ja5b04548_si_001.pdf (1.59 MB)
Highly Active Nickel Catalysts for C–H Functionalization Identified through Analysis of Off-Cycle Intermediates
journal contribution
posted on 2015-06-24, 00:00 authored by Alex J. Nett, Wanxiang Zhao, Paul M. Zimmerman, John MontgomeryAn
inhibitory role of 1,5-cyclooctadiene (COD) in nickel-catalyzed
C–H functionalization processes was identified and studied.
The bound COD participates in C–H activation by capturing the
hydride, leading to a stable off-cycle π-allyl complex that
greatly diminished overall catalytic efficiency. Computational studies
elucidated the origin of the effect and enabled identification of
a 1,5-hexadiene-derived pre-catalyst that avoids the off-cycle intermediate
and provides catalytic efficiencies that are superior to those of
catalysts derived from Ni(COD)2.