Polynuclear lanthanide–diketonato clusters for the catalytic hydroboration of carboxamides and esters

Catalytic reduction of carboxamides into their corresponding amines is an attractive but extremely challenging transformation, which often meets with limited success; the valuable amine products drive ongoing research in this area. Here we show the direct deoxygenation of carboxamides using earth-abundant lanthanum catalysts in the presence of HBpin, presenting good to excellent yields with broad substrate scope and functional group/heteroatom tolerance. Moreover, this method is also effective in catalysing the hydroboration of esters. Finally, selective cleavage of the amide group bonds (C–N versus C–O) could be achieved based on the nature of the nitrogen substituents.