Name: 6728-26-3|trans-2-Hexenal|98%
Brand: Ambeed
SKU: A289083
Price: 18.0 USD
Availability: InStock
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1
[ 6728-26-3 ]
[ 928-95-0 ]

Yield	Reaction Conditions	Operation in experiment
93%	With bis(cyclopentadienyl)dihydrozirconium In isopropyl alcohol at 130℃; for 8h;
93%	With phosphotungstic acid; sodium tetrahydroborate In methanol
92%	With isopropyl alcohol for 6h; Heating;

92%	With isopropyl alcohol for 6h; Heating;
71%	With diisobutylaluminium hydride In hexane; dichloromethane at 0℃; for 1h; Inert atmosphere;
62%	With methanol; sodium tetrahydroborate at 0 - 20℃; for 0.5h;
	With sodium tetrahydroborate In methanol; dichloromethane at -78℃; Competition with ..(aldehydes 1a, 1b, 1c, 1d).. and ..(ketones 3a, 3d, 3e, 3f,).. and ..(enones 4a, 4f).. Studies on the chemoselective reduction of various types of aldehydes and ketones with sodium borohydride.;
	With isopropyl alcohol for 6h; Heating;
	With lithium aluminium tetrahydride
100 % Chromat.	With (1,4-diazabicyclo{2.2.2}-octane)zinc(II) tetrahydoborate In tetrahydrofuran for 1.7h; Heating;
	With N-tert-butylaminoborane In tetrahydrofuran; water at 10 - 15℃; Yield given;
	With sodium hydroxide; sodium tetrahydroborate; zinc 2-ethylhexanoate 1.) THF, reflux, 2.) 40 deg, 1 h; Yield given; Multistep reaction;
		C.1 trans-2-Hexenol (Meerwein-Ponndorf-Verley reduction) Comparative Example 1 trans-2-Hexenol (Meerwein-Ponndorf-Verley reduction) In a round-bottomed flask provided with magnetic stirrer and reflux condenser, 0.5 g (5.1 mmol) of trans-2-hexenal, 12 g of isopropyl alcohol and 3.9 g of catalyst were heated under reflux. After the end of the reaction time, the reaction mixture was analyzed by gas chromatography and the yield was determined. The results are summarized in Table 1 below:
	With 2,3,4,5,6-pentahydroxy-hexanal; Bacillus subtilis glucose dehydrogenase; Saccharomyces cerevisiae dehydrogenase Gre₂p; NADPH; magnesium chloride at 30℃; aq. buffer; Enzymatic reaction;
	With D-glucose; D-glucose dehydrogenase; a putative aldehyde reductase (OsAR) from Oceanospirillum sp.MED₉₂; NADPH In aq. phosphate buffer at 25℃; for 18h; Enzymatic reaction; chemoselective reaction;	2.7. Selective reduction of aldehydes General procedure: The bioreduction of 4-acetylbenzaldehyde was carried out as follows: d-Glucose (280 mg), d-glucose dehydrogenase (11 U), NADPH (10 mg), QsAR (40 U) and 4-acetylbenzaldehyde (50 mg) were mixed in sodium phosphate buffer (25 ml, 100 mM, pH 6.5). The mixture was stirred at 25 °C for 18 h. The mixture was extracted with methyl tert-butyl ether. The organic extract was dried over anhydrous sodium sulfate and removal of the solvent gave product, 4-acetylbenzyl alcohol (38.2 mg, 76.4% yield). 1H NMR (CDCl3), δ: 2.58 (d, 3H), 4.76 (s, 2H,), 7.44(d, 2H, 2JH-H = 7.2 Hz,), 7.93 (d, 2H, 2JH-H = 7.2 Hz)). The bioreductions of hexanal and 2-nonanone were as follows: d-Glucose (36 mg), d-glucose dehydrogenase (2 U), NADPH (1.0 mg), QsAR (4 U), hexanal (10 mM) and 2-nonanone (10 mM) were mixed in sodium phosphate buffer (2 ml, 100 mM, pH 6.5). The mixture was stirred at 25 °C for 12 h. The mixture was extracted with methyl tert-butyl ether. The products were identified by comparison with authentic samples in an Agilent 7890 gas chromatography with Gamma DEXTM 225 capillary column (30 m × 0.25 mm × 0.25 mm, SUPELCO, Japan). The column temperature was controlled as follows: 50 °C for 5 min; 30 °C/min to 80 °C; 80 °C for 5 min; 20 °C/min to 100 °C; 100 °C for 8 min. The retention times for hexanal and hexanol were 6.99 and 8.66 min; 16.08 and 16.44 min for 2-nonanone and 2-nonanol, respectively.
	With hydrogen In hexane at 50℃; for 18h; Autoclave; chemoselective reaction;
	With aldehyde reductase; nicotinamide adenine dinucleotide phosphate Enzymatic reaction;
	With hydrogen In neat (no solvent) at 90℃; for 36h; chemoselective reaction;
	With potassium formate In water; N,N-dimethyl-formamide at 100℃; for 5h; Inert atmosphere; chemoselective reaction;
	With hydrogen In isopropyl alcohol at 70℃; for 2h; Autoclave; chemoselective reaction;
	With sodium tetrahydroborate In ethanol at 0℃; for 0.5h;
	With hydrogen; C₂₇H₄₁IrN₃P In 2-methyltetrahydrofuran at 25℃; for 24h; Inert atmosphere; Glovebox; chemoselective reaction;
	With hydrogen In water at 100℃; for 8h; Autoclave;
	With sodium formate; 5Ru⁽²⁺⁾5Cl^(1-)K⁽¹⁺⁾5C₂H₈N₂5C₁₀H₁₄*P₂W₁₈O₆₂^(6-) In water at 110℃; for 4h; Autoclave; Inert atmosphere;	2.4. A typical procedure for the catalytic reaction General procedure: Transfer hydrogenation reaction of ML was carried out with magneticstirring in a 50 ml stainless steel autoclave containing 5 mL 0.2 MML aqueous solution, 10 mg catalyst, and 3 mmol HCOONa was used ineach run of the reaction. The reactor was flushed thrice with 0.5 MPa N2and then 1.0 MPa N2 was flushed in the autoclave and placed in anelectric stove maintained at the reaction temperature. The reaction wasstopped at a selected time by cooling the reactor in an ice water bath. The liquid products were qualitatively analyzed by an Agilent 6890/5973 GC-MS system equipped with an HP-5MS column (30 m × 0.25mm × 0.25 m) and a flame ionization detector (FID). For quantitativemeasurements, analysis was performed on a GC128 (INESA AnalyticalInstrument Co., Ltd) gas chromatograph equipped with an FFAP capillarycolumn (30 m × 0.25 mm × 0.25 m), and 1,4-dioxane was used asthe internal standard. The conversion of ML was calculated according tothe following equation:Conversion (%) =amount of ML converted (mol)the total amount of ML (mol)×100The selectivity of GVL was normally higher than 99% without specialinstructions. For the transfer hydrogenation reaction with other substratemolecules, a similar procedure has been employed unless indicatedotherwise.

Reference： [1]Nakano, Tatsuya; Umano, Shigetoshi; Kino, Yoshio; Ishii, Yasutaka; Ogawa, Masaya [Journal of Organic Chemistry, 1988, vol. 53, # 16, p. 3752 - 3757]
[2]Heydari, Akbar; Khaksar, Samad; Akbari, Jafar; Esfandyari, Maryam; Pourayoubi, Mehrdad; Tajbakhsh, Mahmoud [Tetrahedron Letters, 2007, vol. 48, # 7, p. 1135 - 1138]
[3]Shibagaki, Makoto; Takahashi, Kyoko; Matasushita, Hajime [Bulletin of the Chemical Society of Japan, 1988, vol. 61, p. 3283 - 3288]
[4]Shibagaki, Makoto; Takahashi, Kyoko; Matasushita, Hajime [Bulletin of the Chemical Society of Japan, 1988, vol. 61, p. 3283 - 3288]
[5]Ariga, Elaine Miho; Carita Correra, Thiago; Matsushima, Jullyane Emi; McIndoe, J. Scott; Moreira Ribeiro, Francisco Wanderson; Omari, Isaac; Papa Spadafora, Bruna; Rodrigues, Alessandro; Soares, Priscila Machado Arruda; Vinhato, Elisângela; de Oliveira-Silva, Diogo [Organic and Biomolecular Chemistry, 2021, vol. 19, # 25, p. 5595 - 5606]
[6]Peňaška, Tibor; Mojzes, Melinda Meyer; Filo, Juraj; Jurdáková, Helena; Mečiarová, Mária; Šebesta, Radovan [European Journal of Organic Chemistry, 2019, vol. 2019, # 2, p. 605 - 610]
[7]Ward, Dale E.; Rhee, Chung K. [Canadian Journal of Chemistry, 1989, vol. 67, p. 1206 - 1211]
[8]Inada, Kazushige; Shibagaki, Makoto; Nakanishi, Yukio; Matsushita, Hajime [Chemistry Letters, 1993, # 10, p. 1795 - 1798]
[9]Gruenanger; Grieco [Gazzetta Chimica Italiana, 1958, vol. 88, p. 296,305]
[10]Firouzabadi, Habib; Zeynizadeh, Behzad [Bulletin of the Chemical Society of Japan, 1997, vol. 70, # 1, p. 156 - 168]
[11]Lukin, Kirill A.; Yang, ChengXi; Bellettini, John R.; Narayanan; Leanna, M. Robert; Rasmussen, Michael [Synlett, 1999, # 1, p. 59 - 60]
[12]Mimoun [Journal of Organic Chemistry, 1999, vol. 64, # 7, p. 2582 - 2589]
[13]Current Patent Assignee: LONZA GROUP AG - US6075145, 2000, A
[14]Location in patent: experimental part Mueller, Marion; Katzberg, Michael; Bertau, Martin; Hummel, Werner [Organic and Biomolecular Chemistry, 2010, vol. 8, # 7, p. 1540 - 1550]
[15]Li, Guangyue; Ren, Jie; Wu, Qiaqing; Feng, Jinhui; Zhu, Dunming; Ma, Yanhe [Journal of Molecular Catalysis B: Enzymatic, 2013, vol. 90, p. 17 - 22]
[16]Cano, Israel; Huertos, Miguel A.; Chapman, Andrew M.; Buntkowsky, Gerd; Gutmann, Torsten; Groszewicz, Pedro B.; Van Leeuwen, Piet W. N. M. [Journal of the American Chemical Society, 2015, vol. 137, # 24, p. 7718 - 7727]
[17]Kunishima, Mikiko; Yamauchi, Yasuo; Mizutani, Masaharu; Kuse, Masaki; Takikawa, Hirosato; Sugimoto, Yukihiro [Journal of Biological Chemistry, 2016, vol. 291, # 27, p. 14023 - 14033]
[18]Ye, Tian-Nan; Li, Jiang; Kitano, Masaaki; Sasase, Masato; Hosono, Hideo [Chemical Science, 2016, vol. 7, # 9, p. 5969 - 5975]
[19]Gao, Yanxiu; Wang, Jie; Han, Aijuan; Jaenicke, Stephan; Chuah, Gaik Khuan [Catalysis science and technology, 2016, vol. 6, # 11, p. 3806 - 3813]
[20]Hu, Duo; Fan, Wenqian; Liu, Zhi; Li, Ling [ChemCatChem, 2018, vol. 10, # 4, p. 779 - 788]
[21]Colella, Marco; Tota, Arianna; Großjohann, Angela; Carlucci, Claudia; Aramini, Andrea; Sheikh, Nadeem S.; Degennaro, Leonardo; Luisi, Renzo [Chemical Communications, 2019, vol. 55, # 58, p. 8430 - 8433]
[22]Álvarez, Eleuterio; Hernández-Juárez, Martín; López-Serrano, Joaquín; Paneque, Margarita; Rendón, Nuria; Sánchez, Práxedes; Suárez, Andrés [Organometallics, 2021, vol. 40, # 9, p. 1314 - 1327]
[23]Chen, Manyu; Xia, Jie; Li, Huan; Zhao, Xiuge; Peng, Qingpo; Wang, Jiajia; Gong, Honghui; Dai, Sheng; An, Pengfei; Wang, Haifeng; Hou, Zhenshan [ChemCatChem, 2021, vol. 13, # 17, p. 3801 - 3814]
[24]Chen, Manyu; Cui, Kai; Hou, Zhenshan; Peng, Qingpo; Wang, Jiajia; Wei, Xinjia; Zhao, Xiuge [Molecular catalysis, 2022, vol. 517]

2
[ 928-96-1 ]
[ 6728-26-3 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium dichromate; sulfuric acid; benzene
	With oxygen In α,α,α-trifluorotoluene at 110℃;	2 In the oxidation reaction of unsaturated aliphatic alcohols, the maximal oxidation rates obtained for secondary alcohols was higher than those observed for primary alcohols, as presented in Table 2. The only significant by-products in these reactions were the saturated aldehdyes or ketones, namely propanal, hexanal, butanone and so forth, and in the cases where the alcohols were pure E/Z hexen-1-ol isomers, the E-2-hexenal was the major product. No significant amounts of carboxylic acids were formed.Table 2 presents the results obtained for unsaturated alcohols under reaction conditions of 0.1 mmol alcohol, 5 μmol Pd-POM-1, 1 ml TFT, 2 bars O2, and 110° C.,wherein the rate of oxidation yields, determined by GC analysis, is shown as molar percentage, the time for completion/arrest in minutes, and the selectivity for the major product (β-unsaturated aldehyde or ketone respectively) in molar percentage. As can be seen in Table 2, the cis isomers were isomerized to trans products, to and as noticeable from the formation of saturated aldehydes and ketones as by-products, the isomerisation of the double bond competed with the alcohol oxidation reaction.

Reference： [1]Ohloff [Archiv der Pharmazie, 1954, vol. 287, p. 272,278]
[2]Current Patent Assignee: WEIZMANN INSTITUTE OF SCIENCE - US2012/197033, 2012, A1 Location in patent: Page/Page column 10-11

3
[ 6728-26-3 ]
[ 67-66-3 ]
[ 96349-57-4 ]

Yield	Reaction Conditions	Operation in experiment
81%	With tetrachloromethane In N,N-dimethyl-formamide electroreduction;
	With potassium hydroxide In methanol; N,N-dimethyl-formamide at 0℃; for 2h;	4.2. Typical procedure for substrates 8f, 8i-l preparation General procedure: To a 25 mL RBF was added α,β-unsaturated aldehyde (5 mmol), CHCl3 (20 mmol, 1.6 mL), and DMF (4 mL), the mixture was stirred at room temperature for about 10 min, then a solution of KOH (5 mmol, 280 mg) in MeOH (4 mL) was added dropwise at 0 °C and the reaction was carried out at this temperature for 2 h (monitored by TLC). The mixture was acidated to pH 4-7 and extracted with ethyl acetate (20 mL). The organic phase was washed with brine (10 mL) and dried over Na2SO4, and concentrated in vacuo. This crude secondary alcohol was used without further purification. Under argon atmosphere, the solution of crude secondary alcohol, MnO2 (15 equiv), DCM (25 mL) was stirred at room temperature for 24-48 h. The residue was filtrated by Celite, concentrated in vacuo, and purified by flash column chromatography on silica gel (petroleum ether) to give the substrates 8.

Reference： [1]Shono, Tatsuya; Kise, Naoki; Masuda, Mitsuharu; Suzumoto, Takeshi [Journal of Organic Chemistry, 1985, vol. 50, # 14, p. 2527 - 2533]
[2]Wang, Hai-Feng; Li, Peng; Cui, Hai-Feng; Wang, Xiao-Wei; Zhang, Jun-Kang; Liu, Wen; Zhao, Gang [Tetrahedron, 2011, vol. 67, # 10, p. 1774 - 1780]

4
[ 6728-26-3 ]
[ 7677-24-9 ]
[ 148811-03-4 ]

Yield	Reaction Conditions	Operation in experiment
83%	Stage #1: (E)-2-Hexenal; trimethylsilyl cyanide With zinc(II) iodide at 20℃; for 0.5h; Stage #2: With hydrogen fluoride In acetonitrile at 20℃; for 1h;
	With hydrogenchloride; zinc(II) iodide
	With hydrogenchloride; zinc(II) iodide Yield given;

Reference： [1]Takeda, Kei; Haraguchi, Hidekazu; Okamoto, Yasushi [Organic Letters, 2003, vol. 5, # 20, p. 3705 - 3707]
[2]Murahashi, Shun-ichi; Naota, Takeshi; Nakajima, Nobuyuki [Tetrahedron Letters, 1985, vol. 26, # 7, p. 925 - 928]
[3]Murahashi; Naota [Russian Journal of Organic Chemistry, 1996, vol. 32, # 2, p. 203 - 213]

5
[ 6728-26-3 ]
[ 311-46-6 ]
[ 60388-61-6 ]

Reference： [1]Journal of the Indian Chemical Society,1990,vol. 67,p. 37 - 38

6
[ 6728-26-3 ]
[ 37555-23-0 ]
(E)-7-Methylene-undec-4-en-6-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	With chromium dichloride In N,N-dimethyl-formamide at 25℃; for 4h;

Reference： [1]Takai, Kazuhiko; Tagashira, Mizuki; Kuroda, Tooru; Oshima, Koichiro; Utimoto, Kiitiro; Nozaki, Hitosi [Journal of the American Chemical Society, 1986, vol. 108, # 19, p. 6048 - 6050]

7
[ 6728-26-3 ]
[ 28075-50-5 ]
(E)-1-Cyclohex-1-enyl-hex-2-en-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
41%	With chromium dichloride In N,N-dimethyl-formamide at 25℃; for 4h;

Reference： [1]Takai, Kazuhiko; Tagashira, Mizuki; Kuroda, Tooru; Oshima, Koichiro; Utimoto, Kiitiro; Nozaki, Hitosi [Journal of the American Chemical Society, 1986, vol. 108, # 19, p. 6048 - 6050]

8
[ 6728-26-3 ]
(Z)-1-ethylthio-1-(trimethylsiloxy)propene [ No CAS ]
[ 133910-36-8 ]

Yield	Reaction Conditions	Operation in experiment
91%	With tin(II) trifluoromethanesulfonate; dibutyltin diacetate; (2S)-1-methyl-2-<(N-1-naphthylamino)methyl>pyrrolidine In dichloromethane at -78℃;

Reference： [1]Kobayashi, Shu; Uchiro, Hiromi; Fujishita, Yuko; Shiina, Isamu; Mukaiyama, Teruaki [Journal of the American Chemical Society, 1991, vol. 113, # 11, p. 4247 - 4252]

9
[ 6728-26-3 ]
[ 13419-69-7 ]

Yield	Reaction Conditions	Operation in experiment
99%	With diphenyl diselenide; dihydrogen peroxide In water at 20℃; for 6h; Green chemistry;	3.2. General Procedure for the Synthesis of Carboxylic Acids 2 General procedure: Diphenyl diselenide (3, 0.006 g; 0.02 mmol) was treated with H2O2 (30%·w/w, 0.1 mL, 1 mmol) andwater (0.2 mL) and stirred at room temperature at 800 rpm until the discoloration of the reaction mixture;then, the aldehyde 1 (1 mmol) was added. After 6 h, the aqueous mixture was extracted three times withEtOAc (3 × 20 mL). The collected organic layers were dried over Na2SO4 and the solvent evaporatedunder reduced pressure.
88%	With sodium chlorite; sodium dihydrogenphosphate; dihydrogen peroxide In water; acetonitrile at 10℃; for 1h;
88%	With Iron(III) nitrate nonahydrate; oxygen; sodium 2,2,2-trifluoroacetate In ethyl acetate at 25℃; for 16h;	Typical procedure for the oxidation reaction (Table 1, entry 14). General procedure: In a test tube, trans-2-decenal (167 mg, 1.0 mmol) was added to a suspension of Fe(NO3)3·9H2O(4.1 mg, 0.010 mmol) and CF3COONa (28 mg, 0.20 mmol) in EtOAc (0.50 mL). O2 balloon (1atm) was attached at top of the test tube, and inner atmosphere was replaced by O2. After stirring16 h at 25 °C, EtOAc (3 mL) and 1M HCl aq. (1 mL) were added and resulting biphasic mixture wasstirred for 1 min. Organic phase was separated, and water phase was extracted by EtOAc (3 mL X2). To the collected organic phase was then added measured amount of biphenyl (as an internalstandard for NMR analysis). The conversion of substrate and the yield of products weredetermined by NMR analysis (400 MHz, CDCl3, 25 °C). Products were identified by comparison tothe NMR signals of authentic samples. The same reaction was performed twice for each reaction.

87%	With iron oxide; oxygen; ethyl acetoacetate at 75 - 80℃; for 24h; Green chemistry;	Typical procedure for the oxidation of aldehydes to carboxylic acids General procedure: To a vial with the catalyst (20 mol %) under air, aldehyde (0.0625 mmol) and ethyl acetoacetate (1 equiv) were added. The mixture was heated at 75-80 °C for 24 h. After cooling at rt, ethyl acetate (1.0 ml) was added and the catalyst was separated by simple magnetic decantation. Then, the combined solvent was removed in vacuo and the mixture was purified via trituration or flash column. Spectroscopic data of products 2 were consistent with those reported in the literature (2a,14 2b,15 2c,16 2d,14 2e,17 2f,14 2h,18 2i,19 2j20 and 2k21). trans-Hex-2-enoic acid (2j): ;6.2 mg, 87% yield. 1H NMR (400 MHz, CDCl3) δ 7.06 (dt, 1H, J = 15.6, 6.8 Hz), 5.83 (d, 1H, J = 15.6 Hz), 2.25-2.19 (m, 2H), 1.54-1.46 (m, 2H), 0.95 (t, 3H, J = 7.6 Hz). 13C NMR (100 MHz, CDCl3) δ 171.5, 152.4, 120.5, 34.3, 21.1, 13.6.
71 %Chromat.	Stage #1: (E)-2-Hexenal With palladium(II) trifluoroacetate at 10℃; for 0.166667h; Stage #2: With dihydrogen peroxide In water at 10℃; chemoselective reaction;
	With tert.-butylhydroperoxide In water; acetonitrile at 60℃; for 5h;
	With Arabidopsis thaliana aldehyde dehydrogenase 3H₁; NAD aq. phosphate buffer; Enzymatic reaction;

Reference： [1]Sancineto, Luca; Tidei, Caterina; Bagnoli, Luana; Marini, Francesca; Lenardo, Eder J.; Santi, Claudio [Molecules, 2015, vol. 20, # 6, p. 10496 - 10510]
[2]Dalcanale, Enrico; Montanari, Fernando [Journal of Organic Chemistry, 1986, vol. 51, # 4, p. 567 - 569]
[3]Tanaka, Shinji; Kon, Yoshihiro; Uesaka, Yumiko; Morioka, Ryo; Tamura, Masanori; Sato, Kazuhiko [Chemistry Letters, 2016, vol. 45, # 2, p. 188 - 190]
[4]Villano, Rosaria; Acocella, Maria Rosaria; Scettri, Arrigo [Tetrahedron Letters, 2014, vol. 55, # 15, p. 2442 - 2445]
[5]Kon, Yoshihiro; Imao, Daisuke; Nakashima, Takuya; Sato, Kazuhiko [Chemistry Letters, 2009, vol. 38, # 5, p. 430 - 431]
[6]Location in patent: experimental part Chattopadhyay, Tanmay; Kogiso, Masaki; Asakawa, Masumi; Shimizu, Toshimi; Aoyagi, Masaru [Catalysis Communications, 2010, vol. 12, # 1, p. 9 - 13]
[7]Location in patent: experimental part Stiti, Naim; Adewale, Isaac O.; Petersen, Jan; Bartels, Dorothea; Kirch, Hans-Hubert [Biochemical Journal, 2011, vol. 434, # 3, p. 459 - 471]

10
[ 6728-26-3 ]
[ 66-25-1 ]

Yield	Reaction Conditions	Operation in experiment
98%	With hydrogen; sodium dodecyl-sulfate; palladium diacetate In tetrahydrofuran; water at 20℃; for 0.5h; chemoselective reaction;
89%	With N,N,N,N,N,N-hexamethylphosphoric triamide; diisobutylaluminium hydride In tetrahydrofuran; hexane at 0℃; for 1h;
35.2%	With hydrogen In isopropyl alcohol at 110℃; for 3h; Autoclave;	2.3. Hydrogenation reactions General procedure: FFR (99%, Sigma-Aldrich) 1 mL and various amounts of thenickel catalysts were added to 30 mL of a solvent (methanol(99.8%, Duksan), ethanol, IPA, or methyl isobutyl ketone (MIBK;99.5%, TCI)). Raney Ni (Ni 92.5%, TCI) was washed with ethanoland distilled water twice each and dried in a vacuum oven at50 °C before use. The mixed solution was placed in a 100 mL Teflonliner with a magnetic stir-bar and sealed in a stainless steel autoclave.Then the reactor was purged with H2 three times to excludeother gases. The autoclave was heated to 110 °C at which temperaturethe hydrogenation reaction was performed under 30 bar H2and stirring at 700 rpm. After the reaction, the autoclave wascooled, and the solution was subsequently centrifuged at11,000 rpm for 10 min to separate the liquid-phase products fromthe catalyst. For the recycling tests, 1 mL of FFR and 30 mL of IPAwere added to the centrifuged Ni catalyst without any furthertreatment. The products were analyzed by a gas chromatograph(GC; YL 6100) equipped with a capillary column (DB-624, AgilentTechnologies, 30 m 0.53 mm 3.00 lm) and flame ionizationdetector (FID).The selective hydrogenation of various unsaturated aldehydesand ketones was performed according to the following protocol.The reactant 1 mL (3-cyclohexene-1-carboxaldehyde (97%,Sigma-Aldrich), 5-hydroxymethyl-2-furaldehyde (99%, Sigma-Aldrich), 5-methylfurfural (99%, Sigma-Aldrich), 2-thiophenecarboxaldehyde (98%, Sigma-Aldrich), pyrrole-2-carboxaldehyde (98%, Sigma-Aldrich), 3-furancarboxaldehyde(P97%, Sigma-Aldrich), 2-furyl methyl ketone (99%, Sigma-Aldrich), acetophenone (99%, Sigma-Aldrich), cinnamaldehyde(99%, Sigma-Aldrich), or trans-2-hexen-1-al (98%, Sigma-Aldrich))was added to 30 mL of IPA. The 6.8 nm Ni nanoparticle catalyst(20 mg) was charged to the reactor. The hydrogenation reactionswere then performed according to the FFR hydrogenation protocol,except the reaction temperature was 100 °C for 3-cyclohexene-1-carboxaldehyde.

96 % Chromat.	With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate In benzene at 80℃; for 17h;
	With potassium phosphate buffer; 2-alkenal reductase of Mucor griseo-cyanus AHU₆₀₄₄; NADPH; Triton X-100 at 37℃; for 0.166667h; relative rate;
	With hydrogen at 100℃; for 4h; also Ni₆₄Zr₃₆; var. temp., pressure and time;
90 % Chromat.	With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; dibenzylammonium trifluoroacetate salt In tetrahydrofuran at 20℃; for 15h;
	With recombinant barley alkenal hydrogenase 1; NADPH In phosphate buffer; ethanol at 30℃;
	With Chr-OYE₁ (old yellow enzyme from chryseobacterium sp. CA₄₉); β-nicotinamide adenine dinucleotide reduced In aq. phosphate buffer at 30℃; for 0.0333333h; Enzymatic reaction;	2.5 Bioreduction of activated alkenes and product analysis General procedure: The bioreduction of various substrates was performed in 1-ml reaction system containing 100mM potassium phosphate buffer (pH 7.0), 10mM NADH, 5mM substrate, and 50μg purified Chr-OYE1 or 500μg purified Chr-OYE2. After 2-min or 16-h incubation at 30°C for Chr-OYE1 and Chr-OYE2, respectively, the reactions were terminated by extraction with ethyl acetate. The organic phase was analyzed using GC or HPLC. (0013) Preparative-scale biotransformation was performed in 30-ml reaction system for substrates 4a, 6a, and 12a-17a catalyzed with Chr-OYE1. The incubation was continued for 12h. The extracted organic phase was combined and concentrated under reduced pressure. The final product was purified with column chromatography and subjected to GC or HPLC analysis, as well as NMR analysis to confirm the structure and purity.
94 %Spectr.	With 1,2,3-trimethoxybenzene; hydrogen In ethyl acetate at 20℃; Flow reactor; Green chemistry; chemoselective reaction;
	With alkenal reductase Enzymatic reaction;
	With MGSSHHHHHHENLYFQSNGGEVSNKTWVFKKSPSSLPEPGVHTAFEDRPLSLVAPPGGLVIKLLTAGLDPHQRDRMRGAGNVDYVPGYEVNEPITNFSIAKVIRSDNDVFEEGSLIAGSLPIAEYGIIPRELIDARAMASPLVWKVSNDYNLDVKHYVGTLGLAGMTAWNSFYGLVKAVKGETIWVNAASSSVGEVVVQLAKIEGMKVIASVSSDDKLDYVVNELGADVGFNYRKEPVGKALKRLAPDGLDVVFENVGGDHFQAAIENMKWFGRIISCGTASQYNKPVEEQYGVTNLSEIFRRRIKIQGFIFWDDNIYTDNIENFKATMPKWVSEGKIKSRYTQFEGIEQADKAFLSMFTGGSHGKTVLKISDP Enzymatic reaction;
	With recombinant Cyclocybe aegerita ene/yne-reductase CaEnR₁; NADPH In aq. phosphate buffer at 24℃; for 3h; Enzymatic reaction;

Reference： [1]La Sorella, Giorgio; Canton, Patrizia; Strukul, Giorgio; Scarso, Alessandro [ChemCatChem, 2014, vol. 6, # 6, p. 1575 - 1578]
[2]Tsuda, Tetsuo; Hayashi, Toshio; Satomi, Hiroshi; Kawamoto, Tadashi; Saegusa, Takeo [Journal of Organic Chemistry, 1986, vol. 51, # 4, p. 537 - 540]
[3]Jeong, Hojin; Kim, Chanyeon; Yang, Sungeun; Lee, Hyunjoo [Journal of Catalysis, 2016, vol. 344, p. 609 - 615]
[4]Nakamura, Kaoru; Fujii, Masayuki; Ohno, Atsuyoshi; Oka, Shinzaburo [Tetrahedron Letters, 1984, vol. 25, # 36, p. 3983 - 3986]
[5]Miyamura, Naohiro; Matsui, Hirokazu; Tahara, Satoshi; Mizutani, Junya; Chiba, Seiya [Agricultural and Biological Chemistry, 1984, vol. 48, # 1, p. 185 - 192]
[6]Heveling, Josef [Chimia, 1996, vol. 50, # 3, p. 114 - 118]
[7]Yang, Jung Woon; Hechavarria Fonseca, Maria T.; List, Benjamin [Angewandte Chemie - International Edition, 2004, vol. 43, # 48, p. 6660 - 6662]
[8]Hambraeus, Gustav; Nyberg, Nils [Journal of Agricultural and Food Chemistry, 2005, vol. 53, # 22, p. 8714 - 8721]
[9]Pei, Xiao-Qiong; Xu, Meng-Yu; Wu, Zhong-Liu [Journal of Molecular Catalysis B: Enzymatic, 2016, vol. 123, p. 91 - 99]
[10]Nagendiran, Anuja; Sörensen, Henrik; Johansson, Magnus J.; Tai, Cheuk-Wai; Bäckvall, Jan-E. [Green Chemistry, 2016, vol. 18, # 9, p. 2632 - 2637]
[11]Kunishima, Mikiko; Yamauchi, Yasuo; Mizutani, Masaharu; Kuse, Masaki; Takikawa, Hirosato; Sugimoto, Yukihiro [Journal of Biological Chemistry, 2016, vol. 291, # 27, p. 14023 - 14033]
[12]Hai, Yang; Chen, Mengbin; Huang, Arthur; Tang, Yi [Journal of the American Chemical Society, 2020, vol. 142, # 46, p. 19668 - 19677]
[13]Karrer, Dominik; Gand, Martin; Rühl, Martin [ChemCatChem, 2021, vol. 13, # 9, p. 2191 - 2199]

11
[ 928-94-9 ]
[ 6728-26-3 ]

Yield	Reaction Conditions	Operation in experiment
75.8%	With pyridinium chlorochromate In dichloromethane for 1h; Ambient temperature;
62%	With dmap; [2,2]bipyridinyl; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; copper(I) bromide In acetonitrile at 20℃; for 18h; Schlenk technique;
	With oxygen In α,α,α-trifluorotoluene at 110℃;

With oxygen In α,α,α-trifluorotoluene at 110℃;

2 In the oxidation reaction of unsaturated aliphatic alcohols, the maximal oxidation rates obtained for secondary alcohols was higher than those observed for primary alcohols, as presented in Table 2. The only significant by-products in these reactions were the saturated aldehdyes or ketones, namely propanal, hexanal, butanone and so forth, and in the cases where the alcohols were pure E/Z hexen-1-ol isomers, the E-2-hexenal was the major product. No significant amounts of carboxylic acids were formed.Table 2 presents the results obtained for unsaturated alcohols under reaction conditions of 0.1 mmol alcohol, 5 μmol Pd-POM-1, 1 ml TFT, 2 bars O2, and 110° C.,wherein the rate of oxidation yields, determined by GC analysis, is shown as molar percentage, the time for completion/arrest in minutes, and the selectivity for the major product (β-unsaturated aldehyde or ketone respectively) in molar percentage. As can be seen in Table 2, the cis isomers were isomerized to trans products, to and as noticeable from the formation of saturated aldehydes and ketones as by-products, the isomerisation of the double bond competed with the alcohol oxidation reaction.

Reference： [1]Vig; Sharma; Gupta [Journal of the Indian Chemical Society, 1990, vol. 67, # 1, p. 37 - 38]
[2]Könning, Daniel; Olbrisch, Tobias; Sypaseuth, Fanni D.; Tzschucke, C. Christoph; Christmann, Mathias [Chemical Communications, 2014, vol. 50, # 39, p. 5014 - 5016]
[3]Location in patent: scheme or table Barats, Delina; Neumann, Ronny [Advanced Synthesis and Catalysis, 2010, vol. 352, # 2-3, p. 293 - 298]
[4]Current Patent Assignee: WEIZMANN INSTITUTE OF SCIENCE - US2012/197033, 2012, A1 Location in patent: Page/Page column 10-11

12
[ 928-95-0 ]
[ 6728-26-3 ]

Yield	Reaction Conditions	Operation in experiment
100%	With oxygen In N,N-dimethyl-formamide at 25℃; for 1.75h;
100%	With manganese(IV) oxide; 3-mercapto-2-(mercaptomethyl)-ethyl propanoate; 4 A molecular sieve In dichloromethane Heating;
99%	With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 16h; Inert atmosphere;

97%	With oxygen In benzene at 60℃; for 24h;
93%	With bis(cyclopentadienyl)dihydrozirconium; benzaldehyde In toluene at 110℃; for 8h;
91%	With (1,10-phenanthrolino)2-tetrapalladium(CO)(acetate)4; oxygen In benzene at 50℃; for 24h;
84%	With tert.-butylhydroperoxide In 2,2,4-trimethylpentane; dichloromethane for 12h; Ambient temperature;
84%	With 1-methyl-1H-imidazole; [2,2]bipyridinyl; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; copper(ll) bromide In acetonitrile at 20℃; for 2h;
81%	With recombinant Pleurotus eryngii aryl alcohol oxidase; oxygen; catalase In aq. buffer at 30℃; for 18h; Flow reactor; Enzymatic reaction;	Flow reactor experiments General procedure: PFA microreactor coils (750 μm ID) with a volume of 3 and 6 mL were constructed. The reaction mixture was introducedvia a syringe pump (Fusion 200, Chemyx), while the pure oxygen flow was controlled by a mass flow controller (ELFLOW, Bronkhorst), resulting in a segmented flow (SupportingInformation File 1, Figure S8). Residence times were taken as the time between the solution entering and exiting the coil andwere varied by altering the flow, keeping the ratio of oxygen toliquid at three to one. Samples were collected on ice and assoon as enough volume was collected, extracted with ethylacetate and analysed by GC (vide infra).
80%	With mIBX In water at 20℃; for 18h;
71%	With bromine; oxygen In acetic acid at 60℃; for 6h;
66%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; tetrakis(acetonitrile)copper(I) trifluoromethanesulfonate; 5,6,9,10-tetrahydro-4H,8H-pyrido[3,2,1-ij][1,6]naphthyridine; 4,4'-Dimethoxy-2,2'-bipyridin; oxygen In acetonitrile at 147℃; for 15.5h; Schlenk technique; Inert atmosphere;
42%	With 4-(N,N-dimethylamino)pyridinium chlorochromate In dichloromethane for 16h;
91 % Chromat.	With tris(triphenylphosphine)ruthenium(II) chloride In benzene at 25℃; for 4h;
	electrochem. oxidn.;
90 % Chromat.	With tert.-butylhydroperoxide In dichloromethane; 1,2-dichloro-ethane at 20℃; for 12h;
69 % Chromat.	With pyridine; 4 A molecular sieve; oxygen In various solvent(s) at 100℃; for 1h;
90 % Chromat.	With modified o-iodoxybenzoic acid In water at 20℃; for 18h;
	With Celite; pyridinium chlorochromate In dichloromethane at 20℃; for 3h;
67 % Chromat.	With quinolinium monofluorochromate(VI) In hexane at 20℃; for 2h;
100 % Spectr.	With manganese(IV) oxide; Me₂S=CO₂Et In dichloromethane Heating;
93 % Chromat.	With CrO₃/silica gel In dichloromethane at 20℃; for 0.25h;
	With oxygen In dimethyl sulfoxide at 135℃; for 2h;
33 % Chromat.	With oxygen; chloranil; decalin In water at 90℃; for 18h;
46 % Turnov.	With 1,1,1-trifluoro-2-propanone In dichloromethane; toluene at 20℃; for 24h;
81 % Chromat.	With dihydrogen peroxide at 90℃; for 2h;
	Multi-step reaction with 2 steps 1: pyridine / diethyl ether / 5 h / 25 - 30 °C 2: 95 percent Chromat_. / Pd(OAc)2 / acetonitrile / 1 h / 80 °C / Heating
	With oxygen In α,α,α-trifluorotoluene at 110℃;
98 %Chromat.	With acetaldehyde at 30℃; for 24h; aq. phosphate buffer; Microbiological reaction; Combinatorial reaction / High throughput screening (HTS); chemoselective reaction;
	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; N,N′-{1,3-bis[(pyridine-2-ylmethyl)amino]propan-2-al}atodicopper(II)(μ-acetato)diperchlorate; oxygen; sodium hydroxide In water; acetonitrile at 20℃;
	With tert.-butylhydroperoxide In water; acetonitrile at 60℃; for 5h;
	With dimethyl sulfoxide; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In dichloromethane at 0℃; for 1h; Inert atmosphere;
	With oxygen In α,α,α-trifluorotoluene at 110℃;	2 In the oxidation reaction of unsaturated aliphatic alcohols, the maximal oxidation rates obtained for secondary alcohols was higher than those observed for primary alcohols, as presented in Table 2. The only significant by-products in these reactions were the saturated aldehdyes or ketones, namely propanal, hexanal, butanone and so forth, and in the cases where the alcohols were pure E/Z hexen-1-ol isomers, the E-2-hexenal was the major product. No significant amounts of carboxylic acids were formed.Table 2 presents the results obtained for unsaturated alcohols under reaction conditions of 0.1 mmol alcohol, 5 μmol Pd-POM-1, 1 ml TFT, 2 bars O2, and 110° C.,wherein the rate of oxidation yields, determined by GC analysis, is shown as molar percentage, the time for completion/arrest in minutes, and the selectivity for the major product (β-unsaturated aldehyde or ketone respectively) in molar percentage. As can be seen in Table 2, the cis isomers were isomerized to trans products, to and as noticeable from the formation of saturated aldehydes and ketones as by-products, the isomerisation of the double bond competed with the alcohol oxidation reaction.
	With oxygen In toluene at 80℃; for 1h;
> 99 %Chromat.	With palladium in UiO-67; air In toluene at 80℃; for 30h; Green chemistry;
	With Arabidopsis thaliana berberine bridge enzyme-like protein 15 L₁₈₂V; oxygen In dimethyl sulfoxide at 30℃; for 24h; Enzymatic reaction;	2.4. Substrate screening General procedure: Reactions were carried out in 50 mM MES buffer pH 7.0 in the presence of 20% (v/v) DMSO. A total volume of 2 mL reaction mixture was incubated in 11 mL glass test tube with screw cap (Pyrex,Darmstadt, Germany) at 30 C in an orbital shaker at 110 rpm. The reaction was started by the addition of 10 L enzyme to achieve a final enzyme concentration of 1.2 M. After 24 h the reaction mixture was extracted with ethyl acetate (2 1 mL), the combined organic phase was dried with Na2SO4 and subjected to GC analysis to identify putative products.
	With recombinant aryl alcohol oxidase from Pleurotus eryngii; oxygen; catalase In aq. phosphate buffer; dodecane at 20℃; for 336h; Enzymatic reaction;
	With silica gel; pyridinium chlorochromate In dichloromethane for 4h; Molecular sieve; Inert atmosphere;	(E)-Hex-2-enal 6 To a suspension of PCC (0.57 g, 2.64 mmol), Celite (0.9 g), and 4 Å molecular sieves (activated powder, 0.9 g) in CH2Cl2 (15 mL) under an atmosphere of nitrogen was added a solution of 12 (0.22 g, 1.3 mmol) in CH2Cl2 (5 mL) dropwise. After stirring for 4 hours, diethyl ether (40 mL) was added and the mixture stirred for an additional hour before filtering over a Celite and silica pad. The solid was washed with 9:1 pentane:diethyl ether (60 mL) and the mixture was concentrated in vacuo without application of heat. Due to the volatility of 6, it was not isolated, solvent was concentrated in vacuo, and crude 6 was used directly in the next reaction.
	With Dess-Martin periodane In dichloromethane at 0℃; for 1h; Inert atmosphere;

Reference： [1]Semmelhack, M. F.; Schmid, Christopher R.; Cortes, David A.; Chou, Chuen S. [Journal of the American Chemical Society, 1984, vol. 106, # 11, p. 3374 - 3376]
[2]McAllister, Graeme D.; Oswald, Magalie F.; Paxton, Richard J.; Raw, Steven A.; Taylor, Richard J.K. [Tetrahedron, 2006, vol. 62, # 28, p. 6681 - 6694]
[3]Healy, Alan R.; Vinale, Francesco; Lorito, Matteo; Westwood, Nicholas J. [Organic Letters, 2015, vol. 17, # 3, p. 692 - 695]
[4]Kaneda, Kiyotomi; Fujie, Yoko; Ebitani, Kohki [Tetrahedron Letters, 1997, vol. 38, # 52, p. 9023 - 9026]
[5]Nakano, Tatsuya; Ishii, Yasutaka; Ogawa, Masaya [Journal of Organic Chemistry, 1987, vol. 52, # 22, p. 4855 - 4859]
[6]Kaneda, Kiyotomi; Fujii, Masanori; Morioka, Kengo [Journal of Organic Chemistry, 1996, vol. 61, # 14, p. 4502 - 4503]
[7]Choudary, B. M.; Durgaprasad, A.; Valli, V. L. K. [Tetrahedron Letters, 1990, vol. 31, # 40, p. 5785 - 5788]
[8]Location in patent: experimental part Kumpulainen, Esa T. T.; Koskinen, Ari M. P. [Chemistry - A European Journal, 2009, vol. 15, # 41, p. 10901 - 10911]
[9]Van Schie, Morten M.C.H.; De Almeida, Tiago Pedroso; Laudadio, Gabriele; Tieves, Florian; Fernández-Fueyo, Elena; Noël, Timothy; Arends, Isabel W.C.E.; Hollmann, Frank [Beilstein Journal of Organic Chemistry, 2018, vol. 14, p. 697 - 703]
[10]Current Patent Assignee: WESTERN ILLINOIS UNIVERSITY - US2004/30187, 2004, A1 Location in patent: Page Sheet 2
[11]Hirano, Masao; Morimoto, Takashi; Itoh, Keiko [Bulletin of the Chemical Society of Japan, 1988, vol. 61, # 10, p. 3749 - 3751]
[12]Koenning, Daniel; Hiller, Wolf; Christmann, Mathias [Organic Letters, 2012, vol. 14, # 20, p. 5258 - 5261]
[13]Guziec, Frank S.; Luzzio, Frederick A. [Journal of Organic Chemistry, 1982, vol. 47, # 9, p. 1787 - 1789]
[14]Tomioka, Hiroki; Takai, Kazuhiko; Oshima, Koichiro; Nozaki, Hitosi [Tetrahedron Letters, 1981, vol. 22, # 17, p. 1605 - 1608]
[15]Komoschinski, Joachim; Steckhan, Eberhard [Tetrahedron Letters, 1988, vol. 29, # 27, p. 3299 - 3300]
[16]Fung, Wai-Hong; Yu, Wing-Yiu; Che, Chi-Ming [Journal of Organic Chemistry, 1998, vol. 63, # 9, p. 2873 - 2877]
[17]Coleman, Karl S.; Coppe, Maurice; Thomas, Christophe; Osborn, John A. [Tetrahedron Letters, 1999, vol. 40, # 19, p. 3723 - 3726]
[18]Thottumkara, Arun P; Vinod, Thottumkara K [Tetrahedron Letters, 2002, vol. 43, # 4, p. 569 - 572]
[19]Bressette, Andrew R.; Glover IV, Louis C. [Synlett, 2004, # 4, p. 738 - 740]
[20]Rajkumar, G. Abraham; Sivamurugan; Arabindoo, Banumathi; Murugesan [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2004, vol. 43, # 5, p. 936 - 946]
[21]Oswald, Magalie F.; Raw, Steven A.; Taylor, Richard J. K. [Organic Letters, 2004, vol. 6, # 22, p. 3997 - 4000]
[22]Gonzalez-Nunez, Maria Elena; Mello, Rossella; Olmos, Andrea; Accrete, Rafael; Asensio, Gregorio [Journal of Organic Chemistry, 2006, vol. 71, # 3, p. 1039 - 1042]
[23]Khenkin, Alexander M.; Neumann, Ronny [Journal of Organic Chemistry, 2002, vol. 67, # 20, p. 7075 - 7079]
[24]Neumann, Ronny; Khenkin, Alexander M.; Vigdergauz, Inga [Chemistry - A European Journal, 2000, vol. 6, # 5, p. 875 - 882]
[25]Mello, Rossella; Martinez-Ferrer, Jaime; Asensio, Gregorio; Gonzalez-Nunez, Maria Elena [Journal of Organic Chemistry, 2007, vol. 72, # 24, p. 9376 - 9378]
[26]Kon, Yoshihiro; Usui, Yoko; Sato, Kazuhiko [Chemical Communications, 2007, # 42, p. 4399 - 4400]
[27]Minami, Ichiro; Tsuji, Jiro [Tetrahedron, 1987, vol. 43, # 17, p. 3903 - 3916]
[28]Location in patent: scheme or table Barats, Delina; Neumann, Ronny [Advanced Synthesis and Catalysis, 2010, vol. 352, # 2-3, p. 293 - 298]
[29]Location in patent: experimental part Orbegozo, Thomas; De Vries, Johannes G.; Kroutil, Wolfgang [European Journal of Organic Chemistry, 2010, # 18, p. 3445 - 3448]
[30]Striegler, Susanne; Dunaway, Natasha A.; Gichinga, Moses G.; Milton, Lisa K. [Tetrahedron, 2010, vol. 66, # 40, p. 7927 - 7932]
[31]Location in patent: experimental part Chattopadhyay, Tanmay; Kogiso, Masaki; Asakawa, Masumi; Shimizu, Toshimi; Aoyagi, Masaru [Catalysis Communications, 2010, vol. 12, # 1, p. 9 - 13]
[32]Location in patent: experimental part Radha Krishna, Palakodety; Ramana, D. Venkata [Journal of Organic Chemistry, 2012, vol. 77, # 1, p. 674 - 679]
[33]Current Patent Assignee: WEIZMANN INSTITUTE OF SCIENCE - US2012/197033, 2012, A1 Location in patent: Page/Page column 10-11
[34]Chen, Gongzhou; Wu, Shijian; Liu, Hongli; Jiang, Huanfeng; Li, Yingwei [Green Chemistry, 2013, vol. 15, # 1, p. 230 - 235]
[35]Chen, Liyu; Chen, Huirong; Luque, Rafael; Li, Yingwei [Chemical Science, 2014, vol. 5, # 10, p. 3708 - 3714]
[36]Pils, Sabine; Schnabl, Kordula; Wallner, Silvia; Daniel, Bastian; Macheroux, Peter; Kljajic, Marko; Kupresanin, Nina; Breinbauer, Rolf; Fuchs, Michael; Rocha, Raquel; Schrittwieser, Joerg H.; Kroutil, Wolfgang [Journal of Molecular Catalysis B: Enzymatic, 2016, vol. 133, p. S6 - S14]
[37]de Almeida; van Schie; Ma; Tieves; Younes; Fernández-Fueyo; Arends; Riul; Hollmann [Advanced Synthesis and Catalysis, 2019, vol. 361, # 11, p. 2668 - 2672]
[38]Muhl, Jennifer R.; Pilkington, Lisa I.; Deed, Rebecca C. [Tetrahedron Letters, 2020, vol. 61, # 28]
[39]Elizebath, Drishya; Jachak, Gorakhnath R.; Reddy, D. Srinivasa; Shanmugam, Dhanasekaran; Shukla, Anurag [European Journal of Organic Chemistry, 2021, vol. 2021, # 15, p. 2212 - 2218]

13
[ 867-13-0 ]
[ 6728-26-3 ]
[ 60388-61-6 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: diethoxyphosphoryl-acetic acid ethyl ester With sodium hydride In tetrahydrofuran; mineral oil at -20℃; for 1h; Stage #2: (E)-2-Hexenal In tetrahydrofuran; mineral oil at -20℃;
70.2%	Stage #1: diethoxyphosphoryl-acetic acid ethyl ester With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 1h; Inert atmosphere; Stage #2: (E)-2-Hexenal In tetrahydrofuran; mineral oil at -78 - 20℃; for 2h; Inert atmosphere;
64%	Stage #1: diethoxyphosphoryl-acetic acid ethyl ester With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 0.5h; Inert atmosphere; Stage #2: (E)-2-Hexenal In tetrahydrofuran; mineral oil at 0 - 20℃; for 17h; Inert atmosphere; stereoselective reaction;

	With sodium hydride In various solvent(s)
	With sodium hydride In tetrahydrofuran
	Stage #1: diethoxyphosphoryl-acetic acid ethyl ester With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 0.5h; Inert atmosphere; Stage #2: (E)-2-Hexenal In tetrahydrofuran; mineral oil at 0℃; for 1h; Inert atmosphere;
	With sodium hydride In tetrahydrofuran at 0 - 20℃; for 4h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Walleser, Patrick; Brueckner, Reinhard [European Journal of Organic Chemistry, 2010, # 25, p. 4802 - 4822]
[2]Artok, Levent; Bilgi, Yasemin; Kuş, Melih [Organic and biomolecular chemistry, 2020, vol. 18, # 32, p. 6378 - 6383]
[3]Goodreid, Jordan D.; Wong, Keith; Leung, Elisa; McCaw, Shannon E.; Gray-Owen, Scott D.; Lough, Alan; Houry, Walid A.; Batey, Robert A. [Journal of Natural Products, 2014, vol. 77, # 10, p. 2170 - 2181]
[4]Nakanishi, Saburo; Kumeta, Katsuhisa; Nakanishi, Jun-Ichi; Takata, Toshikazu [Tetrahedron Asymmetry, 1995, vol. 6, # 9, p. 2097 - 2100]
[5]Matsumoto, Akikazu; Sada, Kazuki; Tashiro, Kohji; Miyata, Mikiji; Tsubouchi, Takashi; Tanaka, Toshihiro; Odani, Toru; Nagahama, Sadamu; Tanaka, Tomoyuki; Inoue, Katsunari; Saragai, Seishi; Nakamoto, Shinsuke [Angewandte Chemie - International Edition, 2002, vol. 41, # 14, p. 2502 - 2505]
[6]Elizebath, Drishya; Jachak, Gorakhnath R.; Reddy, D. Srinivasa; Shanmugam, Dhanasekaran; Shukla, Anurag [European Journal of Organic Chemistry, 2021, vol. 2021, # 15, p. 2212 - 2218]
[7]Wang, Lei; Wang, Lifan; Li, Mingxia; Chong, Qinglei; Meng, Fanke [Journal of the American Chemical Society, 2021, vol. 143, # 32, p. 12755 - 12765]

14
[ 928-95-0 ]
[ 6728-26-3 ]
[ 106498-75-3 ]

Yield	Reaction Conditions	Operation in experiment
83 % Spectr.	With tert.-butylhydroperoxide; 3 A molecular sieve In 2,2,4-trimethylpentane; cyclohexane Heating;
	With tert.-butylhydroperoxide In decane; toluene at 79.84℃; for 24h;	2.3. Catalytic epoxidation of olefins General procedure: Catalytic tests were carried out in a Carousel 12 Plus ReactionStation from Radleys. A given amount (1.6 mmol) of the olefin substrates- cis-cyclooctene, styrene, 1-octene, trans-2-hexen-1-ol, R-(+)-limonene - was mixed with dibutylether (1.6 mmol) (internalstandard) and 15 μL (5 mol %) of tert-butyl hydroperoxide (5.5M solutionin decane; tbhp). Then the catalyst was added to this mixture.This was either 10 mL of exfoliated materials ExHTCo/Al-met-Au(0.016 mol Au) with an extra 5 mL of acetonitrile or 100 mg of HTCo/Almet-Au (0.016 mol Au) bulk catalyst with 8 mL of toluene. The magneticallystirred mixture was heated to 353 K and kept for 80 h.

Reference： [1]Palombi, Laura; Bonadiesa, Francesco; Scettri, Arrigo [Tetrahedron, 1997, vol. 53, # 46, p. 15867 - 15876]
[2]Leandro, Sónia R.; Fernandes, Cristina I.; Viana; Mourato; Vaz, Pedro D.; Nunes, Carla D. [Applied Catalysis A: General, 2019, vol. 584]

15
[ 6728-26-3 ]
[ 30018-16-7 ]
(2E,4E)-ethyl 2-methylocta-2,4-dienoate [ No CAS ]

Reference： [1]Journal of Organic Chemistry,1998,vol. 63,p. 2948 - 2953

16
[ 6728-26-3 ]
[ 100-51-6 ]
[ 6938-45-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With 1,3-dimethylbenzimidazolium Iodide; 1,8-diazabicyclo[5.4.0]undec-7-ene; phenol In toluene at 110℃;
90%	With 1,3-dimethylbenzimidazolium Iodide; 1,8-diazabicyclo[5.4.0]undec-7-ene; phenol In toluene at 100℃;
71%	With 1,4-bis[2,6-di(2-propyl)phenyl]-3-phenyl-1H-1,2,4-triazol-4-ium chloride; N-ethyl-N,N-diisopropylamine at 100℃; for 6h;

28%

With 1-butyl-3-methylimidazolium tetrafluoroborate; 1,3-bis(mesityl)imidazolium chloride at 60℃; for 2h; Inert atmosphere; Electrolysis;

Reference： [1]Chan, Audrey; Scheidt, Karl A. [Organic Letters, 2005, vol. 7, # 5, p. 905 - 908]
[2]Maki, Brooks E.; Chan, Audrey; Scheidt, Karl A. [Synthesis, 2008, # 8, p. 1306 - 1315]
[3]Yatham, Veera Reddy; Harnying, Wacharee; Kootz, Darius; Neudörfl, Jörg-M.; Schlörer, Nils E.; Berkessel, Albrecht [Journal of the American Chemical Society, 2016, vol. 138, # 8, p. 2670 - 2677]
[4]Feroci, Marta; Chiarotto, Isabella; Orsini, Monica; Pelagalli, Romina; Inesi, Achille [Chemical Communications, 2012, vol. 48, # 43, p. 5361 - 5363]

17
[ 930-88-1 ]
[ 6728-26-3 ]
[ 7223-30-5 ]
N-(4-ethyl-2,3,3a,4,7,7a-hexahydro-2-methyl-1,3-dioxo-1H-isoindol-7-yl)-3-phenylpropiolamide [ No CAS ]

Reference： [1]Tetrahedron,2005,vol. 61,p. 11333 - 11344

18
[ 6728-26-3 ]
[ 7223-30-5 ]
[ 762-42-5 ]
dimethyl 3-(3-phenylpropiolamido)-6-ethylcyclohexa-1,4-diene-1,2-dicarboxylate [ No CAS ]

Reference： [1]Tetrahedron,2005,vol. 61,p. 11333 - 11344

19
[ 6728-26-3 ]
[ 63922-69-0 ]
(1Z,3E)-1-(trimethylsilylmethyl)-4-propyl-1,3-butadiene [ No CAS ]
(E,E)-1-(trimethylsilylmethyl)-4-propyl-1,3-butadiene [ No CAS ]

Reference： [1]Phosphorus, Sulfur and Silicon and the Related Elements,2006,vol. 181,p. 2283 - 2295

20
[ 673-32-5 ]
[ 6728-26-3 ]
(1RS,4SR)-3-methyl-2-phenyl-4-propylcyclopent-2-enol [ No CAS ]
(1RS,4RS)-3-methyl-2-phenyl-4-propylcyclopent-2-enol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethyl borane; tributylphosphine In tetrahydrofuran; methanol at 50℃; for 1h; Title compound not separated from byproducts;
	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; triethyl borane; tributylphosphine In tetrahydrofuran; methanol at 50℃; for 1h; optical yield given as %de; diastereoselective reaction;
	With bis(1,5-cyclooctadiene)nickel⁽⁰⁾; triethyl borane; tributylphosphine In tetrahydrofuran; methanol at 20 - 50℃; Inert atmosphere; optical yield given as %de;

With bis(1,5-cyclooctadiene)nickel⁽⁰⁾; triethyl borane; tris(2,4,6-trimethoxyphenyl)phosphine In tetrahydrofuran; methanol at 20 - 50℃; Inert atmosphere; optical yield given as %de;

Reference： [1]Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2006, vol. 128, # 43, p. 14030 - 14031]
[2]Jenkins, Aireal D.; Herath, Ananda; Song, Minsoo; Montgomery, John [Journal of the American Chemical Society, 2011, vol. 133, # 36, p. 14460 - 14466]
[3]Li, Wei; Montgomery, John [Chemical Communications, 2012, vol. 48, # 8, p. 1114 - 1116]
[4]Li, Wei; Montgomery, John [Chemical Communications, 2012, vol. 48, # 8, p. 1114 - 1116]

21
[ 6728-26-3 ]
[ 1003-99-2 ]
[ 904694-63-9 ]

Yield	Reaction Conditions	Operation in experiment
9.33%	Stage #1: (E)-2-Hexenal; 2-bromo-5-fluoroaniline With phosphoric acid; 3-Nitrobenzenesulfonic acid In water at 80 - 100℃; for 3h; Stage #2: With ammonia In water	38.1 2-Bromo-5-fluoro-aniline (5.00 g, 95 mass% article, 25.0 mmol), m-nitrobenzenesulfonic acid (2.65 g, 13.0 mmol), 20.0 mL of 85 wt% aqueous phosphoric acid solution and ferrous sulfate heptahydrate (65.5 mg, 0.250 mmol) were placed in a 100 mL three-neck flask equipped with a magnetic stirrer, a reflux condenser, a thermometer and a dropping funnel and the mixture was heated to 80°C in an oil bath. Subsequently, trans-2-hexenal (6.51 g, 98 mass% article, 65.0 mmol) was added dropwise thereto through the dropping funnel for 1 hour. After completion of the dropwise addition, the mixture was heated and stirred at 100°C for 2 hours. Then, the reaction mixture was poured into water and neutralized to pH 7 by ammonia water. The neutralized liquid was extracted with dichloromethane, and then dichloromethane was removed under reduced pressure. The resulting crude reaction product was purified by column chromatography (Hexane/AcOEt=100/0->1/10) using silica gel, followed by drying under reduced pressure to give 625 mg of 8-bromo-5-fluoro-2-propylquinoline as a yellowish white solid (yield: 9.33%). 1H-NMR (300 MHz, CDCl3) δ: 8.32 (d, 1H), 7.95-7.90 (m, 1H), 7.40 (d, 1H), 7.08-7.01 (m, 1H), 3.05-3.00 (m, 2H), 1.95-1.85 (m, 2H), 1.05 (t, 3H) [MS] EI (m/z): 268 (M+), CI (m/z): 269 (MH+)

Reference： [1]Current Patent Assignee: UBE INDUSTRIES LIMITED - EP1847545, 2007, A1 Location in patent: Page/Page column 52

22
[ 6728-26-3 ]
[ 14776-35-3 ]
all-syn-tetrahydro-3,5-diphenyl-6-propyl-5H-pyrazolo[1,2-a]pyridazine-1,8-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 45℃; for 2h;

Reference： [1]Chan, Audrey; Scheidt, Karl A. [Journal of the American Chemical Society, 2007, vol. 129, # 17, p. 5334 - 5335]

23
[ 6728-26-3 ]
[ 76292-76-7 ]
CH₂CH₂C₄H₆OC₇H₆NC₃H₁₁C₄O₄ [ No CAS ]
CH₂CH₂C₄H₆OC₇H₆NC₃H₁₁C₄O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With (S)-diphenylprolinol; water In tetrahydrofuran at 4℃; for 72h;

Reference： [1]Vicario, Jose L.; Reboredo, Silvia; Badia, Dolores; Carrillo, Luisa [Angewandte Chemie - International Edition, 2007, vol. 46, # 27, p. 5168 - 5170]

24
[ 6728-26-3 ]
[ 24812-90-6 ]
[ 71-36-3 ]
methyl 8-methoxy-2-n-propylquinoline-5-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; ammonium hydroxide; chloranil;Zinc chloride; In tetrahydrofuran;	REFERENCE EXAMPLE 27 Methyl-8-methoxy-2-n-propylquinoline-5-carboxylate Methyl-<strong>[24812-90-6]3-amino-4-methoxybenzoate</strong> (10.0 g) was treated with concentrated hydrochloric acid (14 ml) and n-butanol (10 ml), under nitrogen, with stirring. The stirred mixture was treated with p-chloranil (13.65 g) and then heated at reflux whilst a mixture of trans-2-hexanal (8 ml) and n-butanol (5 ml) was added dropwise over 2 hours using a syringe pump. After heating at reflux for a further 30 minutes the mixture was treated with a solution of anhydrous zinc chloride (7.52 g) in tetrahydrofuran (60 ml), then allowed to cool slowly to room temperature and then cooled to 0 C. for 18 hours. The reaction mixture was evaporated, then diluted with hydrochloric acid (1M) and then washed with diethyl ether. The pH of the solution was adjusted to 6 and the resulting emulsion was treated with ammonium hydroxide and the solution extracted with diethyl ether. The combined dark green extracts were dried over magnesium sulphate then evaporated. The resulting dark green oil was subjected to flash chromatography on silica eluding with a mixture of ethyl acetate and pentane (3:7, v/v) to give the title compound (1.5 g) as an orange oil. NMR(CDCl3): delta9.36(d,J=8.9 Hz,1 H), 8.26(d,J=8.4 Hz,1 H), 7.47(d,J=8.9 Hz,1 H), 7.03(d,J=8.4 Hz,1 H), 4.14(s,3 H), 3.97(s,3 H), 3.02(m,2 H), 1.86(m,2 H), 1.03(t,J=7.3 Hz,3 H).

Reference： [1]Patent: US6303600,2001,B1

25
[ 67-56-1 ]
[ 6728-26-3 ]
[ 928-49-4 ]
[ 1005396-35-9 ]

Yield	Reaction Conditions	Operation in experiment
52%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 50℃; for 2h;

Reference： [1]Herath, Ananda; Li, Wei; Montgomery, John [Journal of the American Chemical Society, 2008, vol. 130, # 2, p. 469 - 471]

26
C₁₄H₁₂N₂O [ No CAS ]
[ 6728-26-3 ]
[ 1012335-11-3 ]

Yield	Reaction Conditions	Operation in experiment
84%	With 4 A molecular sieve; 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0℃;

Reference： [1]Chan, Audrey; Scheidt, Karl A. [Journal of the American Chemical Society, 2008, vol. 130, # 9, p. 2740 - 2741]

27
(E)-1,3-bis(4-bromophenyl)-N-(4-methoxyphenylsulfonyl)prop-2-en-1-imine [ No CAS ]
[ 6728-26-3 ]
[ 1005772-87-1 ]

Yield	Reaction Conditions	Operation in experiment
77%	With 1,8-diazabicyclo[5.4.0]undec-7-ene In ethyl acetate at 20℃; for 15h;

Reference： [1]He, Ming; Bode, Jeffrey W. [Journal of the American Chemical Society, 2008, vol. 130, # 2, p. 418 - 419]

28
(E)-1,3-diphenyl-N-(4-methoxyphenylsulfonyl)prop-2-en-1-imine [ No CAS ]
[ 6728-26-3 ]
[ 1005772-83-7 ]

Yield	Reaction Conditions	Operation in experiment
81%	With 1,8-diazabicyclo[5.4.0]undec-7-ene In ethyl acetate at 20℃; for 15h;

Reference： [1]He, Ming; Bode, Jeffrey W. [Journal of the American Chemical Society, 2008, vol. 130, # 2, p. 418 - 419]

29
[ 6728-26-3 ]
[ 55962-05-5 ]
[ 1017582-07-8 ]

Yield	Reaction Conditions	Operation in experiment
99%	In dichloromethane at 20℃; for 0.5h;
83%	With pyridine; iron(II) chloride In dichloromethane at 20℃; for 18h; Molecular sieve; Inert atmosphere;

Reference： [1]Chang, Joyce Wei Wei; Chan, Philip Wai Hong [Angewandte Chemie - International Edition, 2008, vol. 47, # 6, p. 1138 - 1140]
[2]Location in patent: experimental part Ton, Thi My Uyen; Tejo, Ciputra; Tania, Stefani; Chang, Joyce Wei Wei; Chan, Philip Wai Hong [Journal of Organic Chemistry, 2011, vol. 76, # 12, p. 4894 - 4904]

30
[ 83-72-7 ]
[ 6728-26-3 ]
C₁₆H₁₆O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With (2S)-2-{bis[3,5-bis(CF₃)phenyl](Me₃SiO)methyl}pyrrolidine In dichloromethane at -20℃; for 72h;

Reference： [1]Rueping, Magnus; Sugiono, Erli; Merino, Estibaliz [Angewandte Chemie - International Edition, 2008, vol. 47, # 16, p. 3046 - 3049]

31
[ 673-32-5 ]
[ 617-86-7 ]
[ 6728-26-3 ]
[ 1035485-05-2 ]

Yield	Reaction Conditions	Operation in experiment
91%	With bis(1,5-cyclooctadiene)nickel⁽⁰⁾; tricyclohexylphosphine In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; stereoselective reaction;

Reference： [1]Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2008, vol. 130, # 26, p. 8132 - 8133]

32
[ 673-32-5 ]
[ 6728-26-3 ]
[ 1035485-08-5 ]

Yield	Reaction Conditions	Operation in experiment
86%	With bis(1,5-cyclooctadiene)nickel⁽⁰⁾; Dimethylphenylsilane; tricyclohexylphosphine In tetrahydrofuran at 50℃; for 1h; Inert atmosphere; stereoselective reaction;

Reference： [1]Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2008, vol. 130, # 26, p. 8132 - 8133]

33
[ 673-32-5 ]
[ 6728-26-3 ]
[ 29681-57-0 ]
[ 1035485-06-3 ]

Reference： [1]Journal of the American Chemical Society,2008,vol. 130,p. 8132 - 8133

34
[ 673-32-5 ]
[ 6728-26-3 ]
[ 789-25-3 ]
[ 1035485-07-4 ]

Yield	Reaction Conditions	Operation in experiment
88%	With bis(1,5-cyclooctadiene)nickel⁽⁰⁾; tricyclohexylphosphine In tetrahydrofuran at 50℃; for 1h; Inert atmosphere; stereoselective reaction;

Reference： [1]Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2008, vol. 130, # 26, p. 8132 - 8133]

35
[ 617-86-7 ]
[ 6728-26-3 ]
[ 928-49-4 ]
[ 1035485-09-6 ]

Yield	Reaction Conditions	Operation in experiment
75%	With bis(1,5-cyclooctadiene)nickel⁽⁰⁾; tricyclohexylphosphine In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; stereoselective reaction;
75%	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; tricyclohexylphosphine In tetrahydrofuran at 20 - 50℃; Inert atmosphere; stereoselective reaction;

Reference： [1]Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2008, vol. 130, # 26, p. 8132 - 8133]
[2]Li, Wei; Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2009, vol. 131, # 46, p. 17024 - 17029]

36
[ 617-86-7 ]
[ 6728-26-3 ]
[ 10229-11-5 ]
[ 1035485-18-7 ]

Yield	Reaction Conditions	Operation in experiment
91%	With bis(1,5-cyclooctadiene)nickel⁽⁰⁾; tricyclohexylphosphine In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; stereoselective reaction;
91%	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; tricyclohexylphosphine In tetrahydrofuran at 20 - 50℃; Inert atmosphere; stereoselective reaction;

Reference： [1]Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2008, vol. 130, # 26, p. 8132 - 8133]
[2]Li, Wei; Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2009, vol. 131, # 46, p. 17024 - 17029]

37
[ 617-86-7 ]
[ 6728-26-3 ]
4-phenyl-but-3-yn-2-ol [ No CAS ]
[ 1035485-17-6 ]

Yield	Reaction Conditions	Operation in experiment
85%	With bis(1,5-cyclooctadiene)nickel⁽⁰⁾; tricyclohexylphosphine In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; stereoselective reaction;
85%	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; tricyclohexylphosphine In tetrahydrofuran at 20 - 50℃; Inert atmosphere; stereoselective reaction;

Reference： [1]Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2008, vol. 130, # 26, p. 8132 - 8133]
[2]Li, Wei; Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2009, vol. 131, # 46, p. 17024 - 17029]

38
[ 617-86-7 ]
[ 6728-26-3 ]
[ 62248-76-4 ]
[ 1035485-19-8 ]

Yield	Reaction Conditions	Operation in experiment
65%	With bis(1,5-cyclooctadiene)nickel⁽⁰⁾; tricyclohexylphosphine In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; stereoselective reaction;
65%	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; tricyclohexylphosphine In tetrahydrofuran at 20 - 50℃; Inert atmosphere; stereoselective reaction;

Reference： [1]Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2008, vol. 130, # 26, p. 8132 - 8133]
[2]Li, Wei; Herath, Ananda; Montgomery, John [Journal of the American Chemical Society, 2009, vol. 131, # 46, p. 17024 - 17029]

39
[ 6728-26-3 ]
[ 119924-96-8 ]
[ 1132746-64-5 ]

Yield	Reaction Conditions	Operation in experiment
79%	With diisopropylamine In toluene at 23℃; for 24h; regioselective reaction;

Reference： [1]Tan, Bin; Shi, Zugui; Chua, Pei Juan; Li, Yongxin; Zhong, Guofu [Angewandte Chemie - International Edition, 2009, vol. 48, # 4, p. 758 - 761]

40
[ 638989-40-9 ]
[ 6728-26-3 ]
[ 1176220-06-6 ]

Yield	Reaction Conditions	Operation in experiment
32%	With N-Methyldicyclohexylamine In 1,4-dioxane; hexane at 20 - 100℃;	26 Example 26(2E)-3-(4,4-Diethyl-2-oxo-1,4-dihydro-2H-3,1-benzoxazin-6-yl)hex-2-enal; (E)-Hex-2-enal (450 μL, 3.88 mmol) and N,N-dicyclohexylmethylamine (832 μL 3.88 mmol) were added to a suspension of 6-bromo-4,4-diethyl-1,4-dihydro-2H-3,1-benzoxazin-2-one (1.0024 g, 3.53 mmol), prepared in step 2 of Example 22, in anhydrous dioxane (10 mL) and the resulting solution put under nitrogen. Tri-tert-butylphosphine (638 μL, 10% by weight in hexane; 0.212 mmol) was added and the solution purged with nitrogen. Tris(dibenzylideneacetone)dipalladium (0) (103.7 mg, 0.113 mmol) was added and the mixture again purged with nitrogen. The reaction was stirred under nitrogen at 100° C. for 6 hours, stood overnight at room temperature and then concentrated under reduced pressure. Purification of the residue on silica gel (500 g; 230-400 mesh) using 3:2 hexane:ethyl acetate as the eluent gave 611.7 mg of a yellow solid. NMR analysis of the solid indicated that it was a mixture of components. Additional purification by reverse phase chromatography using a Luna C18 250×50 mm column and a gradient of acetonitrile/water gave the title compound (343.1 mg, 32%) as a white solid, mp 173-179° C., MS (ESI) m/z 302.

Reference： [1]Current Patent Assignee: PFIZER INC - US2009/197878, 2009, A1 Location in patent: Page/Page column 16

41
[ 62147-49-3 ]
[ 6728-26-3 ]
[ 1186655-96-8 ]

Yield	Reaction Conditions	Operation in experiment
96%	With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine; benzoic acid In chloroform at 20℃; for 16h; optical yield given as %ee; enantioselective reaction;

Reference： [1]Reyes, Efraim; Talavera, Garazi; Vicario, Jose L.; Badia, Dolores; Carrillo, Luisa [Angewandte Chemie - International Edition, 2009, vol. 48, # 31, p. 5701 - 5704][Angewandte Chemie, 2009, vol. 121, # 31, p. 5811 - 5814]

42
[ 6728-26-3 ]
[ 309947-86-2 ]
C₂₁H₃₁N₅O₅ [ No CAS ]

Reference： [1]Chemistry - A European Journal,2011,vol. 17,p. 4095 - 4098

43
[ 6728-26-3 ]
[ 141-97-9 ]
[ 1132746-53-2 ]

Yield	Reaction Conditions	Operation in experiment
65%	Stage #1: ethyl acetoacetate With acetic acid; sodium nitrite In water at 20℃; for 0.5h; Stage #2: (E)-2-Hexenal In water at 20℃; for 24h;	To a solution of ethyl acetoacetate or acetoacetate or methyl 3-oxopentanoate (0.5 mmol) in acetic acid (0.6 mmol) were added sodium nitrite (0.6 mmol) in water (1 mL) dropwise. After stirring at room temperature for 30 minutes (E)-hex-2-enal 2a (1.25 mmol) was added in one portion, followed by adding catalyst VII (0.1 mmol) in water (1 mL). The resulting mixture was stirred vigorously. After the reaction was completed (monitored by TLC), the mixture were quenched with saturated ammonium chloride extracted with dichloromethane three times, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The product 3a was afforded by flash chromatography over silica gel in 65% yield. The product 3o was afforded by flash chromatography over silica gel in 52% yield. The product 3k was afforded by flash chromatography over silica gel in 57% yield.

Reference： [1]Current Patent Assignee: NANYANG TECHNOLOGICAL UNIVERSITY - US2011/124881, 2011, A1 Location in patent: Page/Page column 15-16

44
[ 6728-26-3 ]
[ 306-44-5 ]
[ 1132746-86-1 ]

Yield	Reaction Conditions	Operation in experiment
58%	In toluene at 20℃; for 8h;	Mechanism Investigation (Control Experiments) O-Selective Michael Addition of Enal (E)-3-(2-Oxopropylideneaminooxy)hexanal (9) To a solution of oxime compound 8 (0.2 mmol, 1.0 eq) and (E)-hex-2-enal 2a (0.5 mmol, 2.5 eq) in toluene (1 mL) was added catalyst VII (0.04 mmol, 0.2 eq) at room temperature. The resulting mixture was stirred vigorously. After 8 hours, the product 9 was afforded by flash chromatography over silica gel (EtOAc/Hexane=1:10) in 58% yield.1H-NMR (400 MHz, CDCl3): δ 9.85 (s, 1H), 7.45 (m, 2H), 4.87-4.81 (m, 1H), 2.86 (dd, J=7.6, 16.8 Hz, 1H), 2.66 (dd, J=3.6, 16.8 Hz, 1H), 2.36 (s, 3H), 1.82-1.71 (m, 1H), 1.68-1.61 (m, 2H), 1.50-1.42 (m, 2H), 0.98 (t, J=7.2 Hz, 3H).13C-NMR (100 MHz, CDCl3): δ 199.9, 196.0, 148.2, 80.3, 48.3, 36.0, 25.5, 18.5, 13.9.

Reference： [1]Current Patent Assignee: NANYANG TECHNOLOGICAL UNIVERSITY - US2011/124881, 2011, A1 Location in patent: Page/Page column 16

45
[ 6728-26-3 ]
[ 190656-01-0 ]
(2R,3S)-benzyl 2-(3-(benzyloxy)-3-oxopropyl)-3-formylaziridine-1-carboxylate [ No CAS ]
(9H-fluoren-9-yl)methyl 2-formyl-3-propylaziridine-1-carboxylate [ No CAS ]
(2S,3R)-(9H-fluoren-9-yl)methyl 2-formyl-3-propylaziridine-1-carboxylate [ No CAS ]

Reference： [1]Chemistry - A European Journal,2011,vol. 17,p. 7904 - 7917

46
[ 6728-26-3 ]
[ 552-16-9 ]
[ 68858-20-8 ]
[ 109745-15-5 ]
[ 1003940-66-6 ]

Yield	Reaction Conditions	Operation in experiment
13.5%		General procedure: Fmoc protected Rink Amide-AM Resin (1.0g, 1.0 eq) was added to a vessel and swelled with DMF for 30 mins. The Fmoc group was removed with the treatment of 20% piperidine/DMF for 20 mins at r.t., two times, followed by thorough washing with DMF, MeOH and DCM, respectively, three times of each. Fmoc-D-Glu-Ot-Bu(1.0g, 3.0 eq), HOBt (320 mg, 3.0 eq) and DIC (373 mL, 3.0 eq) were dissolved in DMF, then poured into the vessel, followed by gentle shaking for 3 h at r.t.. Coupling efficacy was determined by Kaiser test. After the coupling reaction finished, Fmoc deprotection and washing procedure were proceeded. Then, repeating the before-coupling step, coupling step and after-coupling step as described above,Fmoc-Val-OH (803 mg, 3.0 eq) and 2-nitro-5-chloro-benzoic acid (474 mg, 3.0 eq) were subsequently sequentially attached onto the resin. Then the resin was treated with a solution of 2 M SnCl2/NMM/DMF for 12 h at r.t.. Finally, resin-bound 1 (100mg, the rest resin-bound 1 was set aside for further derivazation) was cleaved off the resin with 95%TFA/H2O for 1 h. The residue then was dissolved using MeOH and S3 purified by using the ODS column chromatography and elution of MeOH/H2O in agradient with MeOH level ranging from 10%-45%. The collected fraction was concentrated under reduced pressure and lyophilized to produce 1 (14.8 mg) as yellow powder with the yield of 47.2%.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 4292 - 4295

47
[ 6728-26-3 ]
[ 4998-07-6 ]
[ 35661-60-0 ]
[ 109745-15-5 ]
[ 1003940-98-4 ]

Yield	Reaction Conditions	Operation in experiment
15.8%		General procedure: Fmoc protected Rink Amide-AM Resin (1.0g, 1.0 eq) was added to a vessel and swelled with DMF for 30 mins. The Fmoc group was removed with the treatment of 20% piperidine/DMF for 20 mins at r.t., two times, followed by thorough washing with DMF, MeOH and DCM, respectively, three times of each. Fmoc-D-Glu-Ot-Bu(1.0g, 3.0 eq), HOBt (320 mg, 3.0 eq) and DIC (373 mL, 3.0 eq) were dissolved in DMF, then poured into the vessel, followed by gentle shaking for 3 h at r.t.. Coupling efficacy was determined by Kaiser test. After the coupling reaction finished, Fmoc deprotection and washing procedure were proceeded. Then, repeating the before-coupling step, coupling step and after-coupling step as described above,Fmoc-Val-OH (803 mg, 3.0 eq) and 2-nitro-5-chloro-benzoic acid (474 mg, 3.0 eq) were subsequently sequentially attached onto the resin. Then the resin was treated with a solution of 2 M SnCl2/NMM/DMF for 12 h at r.t.. Finally, resin-bound 1 (100mg, the rest resin-bound 1 was set aside for further derivazation) was cleaved off the resin with 95%TFA/H2O for 1 h. The residue then was dissolved using MeOH and S3 purified by using the ODS column chromatography and elution of MeOH/H2O in agradient with MeOH level ranging from 10%-45%. The collected fraction was concentrated under reduced pressure and lyophilized to produce 1 (14.8 mg) as yellow powder with the yield of 47.2%.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 4292 - 4295

48
[ 6728-26-3 ]
[ 64935-38-2 ]

Reference： [1]Journal of Agricultural and Food Chemistry,2011,vol. 59,p. 1449 - 1456

49
[ 60941-07-3 ]
[ 6728-26-3 ]
C₁₂H₂₀O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With indium In tetrahydrofuran; water at 20℃; for 3h;	Typical procedure for the synthesis of butenolide 5a General procedure: To a stirred solution of Morita-Baylis-Hillman bromide 1a(a) and (f) (255 mg, 1.0 mmol) and crotonaldehyde (2a, 91 mg, 1.3 mmol) in aqueous THF (1:1, 3 mL) was added indium powder (114 mg, 1.0 equiv) and stirred for 3 h at room temperature. After the usual aqueous extractive workup and column chromatographic purification process (hexanes/ether/CH2Cl2, 7:1:1), syn-homoallylic alcohol 3a was obtained as colorless oil, 199 mg (81%). To a stirred solution of 3a (172 mg, 0.7 mmol) in CH2Cl2 (1.5 mL) was added p-TsOH (13 mg, 0.1 equiv), and the reaction mixture was stirred at room temperature for 3 h. After the usual aqueous extractive workup and column chromatographic purification process (hexanes/ether/CH2Cl2, 15:1:1), lactone 4a was obtained as colorless oil, 133 mg (89%). A solution of 4a (107 mg, 0.5 mmol) and DBU (23 mg, 0.3 equiv) in toluene (25 mL) was heated to reflux for 3 h. After the usual aqueous extractive workup and column chromatographic purification process (hexanes/ether, 10:1), butenolide 5a was obtained as colorless oil, 97 mg (91%). Other compounds were synthesized similarly, and the selected spectroscopic data of 3a, 3f, 4a, 4f, 5a-c, 5f, 5g, and 6 are as follows.

Reference： [1]Location in patent: experimental part Park, Bo Ram; Kim, Ko Hoon; Lim, Jin Woo; Kim, Jae Nyoung [Tetrahedron Letters, 2012, vol. 53, # 1, p. 36 - 40]

50
[ 6728-26-3 ]
methyl 2-(bromomethyl)-3-phenylacrylate [ No CAS ]
C₁₇H₂₂O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With indium In tetrahydrofuran; water at 20℃; for 3h;	Typical procedure for the synthesis of butenolide 5a General procedure: To a stirred solution of Morita-Baylis-Hillman bromide 1a(a) and (f) (255 mg, 1.0 mmol) and crotonaldehyde (2a, 91 mg, 1.3 mmol) in aqueous THF (1:1, 3 mL) was added indium powder (114 mg, 1.0 equiv) and stirred for 3 h at room temperature. After the usual aqueous extractive workup and column chromatographic purification process (hexanes/ether/CH2Cl2, 7:1:1), syn-homoallylic alcohol 3a was obtained as colorless oil, 199 mg (81%). To a stirred solution of 3a (172 mg, 0.7 mmol) in CH2Cl2 (1.5 mL) was added p-TsOH (13 mg, 0.1 equiv), and the reaction mixture was stirred at room temperature for 3 h. After the usual aqueous extractive workup and column chromatographic purification process (hexanes/ether/CH2Cl2, 15:1:1), lactone 4a was obtained as colorless oil, 133 mg (89%). A solution of 4a (107 mg, 0.5 mmol) and DBU (23 mg, 0.3 equiv) in toluene (25 mL) was heated to reflux for 3 h. After the usual aqueous extractive workup and column chromatographic purification process (hexanes/ether, 10:1), butenolide 5a was obtained as colorless oil, 97 mg (91%). Other compounds were synthesized similarly, and the selected spectroscopic data of 3a, 3f, 4a, 4f, 5a-c, 5f, 5g, and 6 are as follows.

Reference： [1]Location in patent: experimental part Park, Bo Ram; Kim, Ko Hoon; Lim, Jin Woo; Kim, Jae Nyoung [Tetrahedron Letters, 2012, vol. 53, # 1, p. 36 - 40]

51
[ 848821-58-9 ]
[ 6728-26-3 ]
C₂₆H₃₅NOSi [ No CAS ]

Reference： [1]Organic Letters,2012,vol. 14,p. 3740 - 3743

52
[ 6728-26-3 ]
[ 1129294-89-8 ]
[ 98-01-1 ]
[ 496-64-0 ]
[ 88-14-2 ]
[ 13419-69-7 ]
[ 1401094-48-1 ]
[ 1401094-49-2 ]
[ 1309945-34-3 ]

Reference： [1]Journal of Agricultural and Food Chemistry,2012,vol. 60,p. 9967 - 9973,7

53
[ 6728-26-3 ]
[ 72707-66-5 ]
C₁₀H₁₆O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With indium; In tetrahydrofuran; water; at 20℃; for 24h;	General procedure: At room temperature, 1 mmol aldehyde (R1CHO), 1.2 mmol alpha- (bromomethyl) acrylic acid and 1.2mmol indium powder were added to a stirred mixture of THF (5 ml) and deionized water (5 ml). 6 M HCl was added to the above mixture when the starting aldehyde disappeared (monitored by TLC) and stirring went on for 3~6 hours. Then, the mixture was extracted with ethylacetate (3 × 10ml) and the organic phase dried over anhydrous Na2SO4 and evaporated. The resulting residue was purified by using the Biotage IsoleraTM Spektra One preparative chromatography (silica gel, elution with 0-40% of ethyl acetate in petroleum ether). Structures and yields are showed as follows.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 4393 - 4397

54
[ 6728-26-3 ]
(Z)-4-benzylidene-2-(2,5-difluorophenyl)-1H-imidazol-5(4H)-one [ No CAS ]
6-butyl-2-(2,5-difluorophenyl)-7-phenyl-6,7-dihydropyrano[2,3-d]imidazol-5(3H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With (5aR,10bS)-2-(2,6-diethylphenyl)-4,5a,6,10b-tetrahydroindeno[2,1-b][1,2,4]triazolo[4,3-d][1,4]oxazin-2-ium tetrafluoroborate; tetrabutylammonium acetate; acetic acid In tetrahydrofuran at 23℃; Inert atmosphere; enantioselective reaction;
90%	With (5aR,10bS)-2-(2,6-diethylphenyl)-4,5a,6,10b-tetrahydroindeno[2,1-b][1,2,4]triazolo[4,3-d][1,4]oxazin-2-ium tetrafluoroborate; tetrabutylammonium acetate; acetic acid In tetrahydrofuran at 23℃; Inert atmosphere; stereoselective reaction;	23 General procedure: Into an oven-dried, screw-capped 1 dram vial equipped with a magnetic stirbar was weighed imidazolidinone (0.300 mmol, 1 equiv). The vial was taken into a nitrogen-filled drybox at which time azolium salt C (0.045 mmol, 0.15 equiv) and tetrabutylammonium acetate (0.090 mmol, 0.30 equiv) were added. The vial was capped with a septum cap, removed from the drybox and put under positive N2 pressure. Into the vial were then successively added THF (2.0 mL, 0.15 M), the cinnamaldehyde-derived enal (0.81 mmol, 2.0 equiv), and acetic acid (0.300 mmol, 1.0 equiv) via a syringe. The reaction was stirred at room temperature until consumption of the imidazolidinone was observed by uPLCMS or for 72 h (most reactions were complete within 24 h). The reaction mixture was filtered over a pad of silica gel washing with dichloromethane and concentrated under reduced pressure. Purification by flash chromatography with EtOAc/hexanes afforded the corresponding lactones. The corresponding racemic compounds were prepared by employing the same protocol but with 2-mesityl-6,7-dihydro-5H-pyrrolo[2,1-c][1,2,4]triazol-2-ium tetrafluoroborate (0.045 mmol, 0.15 equiv, azolium A) as the catalyst. Prepared according to the general procedure using (Z)-4-benzylidene-2-(2,5-difluorophenyl)-1H-imidazol-5(4H)-one and (E)-3-(furan-2-yl)acrylaldehyde. The unpurified residue was purified by flash chromatography using 15% EtOAc/hexanes to afford 16 as an off-white solid (80 mg, 66%). Analytical data for 16: 1H NMR (500 MHz, CDCl3) δ 9.45 (d, J=8.1 Hz, 1H), 7.90 (ddd, J=9.2, 6.1, 3.2 Hz, 1H), 7.37 (ap d, J=1.2 Hz, 1H), 7.37-7.27 (m, 3H), 7.11-7.01 (m, 3H), 7.01-6.94 (m, 1H), 6.34 (dd, J=3.2, 1.9 Hz, 1H), 6.02 (d, J=2.9 Hz, 1H), 4.20 (d, J=6.9 Hz, 1H), 3.70 (ddd, J=10.3, 6.8, 4.1 Hz, 1H), 3.30 (ddd, J=15.9, 4.2, 1.2 Hz, 1H), 2.48 (dd, J=15.8, 10.4 Hz, 1H); 13C NMR (CDCl3, 126 MHz) δ 168.4, 159.1 (d, JCF=243.8 Hz), 155.4 (dd, JCF=241.2, 2.2 Hz), 151.8, 149.1, 141.6, 136.7, 136.5, 129.2, 128.3, 128.0, 118.4 (dd, JCF=12.8, 9.2 Hz), 117.1 (dd, JCF=25.6, 8.8 Hz), 116.6 (dd, JCF=24.9, 9.6 Hz), 114.5 (dd, JCF=26.9, 3.7 Hz), 110.7 (d, JCF=3.9 Hz), 110.4, 107.6, 44.9, 38.5, 25.6; IR (film) cm-1 1770, 1636, 1620, 1529, 1482, 1464, 1452, 1173, 1117, 1008, 919, 902, 885, 875, 814, 766, 736, 700; LRMS (ESI): Mass calcd for [M+H]+ C23H17F2N2O3:407.1. found 407.3; Enantiomeric ratio was measured by chiral phase HPLC (Chiralcel OD-H; 5% IPA/3% MeOH/hexanes 0.5 mL/min, 280 nm), Rt1 (major)=32.4, Rt2 (minor)=36.4 min; er=98:2.

Reference： [1]McCusker, Elizabeth O'Bryan; Scheidt, Karl A. [Angewandte Chemie - International Edition, 2013, vol. 52, # 51, p. 13616 - 13620][Angew. Chem., 2013, vol. 125, # 51, p. 13861 - 13865,5]
[2]Current Patent Assignee: NORTHWESTERN UNIVERSITY (ILLINOIS) - US2014/206886, 2014, A1 Location in patent: Paragraph 0045; 0078; 0101; 0102

55
[ 6728-26-3 ]
[ 90-02-8 ]
[ 1569884-66-7 ]

Yield	Reaction Conditions	Operation in experiment
88%	With 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine In neat (no solvent) at 30℃; for 48h; chemoselective reaction;	Representative procedure for the synthesis of 3-formyl-2H-chromenes 3a-i General procedure: In a screw-capped vial equipped with a magnetic stirrer, salycaldehyde 1a (244 mg, 2 mmol), 3-methyl-3-butenal (2) (168 mg, 2.2 mmol and TBD (28 mg, 0.2 mmol) were consecutively added and the resulting mixture was left under stirring at 30°C.After 48 h the crude mixture was passed through a pad of aluminum oxide(eluent: hexane/ethylacetate 9:1) to yield pure 2,2-dimethyl-2H-chromene-3-carbaldehyde (3a) as a yellow oil (327 mg, 87% yield).

Reference： [1]Lanari, Daniela; Rosati, Ornelio; Curini, Massimo [Tetrahedron Letters, 2014, vol. 55, # 10, p. 1752 - 1755]

56
[ 6728-26-3 ]
[ 1135-12-2 ]
[ 1370728-36-1 ]
[ 1629155-17-4 ]

Reference： [1]Chemistry - A European Journal,2014,vol. 20,p. 5899 - 5904

57
[ 6728-26-3 ]
[ 64951-03-7 ]
1-methoxycarbonyl-2-propyl-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	Stage #1: (E)-2-Hexenal; methyl 2-(3-formyl-1H-indol-2-yl)acetate With 1,4-diaza-bicyclo[2.2.2]octane In water at 60℃; Green chemistry; Stage #2: With hydrogenchloride In water at 60℃; for 48h; Green chemistry;	full text could not be excerpted from SI

Reference： [1]Biswas, Soumen; Majee, Debashis; Dagar, Anuradha; Samanta, Sampak [Synlett, 2014, vol. 25, # 15, p. 2115 - 2120]

58
[ 6728-26-3 ]
[ 5661-50-7 ]
1-(3-hydroxy-5-propyl-4,5-dihydrobenzo[f][1,2]oxazepin-2(3H)-yl)ethanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; silver carbonate; Trimethylacetic acid In acetonitrile at 20℃; for 18h; Glovebox; Inert atmosphere;
88%	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; silver carbonate; Trimethylacetic acid In acetonitrile at 20℃; for 18h; Sealed tube; Glovebox; Inert atmosphere;	9.S92 S92.Preparation of 2-N-acetyl-3-hydroxy-4-hydroxy-5-propyl-1,2-benzoxazepine: In a 15 ml sealed tubeN-phenoxyacetamide (60.5 mg, 0.4 mmol) was added,(Pentamethylcyclopentadiene) rhodium (III) dimer (7.4 mg, 0.012 mmol)Silver carbonate (11.0 mg, 0.04 mmol)And pivalic acid (81.7 mg, 0.8 mmol).And then in the glove box to operate,Three pumping,Three inflatable,Keep the nitrogen atmosphere in the system.To the tube(E) -hexyl-2-enal (92.8 ul, 0.8 mmol)And acetonitrile (2.0 ml).After stirring, the mixture was stirred at room temperature for about 18 hours.After the reaction,filter,Get the crude.The crude product was purified by column chromatography to give the product I-i,Yield 88%.

Reference： [1]Duan, Pingping; Lan, Xia; Chen, Ying; Qian, Shao-Song; Li, Jie Jack; Lu, Liang; Lu, Yanbo; Chen, Bo; Hong, Mei; Zhao, Jing [Chemical Communications, 2014, vol. 50, # 81, p. 12135 - 12138]
[2]Current Patent Assignee: PEKING UNIVERSITY - CN104262283, 2017, B Location in patent: Paragraph 0160; 0161; 0162; 0163

59
[ 6728-26-3 ]
1-hydroxyhexane-1,3-disulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With sodium hydrogensulfite; triethylamine In methanol; water at 20℃; for 12h; Inert atmosphere;	Synthesis and data for 1-hydroxyhexane-1,3-disulfonic acid (3): (E)-Hex-2-enal(1 mL, 8.62 mmol) was added to a solution of NaHSO3 (40% w/v aqueoussolution, 4.71 g, 18.1 mmol) and Et3N (0.126 mL, 1.72 mmol) in MeOH (3 mL),and the resulting mixture stirred for 12 h under an atmosphere of nitrogen. Thesolvent was removed in vacuo, and the crude product was purified using flashchromatography (99:1 MeOH/AcOH) to give the disulfonic acid 3 (2.00 g, 88%)as a white solid. dH (400 MHz; D2O): 0.96 (3H, t, J = 7.6 Hz, 6-CH3), 1.50-1.62 (2H, m, 5-CH2), 1.64-1.73 (1H, m, 4-Ha), 1.84-1.93 (1H, m, 4-Hb), 2.15-2.21(1H, ddd, J = 3.5, 9.6, 14.1 Hz, 2-Ha), 2.27-2.34 (1H, ddd, J = 3.5, 11.1, 14.6 Hz, 2-Hb), 3.04-3.11 (1H, m, 3-H), 4.56-4.59 (1H, m, 1-H); dC (100 MHz; D2O): 13.1(C-6), 13.4 (C-6), 19.3 (C-5), 19.8 (C-5), 31.3 (C-2), 32.0 (C-2), 32.1 (C-4), 32.7(C-4), 56.0 (C-3), 56.2 (C-3), 81.3 (C-1), 82.1 (C-1); denotes the minordiastereomers different in relative stereochemistry at C-1 and C-3. HRMS(ESI) Found [M2H+Na]+: 282.9937, C6H12NaO7S2 requires 282.9928; IR:mmax cm1 3433, 2968, 2874, 1636, 1459, 1184, 1165; Mp >230 C.

Reference： [1]Duhamel, Nina; Piano, Federico; Davidson, Samuel J.; Larcher, Roberto; Fedrizzi, Bruno; Barker, David [Tetrahedron Letters, 2015, vol. 56, # 13, p. 1728 - 1731]

60
[ 6728-26-3 ]
[ 475-38-7 ]
5-ethyl-1,4-dihydroxyanthracene-9,10-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With benzoic acid; <i>L</i>-proline In toluene at 50℃; for 5h; Inert atmosphere; Enzymatic reaction;

Reference： [1]Somai Magar, Krishna Bahadur; Xia, Likai; Lee, Yong Rok [Chemical Communications, 2015, vol. 51, # 41, p. 8592 - 8595]

61
[ 6728-26-3 ]
[ 14340-32-0 ]
(E)-N-((E)-hex-2-enylidene)-4-phenylpiperazin-1-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	In toluene at 100℃; for 3h;	31 4.2.3. General procedure (GP-1) General procedure: An aluminum reaction block was placed on a hotplate stirrer. A brown 10 mL reaction vessel was charged consecutively with 1.00 equiv 4-phenylpiperazin-1-amine, toluene, 1.00 equiv aldehyde and a magnetic stirring bar. The vessel was crimped with a cap, placed in the preheated (100°C) reaction block and stirred vigorously at 100°C. GC-MS analysis indicated full conversion of the starting material. After cooling to rt the cap was removed, the reaction mixture was transferred into a one-neck round bottom flask and concentrated under reduced pressure to yield the product.

Reference： [1]Mayer, Nicole; Schweiger, Martina; Melcher, Michaela-Christina; Fledelius, Christian; Zechner, Rudolf; Zimmermann, Robert; Breinbauer, Rolf [Bioorganic and Medicinal Chemistry, 2015, vol. 23, # 12, p. 2904 - 2916]

62
[ 40033-08-7 ]
[ 6728-26-3 ]
2-bromo-3-((1E,3E)-hepta-1,3-dienyl)thiophene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57.1%	Stage #1: diethyl (2-bromothiophen-3-yl)methylphosphonate; (E)-2-Hexenal In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Stage #2: With potassium <i>tert</i>-butylate In tetrahydrofuran at 20 - 50℃; for 17h; Inert atmosphere;	2.7 2.2.7 2-Bromo-3-((1E, 3E)-hepta-1, 3-dienyl)thiophene (12a) Under nitrogen atmosphere, compound 7 (0.50g, 1.60mmol) and compound 11 (0.16g, 1.63mmol) were dissolved in THF (25mL) and the solution was stirred at room temperature for 0.5h. Then the mixture of potassium tert-butoxide (0.18g, 1.63mmol) and THF (25mL) was added dropwise to the solution. The reaction mixture was stirred at room temperature for 5h, and then heated to 50°C for 12h. After cooled to room temperature, the mixture was extracted with dichloromethane and washed with dilute HCl. The organic phase was dried over anhydrous MgSO4, and then the solvent was removed by rotary evaporation. The crude product was purified on silica gel chromatography using petroleum ether as eluent to afford a yellow liquid (0.25g, 57.1%). 1H NMR (400MHz, CDCl3, δ/ppm): 7.20-7.19 (d, 1H, J=5.17Hz), 7.09-7.08 (d, 1H, J=6.00Hz), 6.65-6.58 (m, 1H), 6.45-6.41 (m, 1H), 6.24-6.18 (m, 1H), 5.87-5.80 (m, 1H), 2.12-2.11 (m, 2H), 1.47-1.42 (m, 2H), 0.94-0.91 (t, 3H, J=6.94Hz).

Reference： [1]Long, Jun; Liu, Xunshan; Guo, Huan; Zhao, Bin; Tan, Songting [Dyes and Pigments, 2016, vol. 124, p. 222 - 231]

63
[ 931-53-3 ]
[ 6728-26-3 ]
[ 64-19-7 ]
(E)-1-(cyclohexylamino)-1-oxohept-3-en-2-yl acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	at 20℃; for 72h;	General procedure 1 for Passerini products General procedure: A mixture of aldehyde (1.0 equiv), acetic acid (1.0 equiv) and isocyanide (1.0 equiv) was stirred at room temperature for 3 days. The crude was purified by flash chromatography on silica gel.
70%	In neat (no solvent) at 20℃; for 72h;
60%	In neat (no solvent) at 20℃; for 72h; Inert atmosphere;	General Procedure A - Passerini three-component reactions (P-3CR) 1(aa-i) General procedure: Isocyanide (3.0 mmol, 1.0 equiv) was added to the suspension of the aldehyde (3.0 mmol, 1.0equiv) and the carboxylic acid (3.0 mmol, 1.0 equiv) at room temperature under solvent-freeconditions. The mixture was stirred for 3 days under argon atmosphere until completion of thereaction (TLC). Compounds 1(aa-h) were obtained by washing of the crude solid productusing combination of (diethyl ether/petroleum ether: 1/9). Only the pure product 1i wasobtained by column chromatography purification on silica gel.

Reference： [1]Youcef, Sihem Dali; Kerim, Mansour Dolè; Ilitki, Hocine; El Kaïm, Laurent [Tetrahedron Letters, 2019, vol. 60, # 2, p. 102 - 105]
[2]El Mamouni, El Hachemia; Cattoen, Martin; Cordier, Marie; Cossy, Janine; Arseniyadis, Stellios; Ilitki, Hocine; El Kaïm, Laurent [Chemical Communications, 2016, vol. 52, # 100, p. 14490 - 14493]
[3]Abdessalem, Abdelbari Ben; Abderrahim, Raoudha; El Kaïm, Laurent [Synlett, 2015, vol. 26, # 18, p. 2537 - 2540]

64
[ 6728-26-3 ]
[ 67889-07-0 ]

Yield	Reaction Conditions	Operation in experiment
92%	With acetic acid; hydroxylamine-O-sulfonic acid In water at 50℃; for 6h;	General method for the synthesis of nitriles General procedure: In a 10 mL round bottom flask at 0 °C, aldehyde (1.0 mmol, 1.0 equiv) and NH2OSO3H (1.1 mmol, 1.1 equiv) were dissolved in 4 mL of H2O with acetic acid (1.0 mmol, 1 equiv). The reaction was stirred at 50 °C for 6 h or until complete conversion by TLC. The reaction was quenched with aqueous 10% NaHCO3 (1 mL) and the resulting mixture was extracted with EtOAc (3*10 mL), dried (Na2SO4), filtered, and concentrated by rotary evaporation to afford the crude product. The product was directly characterized unless traces of impurities required purification by automated silica gel flash chromatography (three examples).

Reference： [1]Quinn, Dylan J.; Haun, Graham J.; Moura-Letts, Gustavo [Tetrahedron Letters, 2016, vol. 57, # 34, p. 3844 - 3847]

65
[ 36273-89-9 ]
[ 6728-26-3 ]
(E)-2-[(E)-hex-2-en-1-ylidene]-N-(pyridin-2-yl)hydrazinecarbothioamide [ No CAS ]