tert-Butylsulfinamide, (S)-(-)- → (S)-ethyl 2-(tert-butylsulfinylimino)-4-fluoro-3,3-dimethylbutanoate

HRID 520359

Reaction equation

[F:1][CH2:2][C:3]([CH3:12])([CH3:11])[C:4](=O)[C:5]([O:7][CH2:8][CH3:9])=[O:6].[CH3:13][C:14]([S@@:17]([NH2:19])=[O:18])([CH3:16])[CH3:15]>C1COCC1.CCOC(C)=O.[Na+].[Cl-].C(O[Ti](OCC)(OCC)OCC)C>[C:14]([S@@:17]([N:19]=[C:4]([C:3]([CH3:12])([CH3:11])[CH2:2][F:1])[C:5]([O:7][CH2:8][CH3:9])=[O:6])=[O:18])([CH3:16])([CH3:15])[CH3:13]

Participants

Conditions

Temperature: 65 °C

Procedure

To a solution of ethyl 4-fluoro-3,3-dimethyl-2-oxobutanoate (2.3 g, 13.05 mmol) in THF (20 mL) was added (S)-2-methylpropane-2-sulfinamide (1.899 g, 15.67 mmol) and tetraethoxytitanium (5.91 mL, 26.1 mmol). The reaction mixture was heated at 65° C. for 6 h. The reaction mixture was cooled down, diluted with EtOAc and sat. NaCl (40 mL) and stirred at rt for 0.5 h. The solid was filtered and washed with water and EtOAc. The filtrate was separated and the organic layer was washed with water, sat. NaCl, dried (MgSO4) and purified by flash chromatography (EtOAc/hexane) to afford (S)-ethyl 2-(tert-butylsulfinylimino)-4-fluoro-3,3-dimethylbutanoate (1.1 g). 1H NMR (400 MHz, CDCl3) δ ppm 4.46-4.53 (1H, m), 4.28-4.42 (3H, m), 1.59 (3H, s), 1.21-1.31 (15H, m).

Workup

temperatureThe reaction mixture was cooled down
filtrationThe solid was filtered
washwashed with water and EtOAc
customThe filtrate was separated
washthe organic layer was washed with water, sat. NaCl
dry with materialdried (MgSO4)
custompurified by flash chromatography (EtOAc/hexane)

Sources & evidence

ORD record: ord-123710cb3b9642a2a1939182945b1418
Source dataset: uspto-grants-2016_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09326973B2

Linked notes

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