Deoxygenative hydroboration of carboxamides: a versatile and selective synthetic approach to amines

Deoxygenative reduction of amides is considered as an attractive method for preparation of synthetically valuable amines. However, the low electrophilicity of the amide carbonyl group, high thermodynamic stability and kinetic inertness of the amides make their reduction a challenging task. Until recently, most efforts for catalytic deoxygenation of amides to amines were concentrated on hydrogenation and hydrosilylation approaches, which mainly employed precious metal catalysts and often required harsh reaction conditions and showed insufficient selectivities. Moreover, these reactions are mostly limited to secondary and tertiary amides, whereas direct reduction of primary amides to primary amines remained arduous. In contrast, deoxygenative hydroboration of amides, although it appeared less then a decade ago, has already proved advantageous in terms of the amide scope, reaction conditions and selectivity of transformations. This article provides an overview of the developments in hydroboration of amides, focusing on mechanistic aspects of these transformations and advantages of hydroboration compared to hydrogenation and hydrosilylation approaches.

Automated summary

Deoxygenative reduction of amides is a challenging task due to the low electrophilicity of the amide carbonyl group. Previously, efforts focused on hydrogenation and hydrosilylation approaches, which had limitations in terms of selectivity. On the other hand, deoxygenative hydroboration of amides has shown advantages in terms of scope, conditions, and selectivity compared to traditional methods.