On the Mechanism and Selectivity of the Combined C−H Activation/Cope Rearrangement

Jørn H. Hansen, Timothy M. Gregg, Stephanie R. Ovalles, Yajing Lian, Jochen Autschbach, and Huw M. L. Davies

J. Am. Chem. Soc.,
2011, 133, (13), 5075-5085; 10.1021/ja111408v


The Combined C–H Functionalization/Cope-rearrangement of vinyl carbenes, developed by the Davies group, has been proven to be a powerful transformation in the construction of highly functionalized, stereodefined molecules. This collaborative report from the Davies and Autschbach groups delves deeper into the mechanism of this reaction.

Through a combination of experimental and theoretical experiments a detailed picture of the reaction is proposed, providing details on the conformation of the metal-bound carbene, the approach of the substrate and order of electron movement in the reaction.

This report provides an excellent example of the interaction between a synthetic- and theoretical-chemistry group, building a detailed picture of the mechanism and answering questions together.

It is proposed that this will not only expand the scope of this reaction, but help guide the design of carbenes and catalysts that can take advantage of the features of this mechanism and help expand the reaction of these systems.

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