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

Ciaran P. Seath; Glenn A. Burley; Allan J. B. Watson

doi:10.1002/anie.201612288

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

Ciaran P. Seath, Glenn A. Burley, Allan J. B. Watson

Pure And Applied Chemistry

Research output: Contribution to journal › Article

14 Citations (Scopus)

22 Downloads (Pure)

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.

Original language	English
Pages (from-to)	3314-3318
Number of pages	5
Journal	Angewandte Chemie International Edition
Volume	56
Issue number	12
Early online date	16 Feb 2017
DOIs	https://doi.org/10.1002/anie.201612288
Publication status	Published - 13 Mar 2017

Keywords

kinetic analysis
spectroscopic analysis
chemoselectivity
copper-catalyzed azide-alkyne click
rate-determining step
aromatic ynamine class
acetylide formation
azide ligation
/migratory insertion

Access to Document

10.1002/anie.201612288

Seath-etal-AWIE2017-Determining-the-origin-of-rate-independent-chemoselectivityAccepted author manuscript, 900 KB

http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1521-3773

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Glenn Burley

glenn.burley@strath.ac.uk

Pure And Applied Chemistry - Professor

Person: Academic

Cite this

Seath, C. P., Burley, G. A., & Watson, A. 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), 3314-3318. https://doi.org/10.1002/anie.201612288

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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.",

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