Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 141, Issue 25, Pages 10016-10032Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b03890
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Funding
- NIH [GM-112684, GM-08765]
- NSF [1S10RR023444, 1S10RR022442, CHE-0840438, CHE-0848460, 1S10OD011980, CHE1464778, CHE1764298]
- XSEDE [TG-CHE120052]
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A highly chemoselective phenol cross-coupling reaction catalyzed by a Cr-salen catalyst was developed. Kinetic studies showed that the oxidation of Cr(III) to Cr(V) is the rate-determining step of the reaction. In addition, experimental stoichiometric analysis showed that a high valent Cr(V) species is the active catalyst for this process. The selectivity of the reaction was found to be determined by the cross-coupling carbon-carbon bond forming reaction, rather than any precoordination species. It appears that the lowest energy cross-coupling pathway requires a lesser degree of electronic reorganization in its transition state vs the lowest energy homocoupling pathway. This result was supported by stoichiometric Cr(V) kinetics, C-13 kinetic isotope effects, and density functional theory (DFT) calculations. The understanding of the full landscape of this reaction allowed us to develop a general analysis to predict the regioselectivity of the cross-coupling reaction.
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