Chlorotrimethylsilane → HCID 18987898, compound

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.

1. customcapped with a septum
2. customis placed in a -78° C.
3. customThereaction mixture is quenched with NH4Cl (sat'd) (50 ml) and Et2O (25 ml)
4. additionis added
5. extractionto further extraction of the organic layer with 0.5M HCl (50 ml), water (50 ml), and brine (50 ml)
6. extractionThe combined aqueous layers are back extracted with Et2O (30 ml)
7. dry with materialThe combined organic layers are dried with MgSO4

ORD record

ord-54defe546e41414db5fae53c5b67c50f

Source dataset

uspto-grants-1996_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05490952