+++ Поиск в Реаксис / SF

[MrChem]

Здравствуйте, уважаемые коллеги! Помогите пожалуйста с поиском альтернативных методов получения илида C[S+]©([CH2-])=O, интересуют методики без использования гидрида натрия или алкиллитиевых соединений.

[mishka]

есть разные (поиск прикреппил), например

из иодида

With potassium tert-butylate In tert-butyl alcohol at 50℃; for 0.5h;
Cwynar, Valerie; Donahue, Matthew G.; Hart, David J.; Yang, Dexi
[Organic Letters, 2006, vol. 8, # 20, p. 4577 - 4580]


With potassium tert-butylate In tert-butyl alcohol at 50 - 70℃;
Butova, Ekaterina D.; Barabash, Anastasiya V.; Petrova, Anna A.; Kleiner, Christian M.; Schreiner, Peter R.; Fokin, Andrey A.
[Journal of Organic Chemistry, 2010, vol. 75, # 18, p. 6229 - 6235]

With potassium tert-butylate In tetrahydrofuran for 2h; Inert atmosphere; Reflux;
Wang, Dengjin; Nugent, William A.; Kowal, Jason J.; Mathre, David J.
[Organic Syntheses, 2007, vol. 84, p. 58 - 67]


With potassium hydroxide In dimethyl sulfoxide at 20℃; for 2 - 2.5h; Product distribution / selectivity;

Experimental Procedure
Current Patent Assignee: ELI LILLY - WO2008/103185, 2008, A2
Location in patent: Page/Page column 15-16


Abstract
A.i
Preparation of (R,R)-2-Methylcvclopropanecarboxylic Acid, also described as (R,R)-trans-2-Methylcyclopropanecarboxylic Acid:; A. Preparation of Racemic 2-Methylcvclopropanecarboxylic Acid:; i. Dimethyloxosufonium Methylide (solution in DMSO):; To a stirred suspension under nitrogen of trimethylsulfoxonium iodide (2.47 kg, 1.05 equivalent) in DMSO (8.00 L) is added potassium hydroxide (90% by weight, 0.69 kg, 1.05 equivalent) portion wise in 100 g portions. (Alternatively, the base may be added all at once, in which case an exotherm occurs.) Additional DMSO (4.00 L) is added and the reaction mixture is stirred at ambient temperature until the mixture becomes homogeneous (except for some undissolved KOH pellets, which are not added in the following step) and ylide formation is complete (about 2-2.5 h).


With potassium tert-butylate In dimethyl sulfoxide at 20 - 35℃; Product distribution / selectivity;

Experimental Procedure
Current Patent Assignee: ELI LILLY - WO2008/103185, 2008, A2
Location in patent: Page/Page column 18

Abstract
i
Telescoped Preparation of (R,R)-2-Methylcvclopropanecarboxylic Acid for formation of(S)-2-Amino-3 -phenyl- 1-propanol (R,R)-2-methylcyclopropanecarboxylic Acid (1: 1)Salt:; i. Dimethyloxosufonium Methylide (solution in DMSO): To a stirred suspension under nitrogen of trimethylsulfoxonium iodide(1.18 equivalent) in DMSO (about 3.3 mL per g of iodide) is added potassium t-butoxide (1.05 equivalent) at once. An exotherm occurs. The reaction mixture is stirred at 20-35 0C until the mixture becomes homogeneous and ylide formation is complete,

With potassium tert-butylate In dimethyl sulfoxide at 20℃; for 1h; Inert atmosphere;
Jiang, Baiyang; Dai, Mingji
[Organic Letters, 2020, vol. 22, # 11, p. 4176 - 4179]



With sodium hexamethyldisilazane In tetrahydrofuran

Experimental Procedure
Shivers, Grant N.; Tun, Soe L.; McLean, Shay L.; Pigge, Chris
[Synlett, 2022]


Abstract
Pyridine (6):
Dimethylsulfoxonium methylide was prepared from NaHMDS (5.45 mL, 10.9 mmol, 1.2 equiv) andtrimethylsulfoxonium iodide (2.0 g, 9.09 mmol, 1.0 equiv) in dry THF (15.0 mL, 0.6 M). 4-(1-(4-Chlorophenyl)vinyl)pyridine (2n) (100 mg, 0.46 mmol, 1 equiv) was added to an oven-dried 25 mL round-bottomedflask containing MTBE (1 mL, 0.46 M). Dimethylsulfoxonium methylide solution (1.2 mL, 0.92 mmol, 2.0 equiv)was added in two portions, and the mixture was stirred at room temperature for one hour. The reaction was thenquenched with sat. aq. NaHCO3 solution (5 mL) and extracted with EtOAc (3 x 5 mL). The combined organic extractwas dried over anhydrous Na2SO4, filtered, concentrated in vacuo, and purified by flash column chromatography using50% EtOAc in hexane as eluent to give 6 as yellow oil (36 mg, 34%). 1H NMR (CDCl3, 400 MHz) 8.40 (d, J =6.3 Hz, 2H), 7.29 (m, 2H), 7.21 (m, 2H), 6.89 (dd, J = 6.3, 1.5 Hz, 2H), 1.35 (m, 4H);13C{1H} NMR (CDCl3, 100MHz) = 154.9, 149.7, 141.7, 132.9, 131.2, 128.9, 121.7, 28.6, 17.8; HRMS (ESI) m/z Calcd for C14H13ClN [M+H]+230.0731, found 230.0734.

With potassium tert-butylate In tetrahydrofuran at 0 - 90℃; Inert atmosphere;
Choi, Hosam; Choi, Joohee; Lee, Kiyoun
[Organic Letters, 2022, vol. 24, # 50, p. 9238 - 9242]


With potassium tert-butylate In dimethyl sulfoxide at 15 - 25℃; Temperature; Reagent/catalyst; Large scale;

Experimental Procedure
Pund, Amit; Rane, Vipul; Pursani, Rajesh; Ahirrao, Vinod; Rafeeq, Mohammad; Yadav, Ram Prasad; Yeole, Ravindra; Merwade, Arvind
[Research on Chemical Intermediates, 2023, vol. 49, # 6, p. 2495 - 2506]


Abstract
General procedure forthesynthesis of(5S)-5-benzyloxycarbonyl-5-tert-butoxy carbonylamino-2-oxo-hexylide-dimethylsulfoxonium (4)
To a stir clear solution of TMSOI (22.39 kg, 1.3 mol) in DMSO (50 lit.). The KTB (9.65kg, 1.1mol) was added in (highly reactive with water) and stirred at 15-25 °C to get sulphur ylide (Used PPE kit; Caution: In case of skin contact wash of with soap and plenty of water). The obtained clear solution was added in to the clear solution of compound 3 (25 kg, 1.0 mol) in DMSO (75 lit.) at 15-25°C. Reaction progress is monitored by HPLC, and after completion of the reaction, sulfoxonium is isolated by adding water (375 lit.) followed by toluene (12.5 lit.) in the reaction mass. Filtered and dried under vacuum at 50°C to get of white powder. Weight 27kg, (yield:83.90% and chiral HPLC purity 99.81%).

и т.д.

[MrChem]

Огромное спасибо!