Air-Stable Iron(III) Salen Complexes for Selective Hydroboration of Ketones and Unactivated Imines without Base Activation.

Abstract

Herein, we designed and synthesized a series of air-stable, cost-effective, and readily synthesizable iron(III) salen complexes (Fe-1 and Fe-2) for facilitating the selective hydroboration of ketones and unactivated imines with pinacolborane in the absence of any additive. These catalyst systems exhibited good yields, chemoselectivity, high atom economy, and a broad substrate scope under mild reaction conditions with a minimal catalyst loading of 0.2 mol %. The catalytic efficiency of Fe-1 has been demonstrated through the hydroboration of diverse aromatic, aliphatic, and heterocyclic ketones and imines with a turnover number of up to 1000, highlighting its broad substrate scope. Ketones are chemoselectively hydroborated over other functional groups such as imines, alkenes, esters, nitriles, acids, and alcohols. Besides, the synthetic utility of this strategy has also been showcased by the construction of a natural chiral monoterpenoid carveol. This protocol can be readily scaled up for gram-scale synthesis of alcohols, which underscores the potential industrial applicability of our catalyst system in the synthesis of secondary alcohols on a larger scale.