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.