Silane, [(3-bromo-3-butenyl)oxy](1,1-dimethylethyl)dimethyl- → (S)-2-methyl-N-((S)-2,2,3,3,11,11,12,12-octamethyl-7-methylene-4,10-dioxa-3,11-disilatridecan-6-yl)propane-2-sulfinamide

HRID 627281Notes

Reaction equation

HRID 627281 reaction equation
Br[C:2](=[CH2:13])[CH2:3][CH2:4][O:5][Si:6]([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:8])[CH3:7].C([Li])(C)(C)C.[Si:19]([O:26][CH2:27]/[CH:28]=[N:29]/[S@:30]([C:32]([CH3:35])([CH3:34])[CH3:33])=[O:31])([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20]>C1COCC1>[CH3:33][C:32]([S@@:30]([NH:29][C@@H:28]([C:2](=[CH2:13])[CH2:3][CH2:4][O:5][Si:6]([CH3:8])([CH3:7])[C:9]([CH3:10])([CH3:11])[CH3:12])[CH2:27][O:26][Si:19]([CH3:21])([CH3:20])[C:22]([CH3:25])([CH3:24])[CH3:23])=[O:31])([CH3:35])[CH3:34]

Participants

5

Reactant 3

HCID 11129203Silane, [(3-bromo-3-butenyl)oxy](1,1-dimethylethyl)dimethyl-2×HCID 16007023(NE,S)-N-[2-[tert-butyl(dimethyl)silyl]oxyethylidene]-2-methylpropane-2-sulfinamide2×HCID 178418306HCID 178418306, compound

Product 1

HCID 131735298(S)-2-methyl-N-((S)-2,2,3,3,11,11,12,12-octamethyl-7-methylene-4,10-dioxa-3,11-disilatridecan-6-yl)propane-2-sulfinamideYield 73.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of ((3-bromobut-3-en-1-yl)oxy)(tert-butyl)dimethylsilane (Intermediate 273, 24.66 g, 92.97 mmol) in THF (200 mL) at −78° C. was added tert-butyllithium (1.7M in pentane) (120 mL, 204.54 mmol) dropwise via cannula. The reaction mixture was stirred for 45 minutes at −78° C. The (S,E)-N-(2-((tert-butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (Intermediate 274, 17.2 g, 61.98 mmol) in THF (50 mL) was added dropwise. The reaction mixture was stirred for ˜1.5 hours at −78° C. The reaction was quenched with saturated sodium bicarbonate and extracted twice with ether. The combined organic extracts were dried over magnesium sulfate, filtered and concentrated. Silica gel chromatography (0%-15% ethyl acetate/hexanes) afforded the title compound (21.07 g, 73.3%) as a colorless oil.

Workup

  1. stirringThe reaction mixture was stirred for ˜1.5 hours at −78° C
  2. customThe reaction was quenched with saturated sodium bicarbonate
  3. extractionextracted twice with ether
  4. dry with materialThe combined organic extracts were dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-ada3f659a0104ef0bc4fcbaa0dbc3efb
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

Loading…