Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 137, Issue 5, Pages 2006-2014Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja512374g
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Funding
- National Science Foundation of China [21173263, 21373216]
- University of Colorado Denver
- National Science Foundation [ACI-1053575]
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Density functional theory (DFT) computations (BP86 and M06-L) have been utilized to elucidate the detailed mechanism of a palladium-catalyzed reaction involving pyridine-type nitrogen-donor ligands that significantly expands the scope of C(sp(3))-H activation and arylation. The reaction begins with precatalyst initiation, followed by substrate binding to the Pd(II) center through an amidate auxiliary, which directs the ensuing bicarbonate-assisted C(sp(3))-H bond activation producing five-membered-ring cyclopalladate(II) intermediates. These Pd(II) complexes further undergo oxidative addition with iodobenzene to form Pd(IV) complexes, which proceed by reductive C-C elimination/coupling to give final products of arylation. The base-assisted C(sp(3))-H bond cleavage is found to be the rate-determining step, which involves hydrogen bond interactions. The mechanism unravels the intimate involvement of the added 2-picoline ligand in every phase of the reaction, explains the isolation of the cyclopalladate intermediates, agrees with the observed kinetic hydrogen isotope effect, and demonstrates the Pd(II)/Pd(IV) redox manifold.
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