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Determining the Origin of Rate‐Independent Chemoselectivity in CuAAC Reactions: An Alkyne‐Specific Shift in Rate‐Determining Step
Author(s) -
Seath Ciaran P.,
Burley Glenn A.,
Watson Allan J. B.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201612288
Subject(s) - chemoselectivity , alkyne , azide , acetylide , chemistry , click chemistry , combinatorial chemistry , stereochemistry , catalysis , organic chemistry
We report a kinetic and spectroscopic analysis of alkyne‐dependent 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.