Reactions of Allylic Grignard Reagents and Unsaturated Amines

Article abstract of DOI:10.1021/jo00332a002

Reactions were studied of allylic Grignard reagents with allylic and propargylic amines.Additions were observed to N-allylaniline (1), cinnamylamine (6), N,N-dimethylcinnamylamine (10), and 3-(dimethylamino)-1-phenyl-1-propyne (12) but not to allylamine, diallylamine, N-allyl-N-methylaniline, N,N-dimethylallylamine, or N,N-diethylallylamine.Reactions of 3-amino-1-phenyl-1-propyne (8) furnished phenylacetylene rather than an addition product.By comparing reactivities of the amines and comparablehydrocarbons, it is concluded that tertiary amino functions and metalated primary and secondary amino functions can assist Grignard reagent additions to alkene and alkyne functions.Comparisons of reactivities of theunsaturated amines and comparable alcohols suggest that assistance by a metalated amino function is less effective than by a metalated hydroxyl function but more effective than by a tertiary amino function.Another comparison suggests that a metalated phenylamino group is more effective than a metalated primary amino group.