Dimethyl Sulfoxide → 1-((9RS,10RS)-2-Chloro-9,10-dihydro-9,10-methanoanthracen-9-ylmethyl)-4-formylpiperidine

Participants

Reaction Conditions

Reaction Steps

A solution of oxalyl chloride (4.51 g, 35.6 mmol) in dichloromethane (100 mL) was cooled to ←60° C. and was treated dropwise with dimethylsulfoxide (2.92 g, 37.4 mmol). The resulting solution was stirred at -65° C. for 15 min, then was treated dropwise with a solution of 1-((9RS,10RS)-2-chloro-9,10-dihydro-9,10-methanoanthracen-9-ylmethyl)-4-piperidinemethanol (8.40 g, 23.7 mmol) in dichloromethane (30 mL). The reaction mixture was stirred at -65° C. for 1 h, then was treated with triethylamine (7.20 g, 71.2 mmol) and allowed to warm to room temperature. The mixture was then poured into 10% aqueous sodium hydroxide (100 mL) and was extracted with chloroform (3×150 mL). The organic extracts were washed sequentially with 1N aqueous sodium hydroxide (100 mL) and brine (100 mL), combined, dried (K2CO3), filtered and evaporated to leave the title compound as an amber foam (8.12 g, 23.1 mmol, 97%). 1H NMR (d6-DMSO): 9.57 (s, 1H, CHO), 7.25 (m, 4H), 6.94 (m, 3H), 4.33 (s, 1H, H--C(10)), 3.34 (m, 2H, CH2N), 2.87 (m, 2H, eq-H--C(2')), 2.50 (s, 2H, H--C(11)), 2.29 (m, 3H, ax-H--C(2'), H--C(4')), 1.75 (m, 2H, eq-H--C(3')), 1.46 (m, 2H, ax-H--C(3')).

Provenance & Evidence