Chlorotrimethylsilane → HCID 18987898, compound

Participants

Reaction Steps

In an effort to diminish homocoupling, 3-chlorocyclohexene (3.20 mmol) was weighed in a large vial and capped with a septum. Once under an argon atmosphere, THF (10 ml) was added to the vial. To a stirring active coppersolution (8.23 mmol in 23 ml of THF) at -95° C., the allyl chloride is delivered dropwise from a cannula, over 30 minutes. After 5 minutes, TMSCl (2.84 mmol) is injected neat prior to the neat, dropwise injection of 2-cyclohexenone (0.82 mmol). The reaction flask is placed in a -78° C. bath and allowed to gradually warm to room temperature. Thereaction mixture is quenched with NH4Cl (sat'd) (50 ml) and Et2O (25 ml) is added prior to further extraction of the organic layer with 0.5M HCl (50 ml), water (50 ml), and brine (50 ml). The combined aqueous layers are back extracted with Et2O (30 ml). The combined organic layers are dried with MgSO4 and reduced in volume for column chromatography. 3-(2-cyclohexenyl)cyclohexanone (0.43 mmol) was isolated in 52% yield (not shown in Table III). Rf =0.31 in 9:1 (v/v) hexane and ethyl acetate, respectively. 1H NMR (300 MHz) 5.73-5.67 (m, 1H),5.53-5.50 (m, 1H), 2.37-1.16 (m, 16H). 13C NMR (75 MHz) 212.50, 212.47, 129.1, 128.8, 128.7, 128.5, 45.2, 45.0, 43.6, 41.4, 40.0, 39.9, 28.4, 28.1, 25.52, 25.46, 25.41, 25.3, 25.2, 25.1, 21.8, 21.7.

Provenance & Evidence