tert-Butylsulfinamide, (R)-(+)- → (NZ)-2-methyl-N-[1-(2-methylsulfonyl-1,3-thiazol-5-yl)propylidene]propane-2-sulfinamide

HRID 2067990Notes

Reaction equation

HRID 2067990 reaction equation
[CH3:1][S:2]([C:5]1[S:6][C:7]([C:10](=O)[CH2:11][CH3:12])=[CH:8][N:9]=1)(=[O:4])=[O:3].[CH3:14][C:15]([S@:18]([NH2:20])=[O:19])([CH3:17])[CH3:16]>O1CCCC1.C(OCC)C.O.CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-]>[CH3:1][S:2]([C:5]1[S:6][C:7](/[C:10](=[N:20]\[S:18]([C:15]([CH3:17])([CH3:16])[CH3:14])=[O:19])/[CH2:11][CH3:12])=[CH:8][N:9]=1)(=[O:4])=[O:3]

Participants

7

Reactant 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 592783971-(2-Methanesulfonyl-thiazol-5-yl)-propan-1-one

Product 1

HCID 87126692(NZ)-2-methyl-N-[1-(2-methylsulfonyl-1,3-thiazol-5-yl)propylidene]propane-2-sulfinamideYield 58%

Reagents, catalysts & solvents 4

HCID 11026Titanium isopropoxideCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of crude 1-(2-methanesulfonyl-thiazol-5-yl)-propan-1-one (110 mg, 0.50 mmol), (R)-2-methyl-2-propanesulfinamide (70 mg, 0.55 mmol) and titanium isopropoxide (0.29 mL, 1.00 mmol) in tetrahydrofurane (10 mL) was warmed to reflux for 18 h. The mixture was cooled to room temperature and diluted with diethylether (100 mL) and water (6 mL). The mixture was stirred for 10 min and then dried over sodium sulfate, filtered and concentrated. The crude product was purified by silica gel chromatography, eluting with a gradient of 0-100% ethyl acetate in hexanes to give 2-methyl-propane-2-sulfinic acid [1-(2-methanesulfonyl-thiazol-5-yl)-prop-(Z)-ylidene]-amide (93 mg, 58%). Unreacted 1-(2-Methanesulfonyl-thiazol-5-yl)-propan-1-one (43 mg, 39%) was also isolated.

Workup

  1. temperaturewas warmed
  2. temperatureto reflux for 18 h
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude product was purified by silica gel chromatography
  7. washeluting with a gradient of 0-100% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-3ab9648b5bc64ed5bd45df3b680886e5
Source dataset
uspto-grants-2012_10
Patent number
US08293917B2

Reaction notes

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