tert-Butylsulfinamide, (S)-(-)- → (NE,S)-N-[1-(6-bromo-3-fluoro-4-triethylsilyl-2-pyridinyl)-3-methoxypropylidene]-2-methylpropane-2-sulfinamide

HRID 1752464Notes

Reaction equation

HRID 1752464 reaction equation
[C:1]([S@@:5]([NH2:7])=[O:6])([CH3:4])([CH3:3])[CH3:2].[Br:8][C:9]1[N:14]=[C:13]([C:15](=O)[CH2:16][CH2:17][O:18][CH3:19])[C:12]([F:21])=[C:11]([Si:22]([CH2:27][CH3:28])([CH2:25][CH3:26])[CH2:23][CH3:24])[CH:10]=1>C1COCC1.C(OCC)(=O)C.[Cl-].[Na+].O>[Br:8][C:9]1[N:14]=[C:13](/[C:15](=[N:7]/[S@:5]([C:1]([CH3:4])([CH3:3])[CH3:2])=[O:6])/[CH2:16][CH2:17][O:18][CH3:19])[C:12]([F:21])=[C:11]([Si:22]([CH2:27][CH3:28])([CH2:23][CH3:24])[CH2:25][CH3:26])[CH:10]=1

Participants

6

Reactant 2

HCID 11355477tert-Butylsulfinamide, (S)-(-)-HCID 866891481-(6-Bromo-3-fluoro-4-triethylsilanyl-pyridin-2-yl)-3-methoxy-propan-1-one

Product 1

HCID 141628093(NE,S)-N-[1-(6-bromo-3-fluoro-4-triethylsilyl-2-pyridinyl)-3-methoxypropylidene]-2-methylpropane-2-sulfinamideYield 63.5%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of titantetraethoxide (11.03 g, 48.4 mmol), (S)-tert.-butylsulfinamide (3.52 g, 29 mmol) and 1-(6-Bromo-3-fluoro-4-triethylsilanyl-pyridin-2-yl)-3-methoxy-propan-1-one (9.1 g, 24.18 mmol) in THF (100 ml) was stirred at 60° C. under a nitrogen atmosphere for 34 hours. The cold reaction mixture was diluted with ethyl acetate and poured onto icecold brine (200 ml) with gentle stirring. The precipitate was filtered through a pad of hyflo and washed with ethyl acetate. The filtrate was diluted with ethyl acetate and washed with brine, dried over sodium sulfate, filtered and evaporated. The crude yellowish-brown oil (10.67 g) was chromatographed over silica gel (Redisep column 120 g, cyclohexane/ethyl acetate 95:5) to give the title compound as a yellow-orange oil. 7.51 g (63.5% yield).

Workup

  1. customThe cold reaction mixture
  2. filtrationThe precipitate was filtered through a pad of hyflo
  3. washwashed with ethyl acetate
  4. additionThe filtrate was diluted with ethyl acetate
  5. washwashed with brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customThe crude yellowish-brown oil (10.67 g) was chromatographed over silica gel (Redisep column 120 g, cyclohexane/ethyl acetate 95:5)

Sources & evidence

ORD record
ord-4148b2440f4f46e8b6234b8fb7b386d7
Source dataset
uspto-grants-2015_10
Patent number
US09163011B2

Reaction notes

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