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 › peer-review

15 Citations (Scopus)

27 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

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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

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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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AU - Watson, Allan J. B.

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AB - 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.

KW - kinetic analysis

KW - spectroscopic analysis

KW - chemoselectivity

KW - copper-catalyzed azide-alkyne click

KW - rate-determining step

KW - aromatic ynamine class

KW - acetylide formation

KW - azide ligation

KW - /migratory insertion

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

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JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

SN - 1433-7851

IS - 12

ER -

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

Abstract

Keywords

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Glenn Burley

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