Mechanistic Insights into Two-Phase Radical C–H Arylations

R. D. Baxter, Y. Liang, X. Hong, T. A. Brown, R. N. Zare, K. N. Houk, P. S. Baran and D. G. Blackmond

ACS Central Science
2015, 1, 456-462; 10.1021/acscentsci.5b00332


In order for a reaction to be optimized and developed to its full potential a detailed understanding of the kinetics and mechanism are required. This collaborative paper brings together the expertize from three groups from across the CCHF to help untangle the details of a multiphasic radical C–H arylation.

Using a combination of kinetic, spectroscopic and computational studies the Blackmond, Zare and Houk groups explored the metal-catalyzed C–H functionalization of heterocycles recently developed by the Baran Group. This reaction contains as many as six different components present in three different phases.

This combined approach highlighted the interplay between chemical and physical rate processes across the multiple phases and reconciled a number of anomalous concentration dependencies that were observed.

This systematic and detailed approach to understanding reaction mechanism provides a highly detailed picture of this transformation, an approach that will help untangle some of the mechanistic details of other transformations currently under development in the CCHF.

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