Chlorotrimethylsilane → HCID 25234411, compound

Participants

Reaction Conditions

Reaction Steps

To a 100 mL round bottom flask containing a stir bar was added 0.185 g of zinc dust (2.83 mmol) and 3 mL of N,N-dimethylacetamide. The flask was placed under nitrogen and 0.08 mL of TMS-chloride (0.63 mmol) and 0.05 mL of 1,2-dibromoethane (0.58 mmol) were added by syringe. The reaction was stirred for 5 min. and 0.09 mL of 2-bromothiazole (0.998 mmol) was added by syringe. The reaction was stirred for 1 hour at room temperature under nitrogen. To a separate 100 mL round bottom flask containing a stir bar was added 0.124 g of 3-bromocyclohex-2-enone (0.708 mmol) and 0.024 g of Pd(PPh3)2Cl2 (4.8 mol %), and 10 mL of anhydrous THF. The previously prepared organozinc species was added to the enone solution dropwise with removal of excess zinc using a syringe fitted with a cotton plug. The reaction was heated overnight at 60° C. in an oil bath with stirring under nitrogen atmosphere. The reaction was worked up by transferring the solution to a vial containing 10 mL of saturated ammonium chloride solution, and the product was extracted with ethyl acetate (2 times with 8 mL). The organic layer was dried with sodium sulfate, filtered, and solvent was concentrated under reduced pressure. The product was purified by flash chromatography using the Biotage system utilizing gradient elution (0% to 80% ethyl acetate/hexanes). Product fractions were combined and concentrated to yield a pale yellow solid (35 mg, 28%). 1H NMR (CDCl3, 300 MHz): δ 2.17 (quintet, J=6.3 Hz, 2H), 2.52 (t, J=6.3 Hz, 2H), 2.97 (td, J=6.3, 1.5 Hz, 2H), 6.69 (br s, 1H), 7.45 (d, J=3.0 Hz, 1H), 7.93 (d, J=3.0 Hz, 1H). 13C NMR (CDCl3, 75 MHz): δ 22.4, 27.0, 37.8, 121.4, 126.6, 144.4, 151.7, 166.7, 199.4. LCMS (ESI): mass calcd for (C9H9NOS) m/z 179.04; measured [M+H]+: m/z 180.03.

Provenance & Evidence