Comparison of Two Zinc Hydride Precatalysts for Selective Dehydrogenative Borylation of Terminal Alkynes: A Detailed Mechanistic Study

Abstract

The conjugated bis-guanidinate-stabilized zinc hydride complex (I)-precatalyzed chemoselective dehydroborylation of a wide array of terminal alkynes with excellent yields is reported. Further, precatalyst I is compared with a newly synthesized DiethylNacNac zinc hydride precatalyst (III) for selective dehydroborylation of terminal alkynes, and it is discovered that precatalyst I is more active than III. We have studied intra- and intermolecular chemoselective dehydroborylation of terminal alkynes over other reducible functionalities such as alkene, ester, isocyanide, nitro, and heterocycles. The highly efficient precatalyst I shows a turnover number of 48.5 and turnover frequency of up to 60.5 h−1 in the dehydroborylation of 1-ethynyl-4-fluorobenzene (1i). A plausible mechanism for selective dehydrogenative borylation of alkynes has been proposed based on active catalyst isolation and a series of stoichiometric reactions.