(NE,S)-N-[(2-cyclopropylsulfanyl-5-nitrophenyl)methylidene]-2-methylpropane-2-sulfinamide → (S)-N-(1-(2-(Cyclopropylthio)-5-nitrophenyl)allyl)-2-methylpropane-2-sulfinamide

HRID 1515548Notes

Reaction equation

[CH:1]1([S:4][C:5]2[CH:18]=[CH:17][C:16]([N+:19]([O-:21])=[O:20])=[CH:15][C:6]=2/[CH:7]=[N:8]/[S@:9]([C:11]([CH3:14])([CH3:13])[CH3:12])=[O:10])[CH2:3][CH2:2]1.[CH:22]([Mg]Br)=[CH2:23]>C1COCC1.COC(C)(C)C>[CH:1]1([S:4][C:5]2[CH:18]=[CH:17][C:16]([N+:19]([O-:21])=[O:20])=[CH:15][C:6]=2[CH:7]([NH:8][S@:9]([C:11]([CH3:14])([CH3:13])[CH3:12])=[O:10])[CH:22]=[CH2:23])[CH2:2][CH2:3]1

Participants

Conditions

Temperature: -78 °C

Procedure

To 85A (3.0 g, 9.2 mmol) in THF (30 mL) and methyl tert-butylether (50 mL) at −78° C. was added vinylmagnesium bromide (1.0 M in THF, 20 mL, 20 mmol) dropwise. The mixture was stirred at −78° C. for 1.0 h before it was quenched with sat. NH4Cl (50 mL) at −78° C. The mixture was extracted with EtOAc (3×50 mL), the organic layer was washed with brine and dried over Na2SO4. After removal of solvent, the crude was purified by silica gel column chromatography using gradient EtOAc in hexanes to give 85B (2.45 g, 78% yield). HPLC and 1H NMR indicated 85B is a mixture of two diastereoisomers in a ratio of 5:1. Major isomer: 1H NMR (400 MHz, CDCl3) δ ppm 0.70-0.81 (m, 2H) 1.17-1.24 (m, 2H) 1.26 (s, 9H) 2.17 (m, 1H) 3.53 (d, J=2.64 Hz, 1H) 5.21-5.32 (m, 3H) 5.91 (m, 1H) 7.72 (d, J=8.79 Hz, 1H) 8.09 (dd, J=8.79, 2.64 Hz, 1H) 8.26 (d, J=2.64 Hz, 1H), LC-MS 355 (M+H).

Workup

customwas quenched with sat. NH4Cl (50 mL) at −78° C
extractionThe mixture was extracted with EtOAc (3×50 mL)
washthe organic layer was washed with brine
dry with materialdried over Na2SO4
customAfter removal of solvent
customthe crude was purified by silica gel column chromatography

Sources & evidence

ORD record: ord-be8a718ffa2545ff91eccff6ddf7d25f
Source dataset: uspto-grants-2012_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08222453B2

Reaction notes

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