Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application

Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, deoxygenative amide reduction has proven to be promising but challenging, as approach necessitates C–O bond cleavage. Herein, we report hydroboration primary, secondary, tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, accessing diverse amines. Various readily reducible functional groups, such esters, alkynes, alkenes, were well tolerated. Furthermore, methodology was extended bio- drug-derived Detailed mechanistic studies revealed reaction pathway entailing aldehyde amido complex formation via unusual C–N cleavage-reformation process, followed