-6 ]

Yield	Reaction Conditions	Operation in experiment
47%	With acetic acid at 20℃; for 16h; Heating;
	With acetic acid

Reference： [1]Zuniga, Miguel A.; Dai, Jifeng; Wehunt, Mark P.; Zhou, Qibing [Chemical Research in Toxicology, 2006, vol. 19, # 6, p. 828 - 836]
[2]Hornbaker; Burger [Journal of the American Chemical Society, 1955, vol. 77, p. 5314,5317]

3
[ 86-51-1 ]
[ 4463-33-6 ]

Reference： [1]Tetrahedron,2007,vol. 63,p. 9382 - 9386
[2]Journal of Organic Chemistry,1984,vol. 49,p. 2130 - 2135
[3]Chemische Berichte,1916,vol. 49,p. 1265
[4]Journal of Organic Chemistry,1943,vol. 8,p. 73,77
[5]Journal of Organic Chemistry,1964,vol. 29,p. 435 - 439
[6]Journal of Medicinal Chemistry,1971,vol. 14,p. 729 - 732

4
[ 2896-67-5 ]
[ 74-88-4 ]
[ 4463-33-6 ]

Reference： [1]Chemische Berichte,1916,vol. 49,p. 1490

5
[ 4885-02-3 ]
[ 4463-33-6 ]
[ 16273-16-8 ]

Yield	Reaction Conditions	Operation in experiment
70%	With tin(IV) chloride In 1,2-dichloro-ethane 1.) 0 deg C, 20 min, 2.) RT, overnight;

Reference： [1]Baudart; Hennequin [Journal of Antibiotics, 1993, vol. 46, # 9, p. 1458 - 1470]

6
[ 4885-02-3 ]
[ 4463-33-6 ]
[ 51234-09-4 ]

Yield	Reaction Conditions	Operation in experiment
95%	With tin(IV) chloride In dichloromethane a) 0 deg C, 1 h, b) 0 deg C, 1 h, c) to room temperature;
	With titanium tetrachloride In dichloromethane at 25℃; for 2h;

Reference： [1]Meier, Herbert; Kretzschmann, Holger; Kolshorn, Heinz [Journal of Organic Chemistry, 1992, vol. 57, # 25, p. 6847 - 6852]
[2]Sinhababu, Achintya K.; Ghosh, Anil K.; Borchardt, Ronald T. [Journal of Medicinal Chemistry, 1985, vol. 28, # 9, p. 1273 - 1279]

7
[ 124-38-9 ]
[ 4463-33-6 ]
[ 77869-39-7 ]

Yield	Reaction Conditions	Operation in experiment
66%	With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In hexane for 18h; Ambient temperature;
	Stage #1: 1,2-dimethoxy-3-methylbenzene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In hexane at 20℃; for 24h; Inert atmosphere; Stage #2: carbon dioxide In hexane at -78℃; Inert atmosphere;

Reference： [1]Gainor, James A.; Weinreb, Steven M. [Journal of Organic Chemistry, 1981, vol. 46, # 21, p. 4317 - 4319]
[2]Serra, Stefano; Fronza, Giovanni [European Journal of Organic Chemistry, 2012, # 25, p. 4838 - 4843]

8
[ 4463-33-6 ]
[ 2896-67-5 ]

Reference： [1]Synthetic Communications,1996,vol. 26,p. 49 - 62
[2]Australian Journal of Chemistry,1985,vol. 38,p. 777 - 792
[3]Journal of the Chemical Society. Chemical communications,1984,p. 227 - 229

9
[ 4463-33-6 ]
[ 74866-17-4 ]

Yield	Reaction Conditions	Operation in experiment
80%	With N-Bromosuccinimide; In acetonitrile; at 20℃; for 24h;Inert atmosphere;	To a solution of 1,2-dimethoxy-3-methyl-benzene 9 (55 g, 361.8 mmol) in ACN (1.8 L) was added NBS (65.3 g, 369 mmol) portion wise and the mixture was stirred at rt for 24 h under nitrogen atmosphere. Reaction mixture was diluted with ethyl acetate and washed with sat. aq NaHCO3, water and dried over Na2SO4. Concentration of the solvent and recrystallization from MeOH gave the pure product as white solid (67 g, 80%). 1H NMR (CDCl3, 400 MHz) delta 7.22 (d, J = 8.8 Hz, 1H), 6.64 (d, J = 8.8 Hz, 1H), 3.82 (s, 3H), 3.76 (s, 3H), 2.32 (s, 3H). 13C NMR (CDCl3, 100 MHz): delta 152.1, 148.0, 132.2, 127.2, 116.0, 110.9, 60.3, 55.8, 16.0; GC-MS: 230, 230 m/z [M+].
	With N-Bromosuccinimide; In tetrahydrofuran; at 20℃;	Preparative Example 22PREPARATION OF 1-BROMO-3,4-DIMETHOXY-2-METHYLBENZENETo a stirred solution of 1,2-dimethoxy-2-methoxy-3-methylbenzene (4 g, 26.3 mmol) in 35 mL THF at room temperature was added NBS (4.68 g, 26.3 mmol). The reaction mixture was stirred at room temperature overnight. The reaction mixture was partitioned between saturated NaHCO3 and EtOAc, the layers were separated, and the aqueous layer was extracted again with EtOAc. The combined organic layers were dried (MgSO4), filtered, and evaporated in vacuo. The resulting material was purified by silica gel chromatography (30% EtOAc in hexane) to provide the product.1H NMR (500 MHz, CDCl3) delta (ppm): 7.28 (d, 1H), 6.70 (d, 1H), 3.90 (s, 3H), 3.86 (s, 3H), 2.40 (s, 3H).
	With N-Bromosuccinimide; In tetrahydrofuran; at 20℃;	PREPARATIVE EXAMPLE 8PREPARATION OF 1 -BROMO-3 ,4-DIMETHOXY^-METHYLBENZENETo a stirred solution of l,2-dimethoxy-2-methoxy-3-methylbenzene (4 g, 26.3 mmol) in 35 mL THF at room temperature was added NBS (4.68 g, 26.3 mmol). The reaction mixture was stirred at room temperature overnight. The reaction mixture was partitioned between saturated NaHCO3 and EtOAc5 the layers were separated, and the aqueous layer was extracted again with EtOAc. The combined organic layers were dried (MgSO4), filtered, and evaporated in vacuo. The resulting material was purified by silica gel chromatography (30% EtOAc in hexane) to provide the product. 1H NMR (500 MHz, CDCI3) delta (ppm): 7.28 (d5 1 H), 6.70 (d, IH), 3.90 (s, 3H), 3.86 (s, 3H), 2.40 (s, 3H).Utilizing the foregoing procedure, the following compound was prepared: l-bromo-4,5-dimethoxy-2-methylbenzene was prepared in 83% yield after purification by silica gel ;hromatography (30% EtOAc in hexane).H NMR (500 MHz, CDCl3) delta (ppm): 7.04 (s, 1 H), 6.78 (s, 1 H), 3.90 (s, 6H), 2.40 (s, 3H).

Reference： [1]Patent: WO2006/83417,2006,A2 .Location in patent: Example 5
[2]Synlett,2011,p. 2663 - 2666
[3]Tetrahedron Letters,2000,vol. 41,p. 1171 - 1174
[4]Heterocycles,2007,vol. 74,p. 895 - 912
[5]Tetrahedron Letters,1997,vol. 38,p. 1535 - 1538
[6]Synlett,1997,vol. 1997,p. 1108 - 1110
[7]Tetrahedron,1998,vol. 54,p. 197 - 212
[8]Tetrahedron Letters,1999,vol. 40,p. 6915 - 6918
[9]Advanced Synthesis and Catalysis,2008,vol. 350,p. 2179 - 2182
[10]Synthesis,1996,p. 230 - 236
[11]Bioorganic and Medicinal Chemistry,2016,vol. 24,p. 2887 - 2896
[12]Journal of the American Chemical Society,1980,vol. 102,p. 6504 - 6512
[13]Patent: US2010/279983,2010,A1 .Location in patent: Page/Page column 18
[14]Organic Process Research and Development,2004,vol. 8,p. 624 - 627
[15]Patent: WO2007/139729,2007,A1 .Location in patent: Page/Page column 24

10
[ 4463-33-6 ]
[ 74866-18-5 ]

Yield	Reaction Conditions	Operation in experiment
97%	With iodine; silver trifluoroacetate In dichloromethane at 0℃; for 8h;
72%	With N-iodo-succinimide; sulfuric acid In acetonitrile at 25℃; for 2h; Inert atmosphere;
57%	With iodine; mercury(II) oxide In ethanol at 70℃; for 0.583333h;

Reference： [1]Lee, Chia-Lin; Huang, Chi-Huan; Wang, Hui-Chun; Chuang, Da-Wei; Wu, Ming-Jung; Wang, Sheng-Yang; Hwang, Tsong-Long; Wu, Chin-Chung; Chen, Yeh-Long; Chang, Fang-Rong; Wu, Yang-Chang [Organic and Biomolecular Chemistry, 2011, vol. 9, # 1, p. 70 - 73]
[2]Della Ca, Nicola; Motti, Elena; Mega, Antonio; Catellani, Marta [Advanced Synthesis and Catalysis, 2010, vol. 352, # 9, p. 1451 - 1454]
[3]McKillop, Alexander; Turrell, Andrew G.; Young, Derek W.; Taylor, Edward C. [Journal of the American Chemical Society, 1980, vol. 102, # 21, p. 6504 - 6512]

11
[ 4463-33-6 ]
[ 108-24-7 ]
[ 5417-20-9 ]

Yield	Reaction Conditions	Operation in experiment
70%	With PPA at 45 - 50℃; for 1.5h;

Reference： [1]Borchardt, Ronald T.; Bhatia, Pramila [Journal of Medicinal Chemistry, 1982, vol. 25, # 3, p. 263 - 271]

12
[ 91-16-7 ]
[ 77-78-1 ]
[ 4463-33-6 ]

Yield	Reaction Conditions	Operation in experiment
83%	Stage #1: 1,2-dimethoxybenzene With n-butyllithium In diethyl ether for 6h; Inert atmosphere; Reflux; Stage #2: dimethyl sulfate In diethyl ether for 16h; Inert atmosphere; Reflux; regioselective reaction;	4.1.1. 1,2-Dimethoxy-3-methyl-benzene 9 To a solution of 1,2-dimethoxy-benzene 8 (15 g, 108.6 mmol) indry ether (340 ml) was added n-BuLi (68 ml, 2.4 M, 163 mmol) at0 C. Reaction mixture was heated at reflux for 6 h; cool to roomtemperature, dimethyl sulfate (63 ml, 652 mmol) was addedslowly to the reaction mixture and heated at reflux for 16 h. Reactionmixture was diluted with ethyl acetate and washed with saturatedaq NH4Cl, water, brine, dried over Na2SO4 and evaporated toget the crude which was purified by silica gel column chromatographyand gave the pure compound 8 as a pale yellow liquid(13.7 g, 83%). 1H NMR (DMSO-d6, 400 MHz) d 6.93 (t, J = 7.8 Hz,1H), 6.84 (d, J = 7.9 Hz, 1H), 6.74 (d, J = 7.4 Hz, 1H), 3.77 (s, 3H),3.68 (s, 3H), 2.18 (s, 3H); 13C NMR (DMSO-d6, 100 MHz): d 152.2,146.7, 130.9, 123.5, 122.3, 110.4, 59.2, 55.3, 15.3; GC-MS (EI):152 m/z [M+].
80 % Chromat.	With n-butyllithium In diethyl ether; hexane

Reference： [1]Malhotra, Rajesh; Rarhi, Chhanda; Diveshkumar; Barik, Rajib; D'Cunha, Ruhee; Dhar, Pranab; Kundu, Mrinalkanti; Chattopadhyay, Subrata; Roy, Subho; Basu, Sourav; Pradeepkumar; Hajra, Saumen [Bioorganic and Medicinal Chemistry, 2016, vol. 24, # 13, p. 2887 - 2896]
[2]Halim, Haroen; Locksley, Harry D.; Memon, Janmohammed J. [Journal of the Chemical Society. Perkin transactions I, 1980, p. 2331 - 2337]

13
[ 77-78-1 ]
[ 488-17-5 ]
[ 4463-33-6 ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium hydroxide In water at 23℃; for 6h; Inert atmosphere;
83%	With potassium carbonate In acetone for 3h; Heating;

Reference： [1]Surendra, Karavadhi; Rajendar, Goreti; Corey [Journal of the American Chemical Society, 2014, vol. 136, # 2, p. 642 - 645]
[2]Borchardt, Ronald T.; Bhatia, Pramila [Journal of Medicinal Chemistry, 1982, vol. 25, # 3, p. 263 - 271]

14
[ 4463-33-6 ]
[ 2207-57-0 ]
[ 611-68-7 ]
[ 90111-36-7 ]
2,3-dimethoxy-4-methylphenol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 27% 2: 9% 3: 5% 4: 4%	With dihydrogen peroxide In formic acid; water at 40℃; for 2h;

Reference： [1]Orita, Hideo; Shimizu, Masao; Hayakawa, Takashi; Takehira, Katsuomi [Bulletin of the Chemical Society of Japan, 1989, vol. 62, # 5, p. 1652 - 1657]

15
[ 4463-33-6 ]
[ 488-17-5 ]

Yield	Reaction Conditions	Operation in experiment
94%	With 1,3-dimethyl-2-imidazolidinone; lithium diisopropyl amide In tetrahydrofuran; n-heptane; ethylbenzene at 185℃; for 12h;
	With pyridine hydrochloride Heating;

Reference： [1]Hwu, Jih Ru; Wong, Fung Fuh; Huang, Jiann-Jyh; Tsay, Shwu-Chen [Journal of Organic Chemistry, 1997, vol. 62, # 12, p. 4097 - 4104]
[2]Kurtz,A.P.; Dawson,C.R. [Journal of Medicinal Chemistry, 1971, vol. 14, p. 729 - 732]

16
[ 4463-33-6 ]
[ 18102-31-3 ]
[ 2896-67-5 ]

Reference： [1]Journal of Organic Chemistry,1997,vol. 62,p. 4097 - 4104
[2]Synlett,2004,p. 1104 - 1106
[3]European Journal of Organic Chemistry,2006,p. 752 - 758

17
[ 4463-33-6 ]
[ 201471-78-5 ]

Yield	Reaction Conditions	Operation in experiment
68%	Stage #1: 1,2-dimethoxy-3-methylbenzene With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In diethyl ether; pentane at -45 - 0℃; for 4.25h; Inert atmosphere; Stage #2: With 1,2-dibromo-1,1,2,2-tetrachloroethane In tetrahydrofuran; diethyl ether; pentane at 20℃; for 17h; Inert atmosphere; enantioselective reaction;
36%	Stage #1: 1,2-dimethoxy-3-methylbenzene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In diethyl ether; hexane at 0 - 20℃; for 2h; Stage #2: With tetrabromo-1,2-dichloro-ethane In diethyl ether; hexane at -78℃; for 0.166667h;	2 n-BuLi 1.6M in hexane (18.5 ml, 29.6 mmol) was added dropwise at 0 °C to a solution of 2,3-dimethoxytoluene (3.00 g, 19.7 mmol) and TMEDA (2.97 ml, 19.7 mmol) in anhydrous ether (50 ml) under nitrogen. After stirring at rt for 2 h, the reaction mixture was cooled to-78 °C and (CBrC12)2 (9.64 g, 29.6 mmol) was added. After stirring for 10 min, the bath was taken off and allowed to warm to rt. The reaction mixture was diluted with ether and washed with water, IN HCI x2 and brine, dried over Na2S04. The solvent was removed under vacuum and purified by flash chromatography (hexane/dichloromethane = 5/1) to afford 15 (1.62 g, 36% yield). 'H-NMR (CDC13): 82.22 (s, 3H), 3.85 (s, 3H), 3.88 (s, 3H), 6.79 (d, J= 8.3Hz, 1H), 7.16 (d, J = 8.3Hz, 1H). ¹3C-NMR (CDC13): No. 15.7,60.4, 60.6,114.6, 126.7,127.4, 132.1, 150.4, 152.5.
	With n-butyllithium; N,N,N,N,-tetramethylethylenediamine; bromine 1) Et₂O, hexane, room temperature, 2 h, 2) Et₂O, hexane, room temperature, 15 h; Yield given. Multistep reaction;

Reference： [1]Lölsberg, Wibke; Werle, Susen; Neudörfl, Jörg-Martin; Schmalz, Hans-Günther [Organic Letters, 2012, vol. 14, # 23, p. 5996 - 5999]
[2]Current Patent Assignee: UNIVERSITY OF LONDON - WO2005/123676, 2005, A1 Location in patent: Page/Page column 41-42
[3]Esteban, Gemma; Lopez-Sanchez, Miguel A.; Martinez, Ma. Eugenia; Plumet, Joaquin [Tetrahedron, 1998, vol. 54, # 1-2, p. 197 - 212]

18
[ 20657-21-0 ]
[ 4463-33-6 ]
3-(3',4'dimethoxy-2'-methylphenyl)cyclopent-1-ene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With <Mo(CO)4Br2>2 In dichloromethane for 2h; Ambient temperature;

Reference： [1]Malkov, Andrei V.; Davis, Stuart L.; Baxendale, Ian R.; Mitchell, William L.; Kocovsky, Pavel [Journal of Organic Chemistry, 1999, vol. 64, # 8, p. 2751 - 2764]

19
[ 4463-33-6 ]
8-benzyloxy-3,7-dimethoxy-2-(toluene-4-sulfonyl)-1,2,3,4-tetrahydro-isoquinoline [ No CAS ]
8-benzyloxy-3-(3,4-dimethoxy-2-methyl-phenyl)-7-methoxy-2-(toluene-4-sulfonyl)-1,2,3,4-tetrahydro-isoquinoline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With boron trifluoride diethyl etherate In dichloromethane at -78 - -30℃;

Reference： [1]Bianchi, Darío A.; Kaufman, Teodoro S. [Synlett, 2000, # 6, p. 801 - 804]

20
[ 4463-33-6 ]
[ 4755-77-5 ]
[ 293731-03-0 ]

Yield	Reaction Conditions	Operation in experiment
94%	With aluminium trichloride In dichloromethane at 20℃;
94%	With aluminium trichloride In dichloromethane at 0℃;
	With aluminum (III) chloride In dichloromethane

Reference： [1]Kaufman, Teodoro S. [Heterocycles, 2001, vol. 55, # 2, p. 323 - 330]
[2]Bianchi, Dario A.; Blanco, Nicolas E.; Carrillo, Nestor; Kaufman, Teodoro S. [Journal of Agricultural and Food Chemistry, 2004, vol. 52, # 7, p. 1923 - 1927]
[3]Connolly, Terrence J.; Matchett, Michael; McGarry, Patrick; Sukhtankar, Sunil; Zhu, Jiang [Organic Process Research and Development, 2004, vol. 8, # 4, p. 624 - 627]

21
[ 4463-33-6 ]
[ 214282-99-2 ]

Yield	Reaction Conditions	Operation in experiment
86%	Stage #1: 1,2-dimethoxy-3-methylbenzene With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In hexane at 20℃; for 13h; Stage #2: With 1,2-Diiodoethane for 2.5h;
75%	Stage #1: 1,2-dimethoxy-3-methylbenzene With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In hexane; pentane at 20℃; for 8h; Stage #2: With 1,2-Diiodoethane at 0 - 20℃; for 2h;

Reference： [1]Tenneti, Srinivasarao; Biswas, Souvagya; Cox, Glen Adam; Mans, Daniel J.; Lim, Hwan Jung; RajanBabu [Journal of the American Chemical Society, 2018, vol. 140, # 31, p. 9868 - 9881]
[2]Chow, Robert; Kocienski, Philip J.; Kuhl, Alexander; LeBrazidec, Jean-Yves; Muir, Kenneth; Fish, Paul [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2001, # 19, p. 2344 - 2355]

22
[ 4463-33-6 ]
[ 98-88-4 ]
(3,4-dimethoxy-2-methyl-phenyl)-phenyl-methanone [ No CAS ]
(3,4-dimethoxy-5-methyl-phenyl)-phenyl-methanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 75% 2: 15%	With niobium pentachloride In 1,2-dichloro-ethane at 20℃; for 1.25h;

Reference： [1]Arai, Shigeru; Sudo, Yukinori; Nishida, Atsushi [Synlett, 2004, # 6, p. 1104 - 1106]

23
[ 4463-33-6 ]
[ 124-63-0 ]
2-methoxy-3-methylphenyl methanesulfonate [ No CAS ]
2-methoxy-6-methylphenyl methanesulfonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 93% 2: 7%	Stage #1: 1,2-dimethoxy-3-methylbenzene With niobium pentachloride In 1,2-dichloro-ethane at 20℃; for 37h; Stage #2: methanesulfonyl chloride With triethylamine

Reference： [1]Arai, Shigeru; Sudo, Yukinori; Nishida, Atsushi [Synlett, 2004, # 6, p. 1104 - 1106]

24
[ 358-23-6 ]
[ 4463-33-6 ]
[ 863727-67-7 ]

Yield	Reaction Conditions	Operation in experiment
74%	Stage #1: 1,2-dimethoxy-3-methylbenzene With niobium pentachloride In 1,2-dichloro-ethane for 1h; Heating; Stage #2: trifluoromethylsulfonic anhydride With pyridine In dichloromethane at 20℃; for 1h;

Reference： [1]Sudo, Yukinori; Arai, Shigeru; Nishida, Atsushi [European Journal of Organic Chemistry, 2006, # 3, p. 752 - 758]

25
[ 91-16-7 ]
[ 74-88-4 ]
[ 4463-33-6 ]

Yield	Reaction Conditions	Operation in experiment
99%	Stage #1: 1,2-dimethoxybenzene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran at 0 - 20℃; for 3h; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran Inert atmosphere;
84%	Stage #1: 1,2-dimethoxybenzene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran; hexane at 20℃; for 3.5h; Stage #2: methyl iodide In tetrahydrofuran; hexane at -78 - 20℃; Further stages.;

Reference： [1]Movahhed, Sohajl; Westphal, Julia; Kempa, Alexander; Schumacher, Christian Eric; Sperlich, Julia; Neudörfl, Jörg-Martin; Teusch, Nicole; Hochgürtel, Matthias; Schmalz, Hans-Günther [Chemistry - A European Journal, 2021, vol. 27, # 45, p. 11574 - 11579]
[2]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

26
[ 4463-33-6 ]
[ 33513-42-7 ]
[ 75889-47-3 ]

Yield	Reaction Conditions	Operation in experiment
93%	Stage #1: 1,2-dimethoxy-3-methylbenzene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In diethyl ether at 0 - 20℃; for 16h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In diethyl ether at 20℃; for 1h; Inert atmosphere;
75%	Stage #1: 1,2-dimethoxy-3-methylbenzene With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In diethyl ether; pentane at 20℃; for 13h; Stage #2: N,N-dimethyl-formamide In diethyl ether; pentane at 20℃; for 0.5h; Further stages.;
74%	Stage #1: 1,2-dimethoxy-3-methylbenzene With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In hexane; pentane at 20℃; for 16.5h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In hexane; pentane at 0 - 20℃; Inert atmosphere;

74%	Stage #1: 1,2-dimethoxy-3-methylbenzene With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In hexane; pentane at 20℃; for 16h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In hexane; N,N-dimethyl-formamide; pentane at 0 - 20℃; for 1h; Inert atmosphere;
58%	Stage #1: 1,2-dimethoxy-3-methylbenzene With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In diethyl ether; pentane at 0 - 20℃; for 18h; Stage #2: N,N-dimethyl-formamide In diethyl ether; pentane at 0℃; for 0.5h; Stage #3: With hydrogenchloride In diethyl ether; water; pentane Cooling with ice;	1.Q To a cooled (0 °C) solution of l,2-dimethoxy-3-methylbenzene (2.05 g,13.45 mmol) and TMEDA (2.8 mL, 18.83 mmol) in diethyl ether (100 mL) was added t-butyllithium (1.7 M in pentane, 9.5 mL, 16.14 mmol). The color of the solution changed to light yellow and after a few minutes a white precipitate was observed. The suspension was stirred at room temperature for 18 h, cooled to 0 °C and dimethylformamide (2.08 mL, 26.90 mmol) was added dropwise. The precipitate disappeared and the color of the solution changed to light pink. After stirring for 0.5 h, ice was added followed by IN HCl (30 mL), the compound was extracted into ethyl acetate, dried (Na2S04) and the solvent was evaporated to obtain light brown oil. Purification by flash column chromatography (5% EtOAc/hexane) generated the title compound: yield 1.4 g (58%). 1H NMR (400 MHz, CDC13) δ (ppm): 10.34 (s, 1 H), 7.49 (d, J=8.2 Hz, 1 H), 7.01 (d, J=7.8 Hz, 1 H), 4.00 (s, 3 H), 3.86 (s, 3 H), 2.33 (s, 3 H). MS (ESI): m/z =181 (M+l, positive).

Reference： [1]Movahhed, Sohajl; Westphal, Julia; Kempa, Alexander; Schumacher, Christian Eric; Sperlich, Julia; Neudörfl, Jörg-Martin; Teusch, Nicole; Hochgürtel, Matthias; Schmalz, Hans-Günther [Chemistry - A European Journal, 2021, vol. 27, # 45, p. 11574 - 11579]
[2]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]
[3]Mans, Daniel J.; Cox, G. Adam; Rajanbabu [Journal of the American Chemical Society, 2011, vol. 133, # 15, p. 5776 - 5779]
[4]Tenneti, Srinivasarao; Biswas, Souvagya; Cox, Glen Adam; Mans, Daniel J.; Lim, Hwan Jung; RajanBabu [Journal of the American Chemical Society, 2018, vol. 140, # 31, p. 9868 - 9881]
[5]Current Patent Assignee: PFIZER INC - WO2012/33858, 2012, A2 Location in patent: Page/Page column 102

27
[ 4463-33-6 ]
5-isopropyl-1,2-dimethoxy-3,8-dimethyl-naphthalene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 9 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C 4.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 5.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 6.1: sec-BuLi / tetrahydrofuran; cyclohexane / 3 h / -78 - -10 °C 6.2: sodium acetate / [Pd(dppf)Cl₂]CH₂Cl₂ / tetrahydrofuran; cyclohexane / -10 °C 6.3: tetrahydrofuran; cyclohexane / 24 h / 85 °C 7.1: TBAF / tetrahydrofuran / 20 °C 8.1: NEt₃; DMAP / CH₂Cl₂ / 16 h / 20 °C 9.1: BF₃*OEt₂ / CH₂Cl₂ / 1 h / 20 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

28
[ 4463-33-6 ]
[ 951161-59-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃*OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C 4.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 5.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

29
[ 4463-33-6 ]
[ 951161-65-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C 4.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 5.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 6.1: sec-BuLi / tetrahydrofuran; cyclohexane / 3 h / -78 - -10 °C 6.2: sodium acetate / [Pd(dppf)Cl₂]CH₂Cl₂ / tetrahydrofuran; cyclohexane / -10 °C 6.3: tetrahydrofuran; cyclohexane / 24 h / 85 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

30
[ 4463-33-6 ]
[ 951161-66-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 7 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C 4.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 5.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 6.1: sec-BuLi / tetrahydrofuran; cyclohexane / 3 h / -78 - -10 °C 6.2: sodium acetate / [Pd(dppf)Cl₂]CH₂Cl₂ / tetrahydrofuran; cyclohexane / -10 °C 6.3: tetrahydrofuran; cyclohexane / 24 h / 85 °C 7.1: TBAF / tetrahydrofuran / 20 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

31
[ 4463-33-6 ]
[ 951161-61-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 8 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C 4.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 5.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 6.1: sec-BuLi / tetrahydrofuran; cyclohexane / 3 h / -78 - -10 °C 6.2: sodium acetate / [Pd(dppf)Cl₂]CH₂Cl₂ / tetrahydrofuran; cyclohexane / -10 °C 6.3: tetrahydrofuran; cyclohexane / 24 h / 85 °C 7.1: TBAF / tetrahydrofuran / 20 °C 8.1: NEt₃; DMAP / CH₂Cl₂ / 16 h / 20 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

32
[ 4463-33-6 ]
[ 951161-56-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃*OEt₂ / tetrahydrofuran / 3 h / 20 °C
	Multi-step reaction with 2 steps 1.1: N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium / hexane; pentane / 16.5 h / 20 °C / Inert atmosphere 1.2: 0 - 20 °C / Inert atmosphere 2.1: potassium hexamethylsilazane / tetrahydrofuran / Inert atmosphere 2.2: 16 h / Reflux; Inert atmosphere
	Multi-step reaction with 2 steps 1.1: tert.-butyl lithium; N,N,N,N,-tetramethylethylenediamine / hexane; pentane / 16 h / 20 °C / Inert atmosphere 1.2: 1 h / 0 - 20 °C / Inert atmosphere 2.1: potassium hexamethylsilazane / tetrahydrofuran / 1 h / 20 °C / Inert atmosphere 2.2: 16 h / Inert atmosphere; Reflux

	Multi-step reaction with 2 steps 1.1: tert.-butyl lithium; N,N,N,N,-tetramethylethylenediamine / hexane / 13 h / 20 °C 1.2: 2.5 h 2.1: cesium fluoride; copper(l) iodide; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / 24 h / 45 °C
	Multi-step reaction with 4 steps 1.1: tert.-butyl lithium; N,N,N,N,-tetramethylethylenediamine / hexane / 13 h / 20 °C 1.2: 2.5 h 2.1: 1-methyl-pyrrolidin-2-one / 4.5 h / 170 °C 3.1: diisobutylaluminium hydride / tetrahydrofuran; hexane / -78 - 0 °C 4.1: potassium hexamethylsilazane / tetrahydrofuran / 1 h / 20 °C / Inert atmosphere 4.2: 16 h / Inert atmosphere; Reflux

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]
[2]Mans, Daniel J.; Cox, G. Adam; Rajanbabu [Journal of the American Chemical Society, 2011, vol. 133, # 15, p. 5776 - 5779]
[3]Tenneti, Srinivasarao; Biswas, Souvagya; Cox, Glen Adam; Mans, Daniel J.; Lim, Hwan Jung; RajanBabu [Journal of the American Chemical Society, 2018, vol. 140, # 31, p. 9868 - 9881]
[4]Tenneti, Srinivasarao; Biswas, Souvagya; Cox, Glen Adam; Mans, Daniel J.; Lim, Hwan Jung; RajanBabu [Journal of the American Chemical Society, 2018, vol. 140, # 31, p. 9868 - 9881]
[5]Tenneti, Srinivasarao; Biswas, Souvagya; Cox, Glen Adam; Mans, Daniel J.; Lim, Hwan Jung; RajanBabu [Journal of the American Chemical Society, 2018, vol. 140, # 31, p. 9868 - 9881]

33
[ 4463-33-6 ]
[ 951161-58-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃*OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

34
[ 4463-33-6 ]
(S)-2-[1-(2,3-dimethoxy-4-methyl-phenyl)-ethyl]-4,4,5,5-tetramethyl-[1,3,2]-dioxaborolane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃*OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

35
[ 4463-33-6 ]
C₁₇H₂₇BO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃*OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

36
[ 4463-33-6 ]
(R)-1-(2,3-dimethoxy-4-methyl-phenyl)-ethanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃*OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C 4.1: NaOH; H₂O₂ / methanol / 0 - 20 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

37
[ 4463-33-6 ]
[ 951161-64-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃*OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C 4.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

38
[ 4463-33-6 ]
[ 135594-89-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 9 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C 4.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 5.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 6.1: sec-BuLi / tetrahydrofuran; cyclohexane / 3 h / -78 - -10 °C 6.2: sodium acetate / [Pd(dppf)Cl₂]CH₂Cl₂ / tetrahydrofuran; cyclohexane / -10 °C 6.3: tetrahydrofuran; cyclohexane / 24 h / 85 °C 7.1: TBAF / tetrahydrofuran / 20 °C 8.1: NEt₃; DMAP / CH₂Cl₂ / 16 h / 20 °C 9.1: BF₃*OEt₂ / CH₂Cl₂ / 1 h / 20 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

39
[ 4463-33-6 ]
[ 135594-87-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 9 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C 4.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 5.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 6.1: sec-BuLi / tetrahydrofuran; cyclohexane / 3 h / -78 - -10 °C 6.2: sodium acetate / [Pd(dppf)Cl₂]CH₂Cl₂ / tetrahydrofuran; cyclohexane / -10 °C 6.3: tetrahydrofuran; cyclohexane / 24 h / 85 °C 7.1: TBAF / tetrahydrofuran / 20 °C 8.1: NEt₃; DMAP / CH₂Cl₂ / 16 h / 20 °C 9.1: Me₂AlCl / benzene; hexane / 0.5 h / 7 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

40
[ 4463-33-6 ]
[ 135683-20-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 9 steps 1.1: TMEDA; t-BuLi / diethyl ether; pentane / 13 h / 20 °C 1.2: 75 percent / diethyl ether; pentane / 0.5 h / 20 °C 2.1: 92 percent / BF₃OEt₂ / tetrahydrofuran / 3 h / 20 °C 3.1: chiral phosphite ligand; catecholborane / [Ph(COD)2]BF₄ / 1,2-dimethoxy-ethane / 2.5 h / -45 °C 3.2: 1,2-dimethoxy-ethane; tetrahydrofuran / -45 - 20 °C 4.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 5.1: n-BuLi / tetrahydrofuran; hexane / -90 - 20 °C 6.1: sec-BuLi / tetrahydrofuran; cyclohexane / 3 h / -78 - -10 °C 6.2: sodium acetate / [Pd(dppf)Cl₂]CH₂Cl₂ / tetrahydrofuran; cyclohexane / -10 °C 6.3: tetrahydrofuran; cyclohexane / 24 h / 85 °C 7.1: TBAF / tetrahydrofuran / 20 °C 8.1: NEt₃; DMAP / CH₂Cl₂ / 16 h / 20 °C 9.1: Me₂AlCl / benzene; hexane / 0.5 h / 7 °C

Reference： [1]Werle, Susen; Fey, Thorsten; Neudoerfl, Joerg M.; Schmalz, Hans-Guenther [Organic Letters, 2007, vol. 9, # 18, p. 3555 - 3558]

41
[ 4463-33-6 ]
[ 899442-93-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: 47 percent / acetic acid / 16 h / 20 °C / Heating 2.1: 92 percent / 18 crown-6 / dimethylformamide / 16 h 3.1: 63 percent / NaOH / ethanol / 18 h 4.1: diisopropylamine; n-butyllithium / tetrahydrofuran / 1 h / -78 °C 4.2: 70 percent / tetrahydrofuran / 18 h / 20 °C

Reference： [1]Zuniga, Miguel A.; Dai, Jifeng; Wehunt, Mark P.; Zhou, Qibing [Chemical Research in Toxicology, 2006, vol. 19, # 6, p. 828 - 836]

42
[ 4463-33-6 ]
[ 899442-84-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: 47 percent / acetic acid / 16 h / 20 °C / Heating 2.1: 92 percent / 18 crown-6 / dimethylformamide / 16 h 3.1: 63 percent / NaOH / ethanol / 18 h 4.1: diisopropylamine; n-butyllithium / tetrahydrofuran / 1 h / -78 °C 4.2: 70 percent / tetrahydrofuran / 18 h / 20 °C 5.1: 60 percent / 4-(dimethylamino)pyridine; N,N-dicyclohexylcarbodiimide / CH₂Cl₂ / 18 h / 20 °C

Reference： [1]Zuniga, Miguel A.; Dai, Jifeng; Wehunt, Mark P.; Zhou, Qibing [Chemical Research in Toxicology, 2006, vol. 19, # 6, p. 828 - 836]

43
[ 4463-33-6 ]
4b,5,6,7,8,8a-trans-hexahydro-2,3-dimethoxy-1,4b,8,8-tetramethylphenanthrenene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 8 steps 1.1: 47 percent / acetic acid / 16 h / 20 °C / Heating 2.1: 92 percent / 18 crown-6 / dimethylformamide / 16 h 3.1: 63 percent / NaOH / ethanol / 18 h 4.1: diisopropylamine; n-butyllithium / tetrahydrofuran / 1 h / -78 °C 4.2: 70 percent / tetrahydrofuran / 18 h / 20 °C 5.1: 60 percent / 4-(dimethylamino)pyridine; N,N-dicyclohexylcarbodiimide / CH₂Cl₂ / 18 h / 20 °C 6.1: 62 percent / BF₃*Et₂O / nitromethane / 4 h / -15 °C 7.1: 73 percent / NaOH / ethanol / 3 h / Heating 8.1: 53 percent / lead(IV)acetate; copper(II)acetate / quinoline / 3 h / 140 °C

Reference： [1]Zuniga, Miguel A.; Dai, Jifeng; Wehunt, Mark P.; Zhou, Qibing [Chemical Research in Toxicology, 2006, vol. 19, # 6, p. 828 - 836]

44
[ 4463-33-6 ]
6,7-dimethoxy-1,1,4a,8-tetramethyl-1,2,3,4,4a,9,10,10a-octahydro-phenanthrene-9-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 7 steps 1.1: 47 percent / acetic acid / 16 h / 20 °C / Heating 2.1: 92 percent / 18 crown-6 / dimethylformamide / 16 h 3.1: 63 percent / NaOH / ethanol / 18 h 4.1: diisopropylamine; n-butyllithium / tetrahydrofuran / 1 h / -78 °C 4.2: 70 percent / tetrahydrofuran / 18 h / 20 °C 5.1: 60 percent / 4-(dimethylamino)pyridine; N,N-dicyclohexylcarbodiimide / CH₂Cl₂ / 18 h / 20 °C 6.1: 62 percent / BF₃*Et₂O / nitromethane / 4 h / -15 °C 7.1: 73 percent / NaOH / ethanol / 3 h / Heating

Reference： [1]Zuniga, Miguel A.; Dai, Jifeng; Wehunt, Mark P.; Zhou, Qibing [Chemical Research in Toxicology, 2006, vol. 19, # 6, p. 828 - 836]

45
[ 4463-33-6 ]
6,7-dimethoxy-1,1,4a,8-tetramethyl-1,2,3,4,4a,9,10,10a-octahydro-phenanthrene-9-carboxylic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1.1: 47 percent / acetic acid / 16 h / 20 °C / Heating 2.1: 92 percent / 18 crown-6 / dimethylformamide / 16 h 3.1: 63 percent / NaOH / ethanol / 18 h 4.1: diisopropylamine; n-butyllithium / tetrahydrofuran / 1 h / -78 °C 4.2: 70 percent / tetrahydrofuran / 18 h / 20 °C 5.1: 60 percent / 4-(dimethylamino)pyridine; N,N-dicyclohexylcarbodiimide / CH₂Cl₂ / 18 h / 20 °C 6.1: 62 percent / BF₃*Et₂O / nitromethane / 4 h / -15 °C

Reference： [1]Zuniga, Miguel A.; Dai, Jifeng; Wehunt, Mark P.; Zhou, Qibing [Chemical Research in Toxicology, 2006, vol. 19, # 6, p. 828 - 836]

46
[ 4463-33-6 ]
[ 6834-56-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 47 percent / acetic acid / 16 h / 20 °C / Heating 2: 92 percent / 18 crown-6 / dimethylformamide / 16 h 3: 63 percent / NaOH / ethanol / 18 h

Reference： [1]Zuniga, Miguel A.; Dai, Jifeng; Wehunt, Mark P.; Zhou, Qibing [Chemical Research in Toxicology, 2006, vol. 19, # 6, p. 828 - 836]

47
[ 4463-33-6 ]
[ 7537-06-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 47 percent / acetic acid / 16 h / 20 °C / Heating 2: 92 percent / 18 crown-6 / dimethylformamide / 16 h

Reference： [1]Zuniga, Miguel A.; Dai, Jifeng; Wehunt, Mark P.; Zhou, Qibing [Chemical Research in Toxicology, 2006, vol. 19, # 6, p. 828 - 836]

48
[ 4463-33-6 ]
[ 100-84-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: NbCl₅ / 1,2-dichloro-ethane / 1 h / Heating 1.2: 74 percent / pyridine / CH₂Cl₂ / 1 h / 20 °C 2.1: 46 percent / dppp; Bu₃N; HCOOH / PdCl₂(PPh₃)2 / dimethylformamide / 8 h / 80 °C

Reference： [1]Sudo, Yukinori; Arai, Shigeru; Nishida, Atsushi [European Journal of Organic Chemistry, 2006, # 3, p. 752 - 758]

49
[ 4463-33-6 ]
(R)-(-)-carquinostatin A [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 11 steps 1.1: 96 percent / NBS / acetonitrile / 20 h / 25 °C 2.1: 80 percent / n-BuLi / tetrahydrofuran / -78 °C 3.1: tetrahydrofuran / -78 - 25 °C 4.1: 100 percent / Et₃N; DMAP / CH₂Cl₂ / 20 h / 25 °C 5.1: 87 percent / HNO₃ / acetic anhydride; acetic acid / 4 h / 0 °C 6.1: 86 percent / H₂ / Pd/C / methanol / 25 °C 7.1: air / acetonitrile / 216 h / 25 °C 7.2: Me₃NO*2H₂O / acetone / 4 h / 56 °C 7.3: 87 percent / Pd/C / o-xylene; various solvent(s) / 4 h / Heating 8.1: 100 percent / NBS; HBr / acetonitrile / 1 h / 25 °C 9.1: tetracarbonylnickel / benzene / 1.5 h / 60 °C 9.2: 94 percent / dimethylformamide / 15 h / 65 °C 10.1: 98 percent / LiAlH₄ / diethyl ether / 0.75 h / 25 °C 11.1: 70 percent / CoF₃ / dioxane; H₂O / 1 h / 25 °C

Reference： [1]Knölker, Hans-Joachim; Baum, Elke; Reddy, Kethiri R. [Tetrahedron Letters, 2000, vol. 41, # 8, p. 1171 - 1174]

50
[ 4463-33-6 ]
[ 201471-98-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: TiCl₄ / CH₂Cl₂ 2: H₂, AcOH / Pd/C 3: 85 percent / PPA
	Multi-step reaction with 4 steps 1: 88 percent / Br₂ / CCl₄ / 2.5 h / Ambient temperature 2: 1) 9-BBN, 2) CH₃ONa / 2) dichloro<1,1'-bis(diphenylphosphino)ferrocene>palladium(II) / 1) THF, room temperature, 3 h, 2) THF, reflux, 4.5 h 3: 82 percent / KOH / ethanol / 2.5 h / Ambient temperature 4: 95 percent / polyphosphonate ester / CHCl₃; diethyl ether / 6.5 h / Ambient temperature

Reference： [1]He, Wei; Huang, Fu-Chih; Gavai, Ashvin; Chan, Wan K.; Amato, George; Yu, Kin-Tak; Zilberstein, Asher [Bioorganic and Medicinal Chemistry Letters, 1998, vol. 8, # 24, p. 3659 - 3664]
[2]Esteban, Gemma; Lopez-Sanchez, Miguel A.; Martinez, Ma. Eugenia; Plumet, Joaquin [Tetrahedron, 1998, vol. 54, # 1-2, p. 197 - 212]

51
[ 4463-33-6 ]
[ 201471-80-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: TiCl₄ / CH₂Cl₂ 2: H₂, AcOH / Pd/C
	Multi-step reaction with 2 steps 1: 88 percent / Br₂ / CCl₄ / 2.5 h / Ambient temperature 2: 1) 9-BBN, 2) CH₃ONa / 2) dichloro<1,1'-bis(diphenylphosphino)ferrocene>palladium(II) / 1) THF, room temperature, 3 h, 2) THF, reflux, 4.5 h

Reference： [1]He, Wei; Huang, Fu-Chih; Gavai, Ashvin; Chan, Wan K.; Amato, George; Yu, Kin-Tak; Zilberstein, Asher [Bioorganic and Medicinal Chemistry Letters, 1998, vol. 8, # 24, p. 3659 - 3664]
[2]Esteban, Gemma; Lopez-Sanchez, Miguel A.; Martinez, Ma. Eugenia; Plumet, Joaquin [Tetrahedron, 1998, vol. 54, # 1-2, p. 197 - 212]

52
[ 4463-33-6 ]
[ 74866-19-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 63 percent / N-bromosuccinimide / CCl₄ / 12 h / Heating 2: 93 percent / thallium(III) trifluoroacetate / trifluoroacetic acid / Ambient temperature

Reference： [1]McKillop, Alexander; Turrell, Andrew G.; Young, Derek W.; Taylor, Edward C. [Journal of the American Chemical Society, 1980, vol. 102, # 21, p. 6504 - 6512]

53
[ 4463-33-6 ]
[ 19965-36-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 57 percent / iodine, mercuric oxide / aq. ethanol / 0.58 h / 70 °C 2: 83 percent / thallium(III) trifluoroacetate / trifluoroacetic acid / Ambient temperature

Reference： [1]McKillop, Alexander; Turrell, Andrew G.; Young, Derek W.; Taylor, Edward C. [Journal of the American Chemical Society, 1980, vol. 102, # 21, p. 6504 - 6512]

54
[ 4463-33-6 ]
[ 86232-53-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 82 percent / 90percent HNO₃ / 0.17 h / -10 °C 2: 95 percent / H₂ / 10percent palladized charcoal / methanol / 586 Torr / Ambient temperature
	Multi-step reaction with 2 steps 1: nitric acid; glacial acetic acid / Reinigung durch Reduktion zu 2.5-Dioxy-3-methoxy-toluol und Oxydation mit Ferrichlorid 2: diethyl ether; zinc; glacial acetic acid
	Multi-step reaction with 2 steps 1: glacial acetic acid; nitric acid 2: diethyl ether; zinc; glacial acetic acid

Reference： [1]Sanchez, Ignacio H.; Larraza, Maria Isabel; Basurto, Fernando; Yanez, Ricardo; Avila, Salvador; et al. [Tetrahedron, 1985, vol. 41, # 12, p. 2355 - 2359]
[2]Majima; Okazaki [Chemische Berichte, 1916, vol. 49, p. 1490]
[3]Majima; Okazaki [Chemische Berichte, 1916, vol. 49, p. 1490]

55
[ 4463-33-6 ]
[ 100668-75-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 82 percent / 90percent HNO₃ / 0.17 h / -10 °C 2: 95 percent / H₂ / 10percent palladized charcoal / methanol / 586 Torr / Ambient temperature 3: 70 percent / NaNO₂ / aq. H₂SO₄ / 0.25 h / Ambient temperature; 50 deg C, 30 min
	Multi-step reaction with 2 steps 1: (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 3,4,7,8-Tetramethyl-o-phenanthrolin / tetrahydrofuran / 48 h / 80 °C / Sealed tube; Glovebox; Inert atmosphere 2: 4-methylmorpholine N-oxide / 3 h / 23 - 80 °C / Sealed tube; Inert atmosphere

Reference： [1]Sanchez, Ignacio H.; Larraza, Maria Isabel; Basurto, Fernando; Yanez, Ricardo; Avila, Salvador; et al. [Tetrahedron, 1985, vol. 41, # 12, p. 2355 - 2359]
[2]Current Patent Assignee: CALIFORNIA INSTITUTE OF TECHNOLOGY - WO2019/18539, 2019, A1

56
[ 148-53-8 ]
[ 4463-33-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: zinc; hydrochloric acid 2: alcoholic KOH-solution / 110 - 120 °C / im Rohr
	Multi-step reaction with 2 steps 1: KOH 2: H₂, aq. H₂SO₄ / Pd-C / ethyl acetate

Reference： [1]Majima; Okazaki [Chemische Berichte, 1916, vol. 49, p. 1490]
[2]Kurtz,A.P.; Dawson,C.R. [Journal of Medicinal Chemistry, 1971, vol. 14, p. 729 - 732]

57
[ 4463-33-6 ]
[ 107-07-3 ]
2,3-Dimethoxy-6-chlorotoluene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	In acetic acid	33.A A. A. 2,3-Dimethoxy-6-chlorotoluene To a mixture of 25 g (0.16 mmol) of 1-methyl-2,3-dimethoxybenzene in 25 mL of acetic acid, was slowly added 26.4 g (0.33 mmol) of 1-chloromethylmethylether. The resultant reaction mixture was reacted overnight at 30° C. and then diluted with cold water, resulting in the formation of a precipitate. This precipitate was purified by recrystallization from hot hexanes and then reduced to dryness under reduced pressure to provide 20.3 g of a white solid (m.p. 69-70° C.). Yield: 62%. 1 H NMR (CDCl3): δ 7.01 (d, J=6.1 Hz, 1H), 6.75 (d, 4.62 (s, 2H), 3.85 (s, 3H), 3.76 (s, 3H), 2.37 (s, 3H). Analysis for C10 H13 O2 Cl: Calcd: C, 59.93; H, 6.54; Found: C, 59.87; H, 6.43.
62%	In acetic acid	33.A A. A. 2,3-Dimethoxy-6-chlorotoluene To a mixture of 25 g (0.16 mmol) of 1-methyl-2,3-dimethoxybenzene in 25 mL of acetic acid, was slowly added 26.4 g (0.33 mmol) of 1-chloromethylmethylether. The resultant reaction mixture was reacted overnight at 30° C. and then diluted with cold water, resulting in the formation of a precipitate. This precipitate was purified by recrystallization from hot hexanes and then reduced to dryness under reduced pressure to provide 20.3 g of a white solid (m.p. 69°-70° C.). Yield: 62%. 1 H NMR (CDCl3): δ7.01 (d, J=6.1 Hz, 1H), 6.75 (d, 4.62 (s, 2H), 3.85 (s, 3H), 3.76 (s, 3H), 2.37 (s, 3H). Analysis for C10 H13 O2 Cl: Calcd: C, 59.93; H, 6.54; Found: C, 59.87; H, 6.43.

Reference： [1]Current Patent Assignee: PFIZER INC - US5952343, 1999, A
[2]Current Patent Assignee: PFIZER INC - US5484926, 1996, A

58
[ 4463-33-6 ]
[ 98-88-4 ]
[ 97-30-3 ]
[ 6748-91-0 ]

Yield	Reaction Conditions	Operation in experiment
	With toluene-4-sulfonic acid In pyridine; acetonitrile	16 Step (A)--Preparation of Methyl 4,6-O-Benzylidene-2,3-di-O-benzoyl-α-D-glucopyranoside (compound 65) Step (A)--Preparation of Methyl 4,6-O-Benzylidene-2,3-di-O-benzoyl-α-D-glucopyranoside (compound 65) To a mixture of 25 g (0.13 mmol) of methyl-α-D-glucopyranoside (64) (commercially available from Aldrich Chemical Co., Milwaukee, Wis., USA) in 750 mL of acetonitrile was added αα-dimethoxytoluene (20 mL) and p-toluenesulfonic acid (600 mg). The resulting mixture was stirred at room temperature for 20 hours and then neutralized with triethylamine and evaporated. The residue was dissolved in pyridine (200 mL) and cooled in an ice bath. Benzoyl chloride (5 eq) was then added and the mixture was stirred overnight at room temperature. After standard work-up procedures, compound 65 (44.2 g, 70%) was crystallized from a mixture of ethyl acetate and ether.

Reference： [1]Current Patent Assignee: LIGAND PHARMACEUTICALS INC - US5874411, 1999, A

59
[ 4463-33-6 ]
[ 6192-52-5 ]
[ 72599-27-0 ]
1,5-(Butylimino)-1,5-dideoxy-4R, 6-0-(phenylmethylene)-D-glucitol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In <i>N</i>-methyl-acetamide	23 1,5-(Butylimino)-1,5-dideoxy-4R, 6-0-(phenylmethylene)-D-glucitol STR27 Example 23 1,5-(Butylimino)-1,5-dideoxy-4R, 6-0-(phenylmethylene)-D-glucitol STR27 p-Toluenesulfonic acid monohydrate (10.4 g, 0.055 mole) was added to a solution of dimethoxytoluene (20.8 g, 0.137 mole) in 150 ml of dimethylformamide. After stirring for 3.5 hrs, 1,5-(butylimino)-1,5-dideoxy-D-glucitol (10.0 g, 0.046 mole) was added and the solution was stirred at room temperature for 18 days. The reaction was concentrated on a rotary evaporator. The residue was passed through a column containing Amberlite IRA-400 ion exchange resin with methanol. The eluant was concentrated to a brown oil. The title compound was purified by silica gel chromatography and crystallized from ethyl acetate-hexane (DSC 118° C.). The structure assignment was supported by NMR, infrared spectra and elemental analysis. Analysis calcd. for C17 H25 NO4: C, 66.43; H, 8.20; N 4.56. Found: C, 66.38; H, 8.20; N, 4.52.
	In <i>N</i>-methyl-acetamide	23 1,5-(Butylimino)-1,5-dideoxy-4R,6-O-(phenylmethylene)-D-glucitol EXAMPLE 23 STR24 1,5-(Butylimino)-1,5-dideoxy-4R,6-O-(phenylmethylene)-D-glucitol p-Toluenesulfonic acid monohydrate (10.4 g, 0.055 mole) was added to a solution of dimethoxytoluene (20.8 g, 0.137 mole) in 150 ml of dimethylformamide. After stirring for 3.5 hrs, 1,5-(butylimino)-1,5-dideoxy-D-glucitol (10.0 g, 0.046 mole) was added and the solution was stirred at room temperature for 18 days. The reaction was concentrated on a rotary evaporator. The residue was passed through a column containing Amberlite IRA-400 ion exchange resin with methanol. The eluant was concentrated to a brown oil. The title compound was purified by silica gel chromatography and crystallized from ethyl acetate-hexane (DSC 118° C.). The structure assignment was supported by NMR, infrared spectra and elemental analysis. Analysis calcd. for C17 H25 NO4: C, 66.43; H, 8.20; N 4.56. Found: C, 66.38; H, 8.20; N, 4.52.
	In <i>N</i>-methyl-acetamide	23 1,5-(Butylimino)-1,5-dideoxy-4R,6-O-(phenylmethylene)-D-glucitol EXAMPLE 23 STR23 1,5-(Butylimino)-1,5-dideoxy-4R,6-O-(phenylmethylene)-D-glucitol p-Toluenesulfonic acid monohydrate (10.4 g, 0.055 mole) was added to a solution of dimethoxytoluene (20.8 g, 0.137 mole) in 150 ml of dimethylformamide. After stirring for 3.5 hrs, 1,5-(butylimino)-1,5-dideoxy-D-glucitol (10.0 g, 0.046 mole) was added and the solution was stirred at room temperature for 18 days. The reaction was concentrated on a rotary evaporator. The residue was passed through a column containing Amberlite IRA-400 ion exchange resin with methanol. The eluant was concentrated to a brown oil. The title compound was purified by silica gel chromatography and crystallized from ethyl acetate-hexane (DSC 118° C.). The structure assignment was supported by NMR, infrared spectra and elemental analysis. Analysis calcd. for C17 H25 NO4: C, 66.43; H, 8.20; N, 4.56. Found: C, 66.38; H, 8.20; N, 4.52.

Reference： [1]Current Patent Assignee: PFIZER INC - US5622972, 1997, A
[2]Current Patent Assignee: PFIZER INC - US5003072, 1991, A
[3]Current Patent Assignee: PFIZER INC - US5310745, 1994, A Current Patent Assignee: PFIZER INC - US5144037, 1992, A

60
[ 79-41-4 ]
[ 4463-33-6 ]
[ 1151863-67-0 ]

Yield	Reaction Conditions	Operation in experiment
76%	With PPA at 70℃; for 3h; Inert atmosphere;
	With polyphosphoric acid

Reference： [1]London, Gábor; Carroll, Gregory T.; Fernández Landaluce, Tatiana; Pollard, Michael M.; Rudolf, Petra; Feringa, Ben L. [Chemical Communications, 2009, # 13, p. 1712 - 1714]
[2]Costil, Romain; Crespi, Stefano; Feringa, Ben L.; Léonard, Jérémie; Olivucci, Massimo; Pfeifer, Lukas; Pierron, Robin; Pooler, Daisy R. S. [Chemical Science, 2021, vol. 12, # 21, p. 7486 - 7497]

61
[ 74866-17-4 ]
[ 4463-33-6 ]

Reference： [1]Tetrahedron Letters,2009,vol. 50,p. 3780 - 3782

62
[ 4463-33-6 ]
[ 1284222-92-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 23 steps 1.1: N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium / hexane; pentane / 16.5 h / 20 °C / Inert atmosphere 1.2: 0 - 20 °C / Inert atmosphere 2.1: potassium hexamethylsilazane / tetrahydrofuran / Inert atmosphere 2.2: 16 h / Reflux; Inert atmosphere 3.1: bi(allylnickel bromide); (R)-2,2'-binaphthoyl-benzyl-(S)-[1-(1-naphthylethyl)]aminoylphosphine; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate / dichloromethane / 2 h / -80 °C / 760.05 Torr / Inert atmosphere 4.1: 9-borabicyclo[3.3.1]nonane dimer / tetrahydrofuran / 2 h / 20 °C / Inert atmosphere 4.2: 0 - 20 °C / Inert atmosphere 5.1: 1H-imidazole; iodine; triphenylphosphine / tetrahydrofuran / 0 - 20 °C / Inert atmosphere 6.1: dimethyl sulfoxide / 2 h / 60 °C / Inert atmosphere 7.1: water; sodium hydroxide / methanol / 16 h / Reflux 8.1: oxalyl dichloride / dichloromethane / 0 - 20 °C / Inert atmosphere 9.1: aluminum (III) chloride / dichloromethane / 0 - 25 °C / Inert atmosphere 10.1: potassium hexamethylsilazane / tetrahydrofuran / 20 °C / Inert atmosphere 10.2: 1.5 h / 20 °C / Inert atmosphere 11.1: tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; triphenyl-arsane; lithium chloride / tetrahydrofuran / 16 h / 20 °C / Inert atmosphere 12.1: bi(allylnickel bromide); sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate; (3,5-dioxa-4-phospha-cyclohepta[2,1-<i>a</i>;3,4-<i>a</i>']dinaphthalen-4-yl)-bis-(1-phenyl-ethyl)-amine / dichloromethane / 0 - 4 °C / 760.05 Torr 13.1: 9-borabicyclo[3.3.1]nonane dimer / tetrahydrofuran / 2 h / 20 °C / Inert atmosphere 13.2: 0 - 20 °C / Inert atmosphere 14.1: ammonia; lithium / tetrahydrofuran; mineral oil / 0.25 h / -78 °C 15.1: oxalyl dichloride; dimethyl sulfoxide / dichloromethane / 0.75 h / -78 °C / Inert atmosphere 15.2: 0.25 h / Inert atmosphere 16.1: sodium dihydrogenphosphate; sodium chlorite; 2,3-Dimethyl-2-butene / tetrahydrofuran; water; <i>tert</i>-butyl alcohol / 1 h 17.1: oxalyl dichloride / dichloromethane / 0 - 20 °C / Inert atmosphere 18.1: aluminum (III) chloride / dichloromethane / 0 - 20 °C / Inert atmosphere 19.1: sodium tetrahydroborate / ethanol / 3.5 h / 20 °C 20.1: camphor-10-sulfonic acid / dichloromethane / 0.75 h / 20 °C 21.1: bi(allylnickel bromide); sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate; (3,5-dioxa-4-phospha-cyclohepta[2,1-<i>a</i>;3,4-<i>a</i>']dinaphthalen-4-yl)-bis-(1-phenyl-ethyl)-amine / dichloromethane / 2.5 h / 20 °C / 760.05 Torr 22.1: ozone / dichloromethane / -78 °C 22.2: -78 - 20 °C 23.1: potassium hexamethylsilazane / tetrahydrofuran / 2 h / 20 °C / Inert atmosphere 23.2: 0 - 20 °C / Inert atmosphere
	Multi-step reaction with 23 steps 1.1: N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium / hexane; pentane / 16.5 h / 20 °C / Inert atmosphere 1.2: 0 - 20 °C / Inert atmosphere 2.1: potassium hexamethylsilazane / tetrahydrofuran / Inert atmosphere 2.2: 16 h / Reflux; Inert atmosphere 3.1: bi(allylnickel bromide); (R)-2,2'-binaphthoyl-benzyl-(S)-[1-(1-naphthylethyl)]aminoylphosphine; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate / dichloromethane / 2 h / -80 °C / 760.05 Torr / Inert atmosphere 4.1: 9-borabicyclo[3.3.1]nonane dimer / tetrahydrofuran / 2 h / 20 °C / Inert atmosphere 4.2: 0 - 20 °C / Inert atmosphere 5.1: 1H-imidazole; iodine; triphenylphosphine / tetrahydrofuran / 0 - 20 °C / Inert atmosphere 6.1: dimethyl sulfoxide / 2 h / 60 °C / Inert atmosphere 7.1: water; sodium hydroxide / methanol / 16 h / Reflux 8.1: oxalyl dichloride / dichloromethane / 0 - 20 °C / Inert atmosphere 9.1: aluminum (III) chloride / dichloromethane / 0 - 25 °C / Inert atmosphere 10.1: potassium hexamethylsilazane / tetrahydrofuran / 20 °C / Inert atmosphere 10.2: 1.5 h / 20 °C / Inert atmosphere 11.1: tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; triphenyl-arsane; lithium chloride / tetrahydrofuran / 16 h / 20 °C / Inert atmosphere 12.1: bi(allylnickel bromide); sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate; (3,5-dioxa-4-phospha-cyclohepta[2,1-<i>a</i>;3,4-<i>a</i>']dinaphthalen-4-yl)-bis-(1-phenyl-ethyl)-amine / dichloromethane / 0 - 4 °C / 760.05 Torr 13.1: 9-borabicyclo[3.3.1]nonane dimer / tetrahydrofuran / 2 h / 20 °C / Inert atmosphere 13.2: 0 - 20 °C / Inert atmosphere 14.1: palladium on carbon; hydrogen 15.1: oxalyl dichloride; dimethyl sulfoxide / dichloromethane / 0.75 h / -78 °C / Inert atmosphere 15.2: 0.25 h / Inert atmosphere 16.1: sodium dihydrogenphosphate; sodium chlorite; 2,3-Dimethyl-2-butene / tetrahydrofuran; water; <i>tert</i>-butyl alcohol / 1 h 17.1: oxalyl dichloride / dichloromethane / 0 - 20 °C / Inert atmosphere 18.1: aluminum (III) chloride / dichloromethane / 0 - 20 °C / Inert atmosphere 19.1: sodium tetrahydroborate / ethanol / 3.5 h / 20 °C 20.1: camphor-10-sulfonic acid / dichloromethane / 0.75 h / 20 °C 21.1: bi(allylnickel bromide); sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate; (3,5-dioxa-4-phospha-cyclohepta[2,1-<i>a</i>;3,4-<i>a</i>']dinaphthalen-4-yl)-bis-(1-phenyl-ethyl)-amine / dichloromethane / 2.5 h / 20 °C / 760.05 Torr 22.1: ozone / dichloromethane / -78 °C 22.2: -78 - 20 °C 23.1: potassium hexamethylsilazane / tetrahydrofuran / 2 h / 20 °C / Inert atmosphere 23.2: 0 - 20 °C / Inert atmosphere
	Multi-step reaction with 8 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: o-tetrachloroquinone / acetonitrile / 48 h / 20 °C / Inert atmosphere

Multi-step reaction with 9 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: dihydrogen peroxide; diphenyl diselenide; magnesium sulfate / water; dichloromethane / 6 h / 20 °C / Inert atmosphere 8.2: 20 h / 0 - 20 °C / Inert atmosphere 9.1: methanesulfonic acid / dichloromethane / 12 h / -78 - -40 °C / Inert atmosphere

Reference： [1]Mans, Daniel J.; Cox, G. Adam; Rajanbabu [Journal of the American Chemical Society, 2011, vol. 133, # 15, p. 5776 - 5779]
[2]Mans, Daniel J.; Cox, G. Adam; Rajanbabu [Journal of the American Chemical Society, 2011, vol. 133, # 15, p. 5776 - 5779]
[3]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]
[4]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

63
[ 1768-37-2 ]
[ 4463-33-6 ]
[ 1293991-80-6 ]

Yield	Reaction Conditions	Operation in experiment
	With ammonium chloride In dichloromethane; cyclohexane; ethyl acetate	1.1 1) 1) Synthesis of N-isopropyl-2,4-dimethoxy-3-methyl-benzamide (IX) 3.04 g (20 mmol, 1 eq.) of dimethoxytoluene and 2.80 g (21 mmol, 1.05 eq.) of AlCl3 are dissolved in 20 mL of CH2Cl2 in a dried round-bottomed flask under argon. 2.36 mL (25 mmol, 1.25 eq.) of isopropyl cyanate are then added to the reaction medium at room temperature. After 10 hours, the reaction is hydrolyzed at 0° C. by adding saturated NH4Cl solution. After extraction with CH2Cl2, the organic phase is washed with 1N HCl solution and then with saturated NaHCO3 solution. The organic phase is then dried with MgSO4, filtered and concentrated under vacuum. After purification by chromatography on silica using a cyclohexane/ethyl acetate mixture (8:2), 4.50 g (95%) of amide (IX) are obtained.

Reference： [1]Current Patent Assignee: UNIVERSITY OF ROUEN NORMANDIE; MACQUARIE UNIVERSITY; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; NATIONAL INSTITUTE OF APPLIED SCIENCES - US2012/214194, 2012, A1

64
[ 4463-33-6 ]
[ 94-36-0 ]
[ 1431371-05-9 ]

Yield	Reaction Conditions	Operation in experiment
53%	With tris(bipyridine)ruthenium(II) dichloride hexahydrate; sodium hydrogencarbonate In acetonitrile at 20℃; for 60h; Inert atmosphere; Irradiation; regioselective reaction;

Reference： [1]Rao, Honghua; Wang, Ping; Li, Chao-Jun [European Journal of Organic Chemistry, 2012, # 33, p. 6503 - 6507]

65
lignin, softwood Kraft black liquor [ No CAS ]
[ 95-87-4 ]
[ 6380-23-0 ]
[ 106-44-5 ]
[ 620-17-7 ]
[ 93-51-6 ]
[ 2785-87-7 ]
[ 4463-33-6 ]
[ 3209-13-0 ]
[ 2896-67-5 ]
[ 7786-61-0 ]
[ 2785-89-9 ]
[ 24599-58-4 ]
[ 5932-68-3 ]
[ 2503-46-0 ]
[ 14059-92-8 ]
[ 121-33-5 ]
[ 95-48-7 ]
[ 90-05-1 ]
[ 498-02-2 ]
[ 108-95-2 ]

Reference： [1]Green Chemistry,2013,vol. 15,p. 2904 - 2912

66
[ 50-00-0 ]
[ 4463-33-6 ]
[ 21831-10-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With hydrogen bromide; acetic acid In tetrachloromethane at 0℃; for 0.5h; Inert atmosphere;

Reference： [1]Surendra, Karavadhi; Rajendar, Goreti; Corey [Journal of the American Chemical Society, 2014, vol. 136, # 2, p. 642 - 645]

67
[ 4463-33-6 ]
[ 1632142-54-1 ]

Yield	Reaction Conditions	Operation in experiment
31%	Stage #1: 1,2-dimethoxy-3-methylbenzene With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In hexane; pentane at 20℃; for 3h; Stage #2: With Triisopropyl borate In hexane; pentane at -78 - 20℃; for 1h;	To a stirred solution of 2,3-dimethoxy toluene (3.0 mL, 20.2 mmol) in hexane (34.8 mL) and TMEDA (0.70 mL, 4.64 mmol) was added dropwise 1.54 M solution of tBuLi in pentane (13.1 mL, 20.2 mmol) at rt. After stirring was continued for 3 h at the same temperature, B(OiPr)3 (4.66 mL. 20.2 mmol) was added dropwise to this reaction mixture at 78°C, and further stirring was continued for 1 h at rt. The reaction mixture was quenched with water, and extracted with AcOEt. The residue upon workup was chromatographed on silica gel with hexane-AcOEt (90:10 v/v ) and recrystallized from hexane-AcOEt to give arylboronic acid 6 (1.21 g, 31%) as colorless crystals. Mp 87.6-89.5°C (recrystallized from AcOEt/hexane); IR (KBr) 3421, 2938, 1605, 1460, 1410, 1336, 1266, 1218, 1034, 1013 cm-1; 1H-NMR (400 MHz, CDCl3) 2.30 (3H, s), 3.81 (3H, s), 3.97 (3H, s), 5.87 (2H, s), 6.98 (1H, d, J = 7.6 Hz), 7.44 (1H, d, J = 7.6 Hz); 13C-NMR (100 MHz, CDCl3) 16.0 (CH3), 59.9 (CH3), 61.1 (CH3), 126.6 (CH), 130.7 (CH), 136.7 (Cq), 150.3 (Cq), 158.2 (Cq); HRMS(ESI) m/z calcd for C9H14O4B [M+H]+ 197.0985, found 197.0983.
	Multi-step reaction with 2 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere

Reference： [1]Yoshida, Masahiro; Kasai, Tomoyo; Mizuguchi, Tomotaka; Namba, Kosuke [Synlett, 2014, vol. 25, # 8, p. 1160 - 1162]
[2]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

68
[ 4463-33-6 ]
[ 30301-37-2 ]
C₁₉H₂₈O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: 1,2-dimethoxy-3-methylbenzene With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 1h; Stage #2: C₁₀H₁₇BrO In tetrahydrofuran; hexane at 0℃;

Reference： [1]Song, Liqiang; Zhu, Guili; Liu, Yongjiang; Liu, Bo; Qin, Song [Journal of the American Chemical Society, 2015, vol. 137, # 42, p. 13706 - 13714]

69
[ 4463-33-6 ]
[ 6880-91-7 ]

Reference： [1]Bioorganic and Medicinal Chemistry,2016,vol. 24,p. 2887 - 2896

70
[ 4463-33-6 ]
[ 73183-34-3 ]
3,4-dimethoxy-5-methylphenylboronic acid pinacol ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	Stage #1: bis(pinacol)diborane With 1,10-Phenanthroline; chloro(1,5-cyclooctadiene)iridium(I) dimer at 20℃; for 1h; Inert atmosphere; Stage #2: 1,2-dimethoxy-3-methylbenzene at 120℃; for 7h;	3 Example 3 Under nitrogen protection,Add to a 25 mL two-necked flask(1,5-cyclooctadiene iridium (I) dimer chloride (20 mg, 0.03 mmol),1,10-Phenanthroline (16 mg, 0.06 mmol),Diboronic acid pinacol ester (2.35 g, 9.26 mmol),After adding 15mLCyclopentyl methyl ether,Stir at room temperature for 1 h,Reaction system turns dark green, then join2,3-Dimethoxytoluene (1.88 g, 12.35 mmol),The temperature was raised to 120 ° C and refluxed for 7h. After the reaction is complete, concentrate and spin dry.Separation on silica gel column3,4-Dimethoxy-5-methylphenylboronic acid pinacol ester(2.33g, 68%).
	With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 3,4,7,8-Tetramethyl-o-phenanthrolin In tetrahydrofuran at 80℃; for 48h; Sealed tube; Glovebox; Inert atmosphere;	2 3,4-Dimethoxy-5-methylphenyl isopropylcarbamate (S4). In a nitrogen-filled glovebox, [Ir(cod)OMe]2 (22.3 mg, 0.034 mmol, 0.005 equiv) and 3,4,7,8-tetramethyl- 1,10-phenanthroline (15.9 mg, 0.067 mmol, 0.01 equiv) were dissolved in 5 mL THF and stirred 30 min. In the meantime, 2,3-dimethoxytoluene (1.00 mL, 6.73 mmol, 1 equiv) and B2Pin2 (1.28 g, 5.05 mmol, 0.75 equiv) were weighed into a 20 mL sealable microwave vial (also in the glovebox) with a teflon-coated stir bar and 5 mL THF was added. Upon complete dissolution, the catalyst solution was transferred to the microwave vial, which was sealed prior to removing from the glovebox. The vial was then placed in a preheated 80 °C oil bath and stirred 48 h, at which time TLC (20% EtO Ac/hex) revealed complete conversion to a single borylated product. The vial was cooled to room temperature and the cap was removed. N-methylmorpholine-N-oxide (2.37 g, 20.2 mmol, 3 equiv) was added in afew small portions and the vial was resealed and returned to the 80 °C oil bath for 3 h, at which time TLC (20% EtOAc/hex) indicated complete oxidation to the intermediate phenol. Triethylamine (4.7 mL, 33.7 mmol, 5 equiv) and isopropyl isocyanate (2.6 mL, 26.9 mmol, 4 equiv) were added at 23 °C and the solution was stirred 16 h, at which time TLC (50% EtO Ac/hex) indicated complete conversion to carbamate S4. The contents of the vial were transferred to a 100 mL roundbottom flask and 10% aq. Na2S2Cb was added to quench the remaining oxidant and citric acid hydrate (4.5 g, >3 equiv) was added to chelate the boron. This solution was stirred 1 h, and concentrated HC1 was added 1 mL at a time until an acidic pH was achieved. The layers were separated and the aqueous phase was extracted with EtO Ac. The combined organic phases were then washed with aqueous K2CO3, dried over MgS04 and concentrated. The product was purified by column chromatography (25% EtO Ac/hex). Colorless solid, 1.16 g, 4.6 mmol, 68% yield. NMR spectra were identical to the previously reported compound. iv NMR (400 MHz, CDCl3) δ 6.55

Reference： [1]Current Patent Assignee: NORTHWEST UNIVERSITY (CHINA) - CN106749363, 2017, A Location in patent: Paragraph 0033; 0034; 0035; 0036; 0037; 0038; 0039-0046
[2]Current Patent Assignee: CALIFORNIA INSTITUTE OF TECHNOLOGY - WO2019/18539, 2019, A1 Location in patent: Page/Page column 68; 69

71
[ 593-60-2 ]
[ 4463-33-6 ]
[ 951161-56-1 ]

Yield	Reaction Conditions	Operation in experiment
35%	Stage #1: 1,2-dimethoxy-3-methylbenzene With N,N,N,N,-tetramethylethylenediamine; tert.-butyl lithium In tetrahydrofuran at 20℃; for 18h; Stage #2: With zinc(II) chloride In tetrahydrofuran at -78 - -60℃; Stage #3: Vinyl bromide With tetrakis(triphenylphosphine) palladium⁽⁰⁾ In tetrahydrofuran

Reference： [1]Tenneti, Srinivasarao; Biswas, Souvagya; Cox, Glen Adam; Mans, Daniel J.; Lim, Hwan Jung; RajanBabu [Journal of the American Chemical Society, 2018, vol. 140, # 31, p. 9868 - 9881]

72
[ 4463-33-6 ]
N-methoxy-N-methylbicyclo[1.1.0]butane-1-carboxamide [ No CAS ]
1-(bicyclo[1.1.0]butan-1-yl)-2-(2,3-dimethoxyphenyl)ethan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	Stage #1: 1,2-dimethoxy-3-methylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; for 2h; Inert atmosphere; Stage #2: N-methoxy-N-methylbicyclo[1.1.0]butane-1-carboxamide In tetrahydrofuran at 0℃; for 0.0833333h;

Reference： [1]Attard, Riley H.; Gardiner, Michael G.; Malins, Lara R.; Schwartz, Brett D.; Zhang, Meng Yao [Chemistry - A European Journal, 2020, vol. 26, # 13, p. 2808 - 2812]

73
[ 121-43-7 ]
[ 4463-33-6 ]
[ 594-19-4 ]
C₁₂H₂₀BO₅^(1-)*Li⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1,2-dimethoxy-3-methylbenzene; tert.-butyl lithium With N,N,N,N,-tetramethylethylenediamine In diethyl ether; hexane; pentane at -78 - 0℃; for 4h; Inert atmosphere; Stage #2: Trimethyl borate In diethyl ether; hexane; pentane at -78 - 20℃; for 24.5h; Inert atmosphere;

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

74
[ 4463-33-6 ]
C₁₄H₁₈O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

75
[ 4463-33-6 ]
[ 1284222-81-6 ]
C₁₄H₁₈O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

76
[ 4463-33-6 ]
C₁₄H₂₀O₃ [ No CAS ]
C₁₄H₂₀O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

77
[ 4463-33-6 ]
C₂₁H₃₃NO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

78
[ 4463-33-6 ]
[ 111466-68-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 7 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

79
[ 4463-33-6 ]
C₂₂H₃₄O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 8 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: dihydrogen peroxide; diphenyl diselenide; magnesium sulfate / water; dichloromethane / 6 h / 20 °C / Inert atmosphere 8.2: 20 h / 0 - 20 °C / Inert atmosphere

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

80
[ 4463-33-6 ]
[ 173040-59-0 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 8 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: o-tetrachloroquinone / acetonitrile / 48 h / 20 °C / Inert atmosphere
	Multi-step reaction with 9 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: dihydrogen peroxide; diphenyl diselenide; magnesium sulfate / water; dichloromethane / 6 h / 20 °C / Inert atmosphere 8.2: 20 h / 0 - 20 °C / Inert atmosphere 9.1: methanesulfonic acid / dichloromethane / 12 h / -78 - -40 °C / Inert atmosphere

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]
[2]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

81
[ 4463-33-6 ]
[ 290810-69-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 10 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: dihydrogen peroxide; diphenyl diselenide; magnesium sulfate / water; dichloromethane / 6 h / 20 °C / Inert atmosphere 8.2: 20 h / 0 - 20 °C / Inert atmosphere 9.1: methanesulfonic acid / dichloromethane / 12 h / -78 - -40 °C / Inert atmosphere 10.1: sodium thioethylate / N,N-dimethyl-formamide / 3 h / 150 °C / Inert atmosphere
	Multi-step reaction with 9 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: o-tetrachloroquinone / acetonitrile / 48 h / 20 °C / Inert atmosphere 9.1: sodium thioethylate / N,N-dimethyl-formamide / 3 h / 150 °C / Inert atmosphere

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]
[2]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

82
[ 4463-33-6 ]
[ 106671-54-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 10 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: dihydrogen peroxide; diphenyl diselenide; magnesium sulfate / water; dichloromethane / 6 h / 20 °C / Inert atmosphere 8.2: 20 h / 0 - 20 °C / Inert atmosphere 9.1: methanesulfonic acid / dichloromethane / 12 h / -78 - -40 °C / Inert atmosphere 10.1: sodium thioethylate / N,N-dimethyl-formamide / 3 h / 150 °C / Inert atmosphere
	Multi-step reaction with 9 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: o-tetrachloroquinone / acetonitrile / 48 h / 20 °C / Inert atmosphere 9.1: sodium thioethylate / N,N-dimethyl-formamide / 3 h / 150 °C / Inert atmosphere

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]
[2]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

83
[ 4463-33-6 ]
(+)-seco-pseudopteroxazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 9 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: sodium thioethylate / N,N-dimethyl-formamide / 3 h / 140 °C / Inert atmosphere 9.1: silver(l) oxide / methanol / 1 h / 90 °C / Inert atmosphere 9.2: 24 h / 90 °C / Inert atmosphere

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

84
[ 4463-33-6 ]
(+)-pseudopteroxazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 10 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: o-tetrachloroquinone / acetonitrile / 48 h / 20 °C / Inert atmosphere 9.1: sodium thioethylate / N,N-dimethyl-formamide / 3 h / 150 °C / Inert atmosphere 10.1: silver(l) oxide / methanol / 1 h / 80 °C / Inert atmosphere 10.2: 19 h / 80 °C / Inert atmosphere
	Multi-step reaction with 11 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: dihydrogen peroxide; diphenyl diselenide; magnesium sulfate / water; dichloromethane / 6 h / 20 °C / Inert atmosphere 8.2: 20 h / 0 - 20 °C / Inert atmosphere 9.1: methanesulfonic acid / dichloromethane / 12 h / -78 - -40 °C / Inert atmosphere 10.1: sodium thioethylate / N,N-dimethyl-formamide / 3 h / 150 °C / Inert atmosphere 11.1: silver(l) oxide / methanol / 1 h / 80 °C / Inert atmosphere 11.2: 19 h / 80 °C / Inert atmosphere

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]
[2]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

85
[ 4463-33-6 ]
[ 199439-75-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 8 steps 1.1: N,N,N,N,-tetramethylethylenediamine / hexane; diethyl ether; pentane / 4 h / -78 - 0 °C / Inert atmosphere 1.2: 24.5 h / -78 - 20 °C / Inert atmosphere 2.1: hydrogenchloride / Inert atmosphere 3.1: chlorobis(ethylene)rhodium(I) dimer; (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene / 1,4-dioxane / 0.08 h / 20 °C / Inert atmosphere 3.2: 3 h / 50 °C / Inert atmosphere 4.1: chlorobis(ethylene)rhodium(I) dimer; 2-aminopyridine; 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene; diphenyl hydrogen phosphate / 1,4-dioxane; water / 48 h / 140 °C / Inert atmosphere; Sealed tube 5.1: sodium tetrahydroborate / methanol / 0.33 h / 20 °C / Inert atmosphere 6.1: triethylamine / dichloromethane / 96 h / 50 °C / Inert atmosphere 7.1: sec.-butyllithium; N,N,N,N,-tetramethylethylenediamine / diethyl ether; cyclohexane / 0.25 h / -78 °C / Inert atmosphere 7.2: 12 h / -78 - 20 °C / Inert atmosphere 7.3: 20 °C / Inert atmosphere 8.1: sodium thioethylate / N,N-dimethyl-formamide / 3 h / 140 °C / Inert atmosphere

Reference： [1]Dong, Guangbin; Hou, Si-Hua; Prichina, Adriana Y.; Zhang, Mengxi [Angewandte Chemie - International Edition, 2020, vol. 59, # 20, p. 7848 - 7856][Angew. Chem., 2020, vol. 132, # 20, p. 7922 - 7930,9]

86
[ 3731-51-9 ]
[ 4463-33-6 ]
C₁₄H₁₆N₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
31%	With 3,6‐di‐tert‐butyl‐9‐mesityl‐10‐phenylacridin‐10‐ium tetrafluoroborate In 1,2-dichloro-ethane at 33℃; for 24h; Sealed tube; Inert atmosphere; Irradiation; regioselective reaction;

Reference： [1]Venditto, Nicholas J.; Nicewicz, David A. [Organic Letters, 2020, vol. 22, # 12, p. 4817 - 4822]

87
[ 5653-67-8 ]
[ 4463-33-6 ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: 2,3-dimethoxybenzyl alcohol With ammonium formate In ethanol; water at 22℃; for 0.166667h; Stage #2: With formic acid In ethanol; water at 22℃; for 4h; chemoselective reaction;	Heterogeneous Palladium-Catalyzed Transfer Hydrogenolysis of Benzylic Alcohols; General Procedure General procedure: A microwave-vial was charged with a solution of 1 (0.4 mmol, 1.0 equiv), HCO2NH4 (6.0 mg, 0.095 mmol, 25 mol%), and Pd(0)-nanocatalyst [Pd(0)-AmP-MFC, 26.8 mg, 0.02 mmol, 8 wt%, 5 mol%]22-24,29 or [Pd(0)-CPG, 569Å, 148.0 mg, 0.02 mmol, 135 mol/g] in EtOH (2.4 mL), and H2O (0.6 mL), and the contents were stirred for 10 min at r.t. Afterwards, formic acid (0.09 mL, 2.4 mmol, 6 equiv) was added and the resulting mixture was stirred at r.t. for the time shown in Table 2. NMR samples for NMR yield were prepared by removing 0.05 mL aliquots from the reaction mixture and filtered through Celite using CDCl3 (1.5 mL) as eluent, and mesitylene was used as an internal standard. Before the purification of the products, the crude reaction mixture was filtered through Celite using CHCl3 (10 mL) as eluent and evaporated. The crude material was purified by silica gel flash column chromatography.

Reference： [1]Afewerki, Samson; Córdova, Armando; Palo-Nieto, Carlos [Synthesis, 2020, vol. 52, # 16, p. 2330 - 2336]

88
[ 4463-33-6 ]
C₂₂H₂₃NO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: polyphosphoric acid 2: titanium tetrachloride; 1,8-diazabicyclo[5.4.0]undec-7-ene 3: dichloromethane / 24 h / 20 °C / Irradiation

Reference： [1]Costil, Romain; Crespi, Stefano; Feringa, Ben L.; Léonard, Jérémie; Olivucci, Massimo; Pfeifer, Lukas; Pierron, Robin; Pooler, Daisy R. S. [Chemical Science, 2021, vol. 12, # 21, p. 7486 - 7497]

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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CAS No. :	4463-33-6	MDL No. :	MFCD00008379
Formula :	C₉H₁₂O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	WMXFNCKPYCAIQW-UHFFFAOYSA-N
M.W :	152.19	Pubchem ID :	78215
Synonyms :

Num. heavy atoms :	11
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.33
Num. rotatable bonds :	2
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	44.39
TPSA :	18.46 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.74 cm/s

Log Po/w (iLOGP) :	2.3
Log Po/w (XLOGP3) :	2.1
Log Po/w (WLOGP) :	2.01
Log Po/w (MLOGP) :	1.8
Log Po/w (SILICOS-IT) :	2.29
Consensus Log Po/w :	2.1

[ CAS No. 4463-33-6 ] {[proInfo.proName]}

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[ 4463-33-6 ] Synthesis Path-Upstream 1~3

[ 4463-33-6 ] Synthesis Path-Downstream 1~88

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[ 4463-33-6 ]

Aryls

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

Log S (ESOL) :	-2.38
Solubility :	0.637 mg/ml ; 0.00419 mol/l
Class :	Soluble
Log S (Ali) :	-2.12
Solubility :	1.16 mg/ml ; 0.00762 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-3.02
Solubility :	0.144 mg/ml ; 0.000948 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.02

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

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

[ CAS No. 4463-33-6 ] {[proInfo.proName]}

Quality Control of [ 4463-33-6 ]

Related Doc. of [ 4463-33-6 ]

Product Details of [ 4463-33-6 ]

Calculated chemistry of [ 4463-33-6 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 4463-33-6 ]

Application In Synthesis of [ 4463-33-6 ]

[ 4463-33-6 ] Synthesis Path-Upstream 1~3

[ 4463-33-6 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 4463-33-6 ]

Aryls

Ethers

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 4463-33-6 ]