Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 74, Issue 17, Pages 6555-6563Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo9009968
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Funding
- National Science Foundation [CHE-0750273, CHE-0447321]
- University at Buffalo's Center for Computational Research
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The mechanism of rhodium-catalyzed cyclopropanation and C-H functionalization reactions with methyl phenyldiazoacetate and methyl diazoacetate has been studied computationally with DFT. In accordance with experimental data, it has been demonstrated that donor/acceptor rhodium carbenoids display potential energy activation barriers consistent with the much higher selectivity in cyclopropa nation and C-H insertion chemistry compared to the traditionally used acceptor carbenoids derived from unsubstituted diazo esters. Significantly higher potential energy barriers were found for transformations of donor/acceptor carbenoids than for those of acceptor systems, primarily due to the inherent stability of the former. Analyses of transition state geometries have led to the development of a rational model for the prediction of the stereochemical outcome of intermolecular C-H insertions with donor/acceptor rhodium carbenoids.
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