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

32 Citations (Scopus)

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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.

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

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

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.",

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

author = "Seath, {Ciaran P.} and Burley, {Glenn A.} and Watson, {Allan J. B.}",

note = "This is the peer reviewed version of the following article: Seath, CP, Burley, GA & Watson, AJB 2017, 'Determining the origin of rate-independent chemoselectivity in CuAAC reactions: an alkyne-specific shift in rate-determining step' Angewandte Chemie International Edition, vol 56, no. 12, pp. 3314-3318, which has been published in final form at http//dx.doi.org/10.1002/anie.201612288. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.",

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doi = "10.1002/anie.201612288",

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AU - Burley, Glenn A.

AU - Watson, Allan J. B.

N1 - This is the peer reviewed version of the following article: Seath, CP, Burley, GA & Watson, AJB 2017, 'Determining the origin of rate-independent chemoselectivity in CuAAC reactions: an alkyne-specific shift in rate-determining step' Angewandte Chemie International Edition, vol 56, no. 12, pp. 3314-3318, which has been published in final form at http//dx.doi.org/10.1002/anie.201612288. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

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N2 - 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.

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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DO - 10.1002/anie.201612288

M3 - Article

SN - 1433-7851

VL - 56

SP - 3314

EP - 3318

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

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

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Keywords

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Glenn Burley

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