Regioselective Hydroboration of Unsymmetrical Internal Alkynes Catalyzed by a Cobalt Pincer-NHC Complex

Highly regioselective hydroboration of unsymmetrical internal alkynes remains a significant challenge for synthesizing valuable alkenylboronate esters. Herein, we describe an easily synthesizable pincer NHC-based Co complex as a catalyst for the cis-α selective hydroboration of unactivated internal alkynes and the cis-β selective hydroboration of activated internal alkynes with pinacolborane. The reaction showcases high chemo-, regio-, and stereoselectivity, and the catalyst displays high efficiency and very low loading under base-free reaction conditions. The reaction scope was demonstrated by alkynes having a variety of functional groups. The mechanistic studies suggest a feasible Co-boryl intermediate to explain the unusual regioselectivity.