(Trimethylsilyl)acetonitrile → (Z)-1-(t-Butoxycarbonyl)-4-(t-butyldimethylsilyloxy)-3-(cyanomethylidene)piperidine

HRID 1171758Notes

Reaction equation

C[Si]([CH2:5][C:6]#[N:7])(C)C.C([N-]C(C)C)(C)C.[Li+].[C:16]([O:20][C:21]([N:23]1[CH2:28][CH2:27][CH:26]([O:29][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:32])[CH3:31])[C:25](=O)[CH2:24]1)=[O:22])([CH3:19])([CH3:18])[CH3:17]>O1CCCC1>[C:16]([O:20][C:21]([N:23]1[CH2:28][CH2:27][CH:26]([O:29][Si:30]([C:33]([CH3:36])([CH3:34])[CH3:35])([CH3:31])[CH3:32])/[C:25](=[CH:5]\[C:6]#[N:7])/[CH2:24]1)=[O:22])([CH3:18])([CH3:17])[CH3:19]

Participants

Conditions

Temperature: -78 °C

Procedure

To a solution of trimethylsilylacetonitrile (1.3 ml) in tetrahydrofuran (THF) (30 ml) was added at −78° C. lithium diisopropylamide (2.0 M in hexane, 4.7 ml). The resulting mixture was stirred at −78° C. for 0.5 hours, and then a solution of 1-(t-butoxycarbonyl)-4-(t-butyldimethylsilyloxy)piperidin-3-one (3 g) in THF (10 ml) was added at the same temperature. The resulting mixture was stirred for one hour while the temperature was raised to room temperature. The mixture was concentrated in vacuo, and the residue was purified by chromatography on silica gel using a mixture of hexane and ethyl acetate (9:1) as the eluent to afford the title compound (880 mg, yield: 27%) as the less polar isomer as a yellow oil.

Workup

stirringThe resulting mixture was stirred for one hour while the temperature
temperaturewas raised to room temperature
concentrationThe mixture was concentrated in vacuo
customthe residue was purified by chromatography on silica gel using
additiona mixture of hexane and ethyl acetate (9:1) as the eluent

Sources & evidence

ORD record: ord-1dc922227a074c8992803e6e194ea0f5
Source dataset: uspto-grants-2010_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07829580B2

Reaction notes

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