Zero-Valent Copper Catalysis Enables Regio- and Stereoselective Difunctionalization of Alkynes

Abstract

The development of a metallic copper-based catalyst system remains a significant challenge. Herein, we report the synthesis of highly stable, active, and reusable Cu⁰ catalyst for the carboboration of alkynes using carbon electrophiles and bis(pinacolato)diboron (B₂pin₂) as chemical feedstocks to afford di- and trisubstituted vinylboronate esters in a regio- and stereoselective manner with appreciable turnover number (TON) of up to 2535 under mild reaction conditions. This three-component coupling reaction works well with a variety of substituted electrophiles and alkynes with broad functional group tolerance. In addition, a wide range of terminal and challenging internal alkynes were efficiently converted into hydroborated products in up to >99 % yield with excellent regioselectivity in the absence of carbon electrophiles. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) analysis confirm that the oxidation state of the copper in the catalyst is zero. The broad range of organic transformations, effectiveness, and recyclability of this Cu⁰ catalyst are the major achievements that provide an environmentally friendly route for the efficient production of tri- and tetrasubstituted olefins, key intermediates in organic synthesis. The gram-scale reaction and synthetic transformations further highlights the usefulness of these methods.