N-Methyl Allylic Amines from Allylic Alcohols by Mitsunobu Substitution Using N-Boc Ethyl Oxamate

We report the practical, scalable synthesis of a range of N -methyl allylic amines. Primary and secondary allylic alcohols underwent a regioselective Mitsunobu reaction with readily accessible N -Boc ethyl oxamate to deliver the corresponding N -Boc allylic amines, including in enantiopure form via stereospecific substitution. Subsequent N -methylation and Boc deprotection without chromatography yielded the amine products as hydrochloride salts. This method solves the problem of converting commercially available alcohols into often volatile N -methyl allylic amines, many of which have limited commercial availability.