Dichloromethane → HCID 131732934, compound

Participants

Reaction Steps

A flask equipped with stirbar was charged with 4 mL tetrahydrofuran and cooled in an ice bath. Titanium(IV) chloride, 1M solution in dichloromethane (2.1 mL, 2.100 mmol) was added by syringe, providing a suspension. After 15 minutes, a solution of Example 93c (0.322 g, 1.034 mmol) and ethyl 2-nitroacetate (0.115 mL, 1.034 mmol) in tetrahydrofuran (0.5 mL) was added. After an additional 15 minutes, a solution of 4-methylmorpholine (0.45 mL, 4.09 mmol) in tetrahydrofuran (0.3 mL) was added dropwise. The solution was allowed to warm to ambient temperature and stirred for 18 hours. The heterogeneous reaction mixture was poured into aqueous ammonium chloride and extracted twice with ether. The combined organics were washed with saturated aqueous sodium chloride then dried over anhydrous magnesium sulfate. Filtration, solvent removal, and chromatography on a 12 g silica gel cartridge eluting with 0-60% ethyl acetate/heptane provided the title compounds as a 2.5:1 mixture of olefin isomers.

Provenance & Evidence