Determining the origin of rate-independent chemoselectivity in CuAAC reactions : an alkyne-specific shift in rate-determining step

Seath, Ciaran P. and Burley, Glenn A. and Watson, Allan J. B. (2017) Determining the origin of rate-independent chemoselectivity in CuAAC reactions : an alkyne-specific shift in rate-determining step. Angewandte Chemie International Edition, 56 (12). pp. 3314-3318. ISSN 1433-7851

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    Abstract

    We report a kinetic and spectroscopic analysis of alkynedependent chemoselectivity in the copper-catalyzed azide-alkyne click (CuAAC) reaction. Studies of six alkyne subtypes reveal that the rate-determining step (RDS) of an aromatic ynamine class is shifted from acetylide formation to the azide ligation/migratory insertion event allowing chemoselectivity independent of overall rate.