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Structure of 16640-68-9 * Storage: {[proInfo.prStorage]}
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Journal of the American Chemical Society, 2007, vol. 129, # 7, p. 1987 - 1995
[2] Journal of Organic Chemistry, 2014, vol. 79, # 3, p. 1386 - 1398
[3] Chemische Berichte, 1961, vol. 94, p. 578 - 584
[4] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1978, p. 786 - 793
[5] Organic Letters, 2011, vol. 13, # 10, p. 2586 - 2589
[6] Angewandte Chemie - International Edition, 2018, vol. 57, # 22, p. 6597 - 6600[7] Angew. Chem., 2018, vol. 130, p. 6707 - 6710,4
2
[ 603-35-0 ]
[ 590-17-0 ]
[ 16640-68-9 ]
Reference：
[1] Patent: WO2012/76435, 2012, A1, . Location in patent: Page/Page column 30
[2] Journal of Organic Chemistry, 2014, vol. 79, # 8, p. 3696 - 3703
[3] Angewandte Chemie, International Edition, 2014, vol. 53, # 36, p. 9462 - 9465,4[4] Angewandte Chemie, 2014, vol. 126, # 36, p. 9616 - 9619,4
3
[ 4336-70-3 ]
[ 16640-68-9 ]
Reference：
[1] Journal of the American Chemical Society, 1984, vol. 106, # 11, p. 3344 - 3353
[2] J. Gen. Chem. USSR (Engl. Transl.), 1987, vol. 57, p. 1366 - 1371[3] Zhurnal Obshchei Khimii, 1987, vol. 57, # 7, p. 1534 - 1540
[4] Journal of Organic Chemistry, 1998, vol. 63, # 22, p. 7764 - 7769
4
[ 603-35-0 ]
[ 16640-68-9 ]
Reference：
[1] International Journal of Chemical Kinetics, 2006, vol. 38, # 8, p. 496 - 502
[2] J. Gen. Chem. USSR (Engl. Transl.), 1979, vol. 49, p. 889 - 894[3] Zhurnal Obshchei Khimii, 1979, vol. 49, p. 1025 - 1031
[4] Chemische Berichte, 1961, vol. 94, p. 578 - 584
[5] Organic Letters, 2011, vol. 13, # 10, p. 2586 - 2589
[6] Journal of Organic Chemistry, 2014, vol. 79, # 3, p. 1386 - 1398
[7] Journal of Heterocyclic Chemistry, 2015, vol. 52, # 3, p. 764 - 772
[8] Journal of Organic Chemistry, 2017, vol. 82, # 3, p. 1389 - 1402
[9] Angewandte Chemie - International Edition, 2018, vol. 57, # 22, p. 6597 - 6600[10] Angew. Chem., 2018, vol. 130, p. 6707 - 6710,4
5
[ 107-14-2 ]
[ 603-35-0 ]
[ 16640-68-9 ]
Reference：
[1] Molecular Crystals and Liquid Crystals (1969-1991), 1987, vol. 150, p. 237 - 246
[2] Journal of the American Chemical Society, 2003, vol. 125, # 35, p. 10608 - 10614
6
[ 47181-92-0 ]
[ 16640-68-9 ]
Reference：
[1] Journal of Organic Chemistry, 2017, vol. 82, # 3, p. 1389 - 1402
7
[ 77785-52-5 ]
[ 16640-68-9 ]
Reference：
[1] Chemistry - A European Journal, 2013, vol. 19, # 7, p. 2311 - 2321
8
[ 1124-58-9 ]
[ 19493-09-5 ]
[ 16640-68-9 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1974, p. 1688 - 1693
9
[ 24463-15-8 ]
[ 16640-68-9 ]
[ 3029-19-4 ]
[ 103698-30-2 ]
Reference：
[1] Angewandte Chemie - International Edition, 2002, vol. 41, # 24, p. 4740 - 4743
10
[ 24463-15-8 ]
[ 16640-68-9 ]
[ 3029-19-4 ]
[ 74833-81-1 ]
Reference：
[1] European Journal of Organic Chemistry, 2006, # 19, p. 4367 - 4378
Reference：
[1] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1982, vol. 21, # 11, p. 1046 - 1048
15
[ 4521-61-3 ]
[ 16640-68-9 ]
[ 4336-70-3 ]
[ 86213-25-4 ]
Reference：
[1] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1982, vol. 21, # 11, p. 1046 - 1048
16
[ 100-07-2 ]
[ 16640-68-9 ]
[ 5067-99-2 ]
[ 4336-70-3 ]
Reference：
[1] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1982, vol. 21, # 11, p. 1046 - 1048
17
[ 122-04-3 ]
[ 16640-68-9 ]
[ 5068-02-0 ]
[ 4336-70-3 ]
Reference：
[1] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1982, vol. 21, # 11, p. 1046 - 1048
18
[ 16331-46-7 ]
[ 16640-68-9 ]
[ 4336-70-3 ]
[ 86213-24-3 ]
Reference：
[1] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1982, vol. 21, # 11, p. 1046 - 1048
19
[ 75-36-5 ]
[ 16640-68-9 ]
[ 4336-70-3 ]
[ 86213-23-2 ]
Reference：
[1] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1982, vol. 21, # 11, p. 1046 - 1048
20
[ 16640-68-9 ]
[ 1187595-85-2 ]
Yield
Reaction Conditions
Operation in experiment
67%
at 20℃;
Three-necked flask was charged with triphenylphosphine acetonitrile (33.14 g, 110 mmol) and dichloromethane (96 mL)And then 1- (ethylsulfonyl) azepin-3-one (prepared from Example 3) was added and reacted at room temperature for 3 to 4 hours. The reaction was quenched by the addition of 240 mL of water. The aqueous phase was extracted three times with ethyl acetate (120 mL). The organic phase was washed with saturated brine (120 mL) and concentrated to recrystallize from isopropyl ether and petroleum ether to give 2- [1-(ethylsulfonyl)-3-azetidinylidene] acetonitrile(16.76 g, 4 steps yield 67percent).
Reference：
[1] Patent: CN106946917, 2017, A, . Location in patent: Paragraph 0064-0066
21
[ 6704-31-0 ]
[ 16640-68-9 ]
[ 1123787-67-6 ]
Yield
Reaction Conditions
Operation in experiment
46%
at 20℃;
To 3-oxanone (0.42 g, 6 mmol) in DCM (20 mL) was added 2-(triphenylphosphoranylidene) acetonitrile (1.8 g, 6 mmol) and stirred overnight at rt. After which time, the solvent was removed under reduced pressure to afford crude product (260 mg, crude), which was purified by chromatography on silica gel (petroleum: EtOAc, 3: 1) to give intermediate 44 (260 mg, yield 46percent) as a white solid.
41.7%
at 20℃; for 16 h;
Example[00669] To a mixture of 92 (2.00 g, 27.8 mmols, 1.0 eq) in dichioromethane (30 mL) was added 2-(triphenylphosphoranylidene)acetonitrile (8.34 g, 27.8 mmols, 1.0 eq) and stirred at room temperature. After 16 hours, the solvent was removed under reduced pressure and the residue was purified by chromatography on silica gel (petroleum ether / ethyl acetate, 3 / 1) to give the desired product 93 (1.10 g, 11.6 mmols, 41.7percent) as a white solid.
Reference：
[1] Journal of Medicinal Chemistry, 2010, vol. 53, # 8, p. 3227 - 3246
[2] Patent: WO2013/134085, 2013, A1, . Location in patent: Page/Page column 50
[3] Patent: WO2016/144792, 2016, A1, . Location in patent: Paragraph 00669
[4] Journal of the American Chemical Society, [5] Journal of the American Chemical Society, 2009, vol. 131, p. 2786 - 2787
With triethylamine; In dichloromethane; at 20℃; for 0.75h;
Synthesis of (E)-5-(tritylthio)pent-2-enenitrile (15) To a suspension of (cyanomtheyl)triphenylphsphonium chloride (5.06 g, 15 mmol, 1.5 equiv) in dry dichloromethane (50 mL) was added triethylamine (3.80 g, 38 mmol, 3.9 equiv). The reaction mixture was stirred at room temperature for 45 min and the solvent was removed under reduced pressure to give (cyanomethylene)triphenylphsphorane as a yellow solid, which was used in the next step without further purification.
To a stirring solution of 30 in benzene (0.4 M) at room temperature under nitrogen was added (triphenylphosphoranylidene)acetonitrile (1.1 eq). The reaction was refluxed overnight. The benzene was removed under reduced pressure. The resulting oil was dissolved in ethyl acetate and washed with 1N hydrochloric acid (1?), saturated sodium bicarbonate (1?) and brine (1?) then dried over sodium sulfate, filtered, concentrated in vacuo and purified by flash chromatography using the ISCO (0-15% gradient methanol/dichloromethane). (98%) 1H NMR (400 MHz, CDCl3) ? 7.31-7.44 (m, 5H), 5.87 (d, 1H), 3.71 (s, 3H), 3.66 (s, 2H).
Wittig reaction of <strong>[24973-22-6]3-methoxy-4-methylbenzaldehyde</strong> with cyanomethyl triphenylphosphorane gave 3-(3-methoxy-4-methylphenyl)acrylonitrile in 77% yield which was further transformed to 3-(3-methoxy-4-methylphenyl)propan-l-amine using the above described procedures.
With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride
1; 4
The reaction scheme for the synthesis of the α-ketoamide Ala-Pro dipeptide analogue is shown in Scheme 4, which is a model reaction for synthesis of the α-ketoamide Ser-Pro dipeptide analogue. Additionally, the α-ketoamide Ala-Pro dipeptide analogue may be a potential inhibitor of cyclophilin.Scheme 4In the first step, the ylide 1 was synthesized from a coupling reaction between EPO commercially available (cyanomethylene)triphenylphosphorane and Boc-L-AlaOH with EDC in the presence of 4-dimethylaminopyridine. Under these conditions, a good yield of 80% was obtained.In the second step, the ylide 1 was oxidized to an α,β-diketonitrile. This labile electrophile then was reacted in situ with HProOBn to form the α-keto amide 2. From NMR and MS spectra, this α-ketoamide 2 appeared to be obtained as a mixture of isomers in 45% yield.
60%
Stage #1: L-N-Boc-Ala With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane for 0.333333h; Inert atmosphere;
Stage #2: cyanomethylene triphenylphosphorane In dichloromethane at 20℃; for 12h; Inert atmosphere;
1.1
To a solution of 28A (1 g, 5.29 mmol) in DCM (10 mL) was added EDCI (1.32 g,6.87 mmol) and DMAP (65 mg, 0.53 mmol) under N2 protection, and the mixture was stirred for 20 minutes. (Cyanomethylene)triphenylphophorane (1.6 g, 5.29 mmol) was added at ambient temperature under N2 atmosphere. Then the resulting solution was stirred at ambient temperature for 12 hrs, and then the mixture was concentrated and purified by column chromatography to give the product 28B (1.5 g, yield: 60%).
In dichloromethane equimolar amts., stirring at room temp. for 30 min; evapn., stirring with Et2O, collection (filtration), drying in air; elem. anal.; isomer mixt. (1:1.2) not sepd., detd. by NMR spectroscopy; total yield 83%;
Stage #1: Z-Leu-OH With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane for 0.5h;
Stage #2: cyanomethylene triphenylphosphorane at 20℃; for 24h;
9 Example 9:Compound 9
Z-L-LeuOH (mg, 2.4 mmol) was dissolved in anhydrous DCM (24 mL). EDCI (464 mg, 2.42 mmol) and DMAP (29 mg, 0.242 mmol) were successively added and the mixture was stirred for 30 min. PPh3CHCN (729 mg, 2.42 mmol) was then added and the mixture was stirred at room temperature for 24h. Reaction was quenched with 2% aqueous HCl solution. The organic phase was then washed with saturated NaHC03 aqueous solution, dried over MgSO4 and concentrated under reduced pressure. The crude solid was purified by flash chromatography (hexane/EtOAc 9:1 to 1:1) to give compound 9 (1.31 mmol, 55%).1H NMR (CDCl3) ? : 0.72 (d, 1H, J=6.0), 0.78 (d=3H, J=6.0), 0.89 (d, 3H, J=6.00), 1.60 (m, 2H), 4.68 (m, 1 H), 4.90 (m, 1 H), 5.50 (s, 2H), 7.30-7.65 (m, 20H)
To 3-oxanone (0.42 g, 6 mmol) in DCM (20 mL) was added 2-(triphenylphosphoranylidene) acetonitrile (1.8 g, 6 mmol) and stirred overnight at rt. After which time, the solvent was removed under reduced pressure to afford crude product (260 mg, crude), which was purified by chromatography on silica gel (petroleum: EtOAc, 3: 1) to give intermediate 44 (260 mg, yield 46%) as a white solid.
41.7%
In dichloromethane; at 20℃; for 16h;
Example[00669] To a mixture of 92 (2.00 g, 27.8 mmols, 1.0 eq) in dichioromethane (30 mL) was added 2-(triphenylphosphoranylidene)acetonitrile (8.34 g, 27.8 mmols, 1.0 eq) and stirred at room temperature. After 16 hours, the solvent was removed under reduced pressure and the residue was purified by chromatography on silica gel (petroleum ether / ethyl acetate, 3 / 1) to give the desired product 93 (1.10 g, 11.6 mmols, 41.7%) as a white solid.
2-(4-isobutyl-2-phenyloxazol-5-yl)acetonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In toluene; for 3h;Inert atmosphere; Reflux;
General procedure: A solution of 1 (0.5 mmol) in CH2Cl2 (5 mL) in a round-bottom flask (25 mL) was cooled with ice-water, and then DIC (0.55 mmol) was added by a syringe. After the resultant mixture was stirred at 0 C for 1 h, CH2Cl2 was removed by sparging N2 followed by adding 3a (0.55 mmol) or 3b (0.6 mmol) and toluene (10 mL). After refluxing for 3 h, the reaction mixture was diluted with EtOAc (6 mL), passed through a silica gel column, and then evaporated. The product 5a or 5b was isolated from the residue by preparative TLC (silica gel, EtOAc/PE 1/2-1/1, v/v).
To a solution of <strong>[22131-92-6]thietan-3-one</strong> (900 mg) in 10 ml of dry methylene chloride was added a solution of (triphenylphosphoranylidene)acetonitrile (3.31 g) in 20 ml of dry methylene chloride at 0C. The solution was allowed to warm to room temperature and after stirring for 15 min the solvent was removed under reduced pressure. The residue was purified by a flash chromatography (silica gel: Dichloromethane as an eluant) to give the title compound (785 mg) as a yellow-brown oil. GC/MS (Method C): rt =2.89 min (54.7 %) m/z: [M+l]+ = 112. 'H-NMR (CDC13, 400 MHz): 5.11 (m, 1H), 4.15 (m, 2H), 4.03 (m, 2H).
785 mg
In dichloromethane; at 0 - 20℃; for 0.25h;
Preparation of 2-(thietan-3-ylidene)acetonitrileTo a solution of <strong>[22131-92-6]thietan-3-one</strong> (900 mg) in 10 ml of dry methylene chloride was added a solution of (triphenylphosphoranylidene)acetonitrile (3.31 g) in 20 ml of dry methylene chloride at 0C. The solution was allowed to warm to room temperature and after stirring for 15 min the solvent was removed under reduced pressure. The residue was purified by a flash chromatography (silica gel: Dichloromethane as an eluant) to give the title compound (785 mg) as a yellow-brown oil. GC/MS (Method C): rt =2.89 min (54.7 %) m/z: [M+l]+ = 112. 'H-NMR (CDC13, 400 MHz): 5.11 (m, 1H), 4.15 (m, 2H), 4.03 (m, 2H).
785 mg
In dichloromethane; at 0 - 20℃;
Example 22: Preparation of 2-(thietan-3-ylidene)acetonitrile To a solution of <strong>[22131-92-6]thietan-3-one</strong> (900 mg) in 10 ml of dry methylene chloride was added a solution of (triphenylphosphoranylidene)acetonitrile (3.31 g) in 20 ml of dry methylene chloride at 0C. The solution was allowed to warm to room temperature and after stirring for 15 min the solvent was removed under reduced pressure. The residue was purified by a flash chromatography (silica gel: Dichloromethane as an eluant) to give the title compound (785 mg) as a yellow-brown oil. GC/MS (Method C): rt =2.89 min (54.7 %) m/z: [M+l]+ = 112. 'H-NMR (CDC13, 400 MHz): 5.11 (m, 1H), 4.15 (m, 2H), 4.03 (m, 2H).
785 mg
In dichloromethane; at 0 - 20℃; for 0.25h;
Example C: 2-(thietan-3-ylidene)acetonitrile To a solution of <strong>[22131-92-6]thietan-3-one</strong> (900 mg) in 10 ml of dry methylene chloride was added a solution of (triphenylphosphoranylidene)acetonitrile (3.31 g) in 20 ml of dry methylene chloride at 0C. The solution was allowed to warm to room temperature and after stirring for 15 min the solvent was removed under reduced pressure. The residue was purified by a flash chromatography (silica gel: Dichloromethane as an eluant) to give the title compound (785 mg) as a yellow-brown oil. GC/MS (Method C): rt =2.89 min (54.7 %) m/z: [M+l]+ = 112. 'H-NMR (CDC13, 400 MHz): 5.11 (m, 1H), 4.15 (m, 2H), 4.03 (m, 2H).
785 mg
In dichloromethane; at 0 - 20℃; for 0.25h;
To a solution of <strong>[22131-92-6]thietan-3-one</strong> (900 mg) in 10 ml of dry methylene chloride was added a solution of (triphenylphosphoranylidene)acetonitrile (3.31 g) in 20 ml of dry methylene chloride at 0C. The solution was allowed to warm to room temperature and after stirring for 15 min the solvent was removed under reduced pressure. The residue was purified by a flash chromatography (silica gel: Dichloromethane as an eluant) to give the title compound (785 mg) as a yellow-brown oil. GC/MS (Method C): rt =2.89 min (54.7 %) m/z: [M+l]+ = 112. 'H-NMR (CDC13, 400 MHz): 5.11 (m, 1H), 4.15 (m, 2H), 4.03 (m, 2H).
With dmap; 1,2-dichloro-ethane; In dichloromethane; at 0 - 20℃; for 13h;Inert atmosphere;
To a stirred, precooled (0 C) solution of <strong>[3959-23-7](phenylsulfonyl)acetic acid</strong> (1.42 g, 7.10 mmol) and (triphenylphosphoranylidene)acetonitrile (2.14 g, 1.0 eq.) in dry CH2Cl2 (30 mL) were added EDC (1.36 g, 1.0 eq.) and DMAP (86.7 mg, 0.1 eq.), and the resulting mixture was stirred at 0 C for 1 h and then at rt for 12 h under Ar. The reaction was quenched by the addition of H2O(20 mL), and the organic layer was separated. The aqueous layer was extracted further with CH2Cl2 (10 mL × 2), and the combined organic layers were dried over MgSO4, filtered, and concentrated. The solid residue was purified by flash chromatography on SiO2 (CH2Cl2/EtOAc, 5/1) to provide 8 (2.95 g, 86 %) as a white solid.
86%
With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 0 - 20℃; for 13h;Inert atmosphere;
After dissolving <strong>[3959-23-7]phenylsulfonyl acetic acid</strong> (1.42 g, 7.10 mmol) and (triphenylphosphoranylidene) acetonitrile (2.14 g, 1.0 eq) in anhydrous CH2Cl2 (30 mL),The resulting solution was cooled to 0 oC, and then 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimideHCl (1.36 g, 1.0 eq.) And 4-dimethylaminopyridine (86.7 mg, 0.1 eq.) ) Was added and stirred under argon gas for 1 hour at 0 oC and 12 hours at room temperature. After completion of the reaction, water (20 mL) was added to the reaction solution and shaken, the lower organic layer was separated with a separating funnel, and the upper aqueous layer was extracted twice more with CH2Cl2 (10 mL). The separated organic layers were combined, then treated with anhydrous magnesium sulfate (5.0 g), filtered, and then the solid residue obtained by removing the solvent with a rotary vacuum evaporator was subjected to flash chromatography (silica gel: Merck 70-230, mobile phase: CH2Cl2 / EtOAc = 5/1) to give the title compound (1, 2.95 g, 86%) as a white solid.
With oxygen; 1,8-diazabicyclo[5.4.0]undec-7-ene; copper dichloride In toluene at 100℃; for 18h; Overall yield = 45 %; Overall yield = 56.7 mg;
3-(4-tert-butylphenyl)acrylonitrile (13c, as a mixture of E/Z isomers)
General procedure: Representative procedure for the reaction of thiols and phosphorous ylides: A mixture of benzyl mercaptan 1a (116 µl, 1 mmol), copper chloride (II) (1.3 mg, 0.01 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (75 µl, 0.5 mmol) and phosporous ylide 5b (174.2 mg, 0.5 mmol) in toluene (0.5M, 1 ml) was taken in a 5 ml round bottom flask and stirred at 100 °C for 18 h under oxygen atmosphere. The reaction mixture was evaporated and purified by flash silica gel column chromatography using 1 % ether/hexane to obtain 7c (64.1 mg, 73 %).
methyl (S)-3-(((benzyloxy)carbonyl)amino)-5-cyano-4-oxo-5-(triphenylphosphoranylidene)pentanoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
44%
With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; for 4h;
Z-L-aspartic acid 3-methyl ester (2 g, 7.11 mmol, 1 eq.), EDC (1.77 g, 9.244 mmol, 1.3 eq.) and DMAP (86.9 mg, 0.711 mmol, 0.1 eq) were combined in a round bottom flask. DCM (40 ml) was then added and with in one minute (triphenylphosphoranylidene)acetonitrile (2.79 g, 9.24 mmol, 1.3 eq) was added in one portion. The reaction was left at RT for 4 hrs and then successively washed with water (1 x 40 ml) and NaHCO3 (satd.aqueous 1 x 40 ml). The organic layer was dried over sodium sulphate and concentrated. The product was purified on normal phase using 0% to 50% ethyl acetate in hexanes as the eluent to give (S)-methyl 3-(((benzyloxy)carbonyl)amino)-5-cyano-4-oxo-5-(triphenylphosphoranylidene)pentanoate as a white foam (1.75 g, 44%). H1 NMR (400 MHz, CDCl3) delta 3.15(1H, dd, J=S, 17 Hz), 3.53(1H, dd, J=S, 17 Hz), 3.65(3H,s), 5.12(2H, s), 5.18(1H, m), 5.84(1H, d, J=7 Hz), 7.21-7.42(20H, m); MS (LC/MS) m/z observed 564.94;expected 565.19 [M+H].
Three-necked flask was charged with triphenylphosphine acetonitrile (33.14 g, 110 mmol) and dichloromethane (96 mL)And then 1- (ethylsulfonyl) azepin-3-one (prepared from Example 3) was added and reacted at room temperature for 3 to 4 hours. The reaction was quenched by the addition of 240 mL of water. The aqueous phase was extracted three times with ethyl acetate (120 mL). The organic phase was washed with saturated brine (120 mL) and concentrated to recrystallize from isopropyl ether and petroleum ether to give 2- [1-(ethylsulfonyl)-3-azetidinylidene] acetonitrile(16.76 g, 4 steps yield 67%).
Stage #1: 2-(3-methoxyphenyl)acetaldehyde With (2S)-2-{diphenyl[(trimethylsilyl)oxy]methyl}pyrrolidine; copper diacetate In dichloromethane at 20℃; for 5h; Inert atmosphere;
Stage #2: cyanomethylene triphenylphosphorane In dichloromethane Inert atmosphere;
With potassium hydrogensulfate; pentafluorophenylthiol; tris[2-phenylpyridinato-C2,N]iridium(III); ascorbic acid In water; acetonitrile at 20℃; for 40h; Inert atmosphere; Irradiation;
Typical procedure for the reaction of ylide and alkene (Scheme 1)
General procedure: Phosphorus ylide 2 (302 mg, 1.00 mmol), fac-Ir(ppy)3 (3.30 mg, 0.005 mmol, 1.0 mol%), ascorbic acid(882 mg, 5.00 mmol), and KHSO4 (207 mg, 1.52 mmol) were added to a vial (Biotage, 2-5 mL) equippedwith a stir bar. The vial was flushed with argon gas and quickly capped with a Teflon septum. 4-Phenylbut-1-ene (1a, 67.6 mg, 0.51 mmol), C6F5SH (20.0 mg, 0.100 mmol, 20 mol%), distilled CH3CN (2.5 mL), andH2O (2.5 mL; degassed with argon gas for 30 min) were added via syringe. The mixture was stirredvigorously for 40 h under blue LED lights (470 nm, 23 W) while the vial being cooled with a fan. Then, themixture was diluted with brine (25 mL) and extracted with CH2Cl2 (25 mL x 3). The organic phase was driedwith Na2SO4. Filtration and the following concentration under reduced pressure gave a residue, which waspurified by silica gel column chromatography (Hexane/Ethyl acetate= 9:1) to give 3a (70.7 mg, 0.41 mmol)in 80% yield.
With potassium hydrogensulfate; pentafluorophenylthiol; tris[2-phenylpyridinato-C2,N]iridium(III); ascorbic acid In water; acetonitrile at 20℃; for 40h; Inert atmosphere; Irradiation;
Typical procedure for the reaction of ylide and alkene (Scheme 1)
General procedure: Phosphorus ylide 2 (302 mg, 1.00 mmol), fac-Ir(ppy)3 (3.30 mg, 0.005 mmol, 1.0 mol%), ascorbic acid(882 mg, 5.00 mmol), and KHSO4 (207 mg, 1.52 mmol) were added to a vial (Biotage, 2-5 mL) equippedwith a stir bar. The vial was flushed with argon gas and quickly capped with a Teflon septum. 4-Phenylbut-1-ene (1a, 67.6 mg, 0.51 mmol), C6F5SH (20.0 mg, 0.100 mmol, 20 mol%), distilled CH3CN (2.5 mL), andH2O (2.5 mL; degassed with argon gas for 30 min) were added via syringe. The mixture was stirredvigorously for 40 h under blue LED lights (470 nm, 23 W) while the vial being cooled with a fan. Then, themixture was diluted with brine (25 mL) and extracted with CH2Cl2 (25 mL x 3). The organic phase was driedwith Na2SO4. Filtration and the following concentration under reduced pressure gave a residue, which waspurified by silica gel column chromatography (Hexane/Ethyl acetate= 9:1) to give 3a (70.7 mg, 0.41 mmol)in 80% yield.
(E)-4-(furan-2-yl)-4-oxobut-2-enenitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With benzoic acid In benzene at 80℃; for 10h; Inert atmosphere;
Preparation of -Cyanoenones 8b-m; General Procedure
General procedure: To a 100 mL two-neck round-bottom flask, SeO2 (2.00 g, 18.0 mmol), H2O (0.31 g, 17.0 mmol) and 1,4-dioxane (10.0 mL) were added and the flask was fitted with a condenser. The mixture was heated to reflux with stirring until the solid dissolved. Then, substituted aryl ketone(10.0 mmol) was added into the solution and the reaction mixture was allowed to reflux. After the reaction was completed, the reaction mixture was cooled to r.t. and filtered through a Celite pad,which was then washed several times with diethyl ether. The combined filtrate was evaporated on a rotary evaporator to afford the crude product, which was used in the next step without further purification. A solution of aryllglyoxal monohydrate (10.0 mmol) in benzene (40 mL) was heated under reflux with azeotropic removal of water (Dean-Stark). Thereafter, cyanomethylidenetriphenylphosphorane(3.80 g, 12.6 mmol) and benzoic acid (211 mg, 1.73 mmol) were added and the mixture was stirred for 10 h under an argon atmosphere at 80 °C. The cooled mixture was concentrated in vacuo and the residue was subjected to column chromatography on silica gel (hexane/EtOAc, 2:1) and recrystallization to give 8 as yellow crystals.
70.3 Step 3: 70-D
To a solution of 70-C (3.9 g, 27.36 mmol) in DCM (150 mL) was added 2- (triphenyl-phosphanylidene) acetonitrile (8.24 g, 27.36 mmol) and stirred at 25 C for 3 hrs. The reaction mixture was concentrated and purified by flash chromatography on silica gel (EA in PE, 0 - 30%) to give 70-D (4.1 g, 24.76 mmol, 90.7%yield) . MS: m/z = 166.1 (M + 1) .
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