Formate ester synthesis via reaction of 2-bromoethylamines with dimethylformamide

Abstract

2-Bromoethylamines are converted to the corresponding formate esters in the presence of DMF. Both primary and secondary bromides are smoothly transformed to the esters in satisfactory yields. The reaction mechanism involves the formation of an aziridinium ion, which upon reaction with DMF forms a Vilsmeier-type intermediate that is further hydrolyzed to the corresponding formates. Participation of the β-amino group appears to control not only the regioselectivity but also the stereoselectivity of the reaction. Application of the reaction conditions to chiral substrates indicated that non-rearranged products are formed with retention of configuration at the reacting center.