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

School of Chemistry

Research output: Contribution to journal › Article › peer-review

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

Chemoselectivity
Click reactions
CuAAC
Reaction kinetics

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10.1002/anie.201612288

https://strathprints.strath.ac.uk/60227/

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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 = "Chemoselectivity, Click reactions, CuAAC, Reaction kinetics",

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

note = "We thank the Carnegie Trust for a PhD Scholarship (C.P.S.), G.A.B. thanks the Alexander von Humboldt Foundation (Visiting Research Fellowship, LMU Munich).",

year = "2017",

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doi = "10.1002/anie.201612288",

language = "English",

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journal = "Angewandte Chemie International Edition",

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T1 - Determining the origin of rate-independent chemoselectivity in CuAAC reactions

T2 - an alkyne-specific shift in rate-determining step

AU - Seath, Ciaran P.

AU - Burley, Glenn A.

AU - Watson, Allan J. B.

N1 - We thank the Carnegie Trust for a PhD Scholarship (C.P.S.), G.A.B. thanks the Alexander von Humboldt Foundation (Visiting Research Fellowship, LMU Munich).

PY - 2017/3/13

Y1 - 2017/3/13

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 - Chemoselectivity

KW - Click reactions

KW - CuAAC

KW - Reaction kinetics

UR - https://www.scopus.com/pages/publications/85013301861

U2 - 10.1002/anie.201612288

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

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Keywords

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