Palladium-catalyzed relay hydroaminocarbonylation of alkenes with hydroxylamine hydrochloride as an ammonia equivalent

Abstract

Amides are prevalent in pharmaceuticals, agrochemicals, and materials. Hydroaminocarbonylation of alkenes has emerged as one of the most direct and rapid approaches to amides. Nowadays, these reactions remain largely confined to using alkylamines as nitrogen sources, leading to sluggish reactions due to their strong binding ability and basicity. Here we show the application of abundantly available hydroxylamine hydrochloride (NH2OH·HCl) as a surrogate of ammonia for the relay hydroaminocarbonylation of simple alkenes in the presence of a convenient palladium catalyst system. The in situ formation of alkylamines from hydroxylamine hydrochloride by hydroaminocarbonylation reaction and Lossen rearrangement allows us to establish an efficient relay hydroaminocarbonylation. Notably, this transformation allows the catalytic formation of two C–N bonds with hydroxylamine hydrochloride as an amine source by incorporation of two molecules of alkene and avoids the use of alkylamines.