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

Research output: Contribution to journal › Article

10 Citations (Scopus)

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.
LanguageEnglish
Pages3314-3318
Number of pages5
JournalAngewandte Chemie International Edition
Volume56
Issue number12
Early online date16 Feb 2017
DOIs
Publication statusPublished - 13 Mar 2017

Fingerprint

Alkynes
Azides
Spectroscopic analysis
Ligation
Copper
Kinetics

Keywords

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

Cite this

Seath, Ciaran P. ; Burley, Glenn A. ; Watson, Allan J. B. / Determining the origin of rate-independent chemoselectivity in CuAAC reactions : an alkyne-specific shift in rate-determining step. In: Angewandte Chemie International Edition. 2017 ; Vol. 56, No. 12. pp. 3314-3318.
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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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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. https://doi.org/10.1002/anie.201612288

Determining the origin of rate-independent chemoselectivity in CuAAC reactions : an alkyne-specific shift in rate-determining step. / Seath, Ciaran P.; Burley, Glenn A.; Watson, Allan J. B.

In: Angewandte Chemie International Edition, Vol. 56, No. 12, 13.03.2017, p. 3314-3318.

Research output: Contribution to journal › Article

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Y1 - 2017/3/13

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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.

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KW - spectroscopic analysis

KW - chemoselectivity

KW - copper-catalyzed azide-alkyne click

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KW - acetylide formation

KW - azide ligation

KW - /migratory insertion

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Seath CP, Burley GA, Watson AJB. Determining the origin of rate-independent chemoselectivity in CuAAC reactions: an alkyne-specific shift in rate-determining step. Angewandte Chemie International Edition. 2017 Mar 13;56(12):3314-3318. https://doi.org/10.1002/anie.201612288

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