Autocatalytic Cycles in a Copper-Catalyzed Azide-Alkyne Cycloaddition Reaction

Sergey N. Semenov, Lee Belding, Brian J. Cafferty, Maral P. S. Mousavi, Anastasiia M. Finogenova, Ricardo S. Cruz, Ekaterina V. Skorb, George M. Whitesides*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

56 Citations (Scopus)

Abstract

This work describes the autocatalytic copper-catalyzed azid-alkyne cycloaddition (CuAAC) reaction between tripropargylamine and 2-azidoethanol in the presence of Cu(II) salts. The product of this reaction, tris-(hydroxyethyltriazolylmethyl)amine (N(C3N3)(3)), accelerates the cycloaddition reaction (and thus its own production) by two mechanisms: (i) by coordinating Cu(II) and promoting its reduction to Cu(I) and (ii) by enhancing the catalytic reactivity of Cu(I) in the cycloaddition step. Because of the cooperation of these two processes, a rate enhancement of >400x is observed over the course of the reaction. The kinetic profile of the autocatalysis can be controlled by using different azides and alkynes or ligands (e.g., ammonia) for Cu(II). When carried out in a layer of 1% agarose gel, and initiated by ascorbic acid, this autocatalytic reaction generates an autocatalytic front. This system is prototypical of autocatalytic reactions where the formation of a product, which acts as a ligand for a catalytic metal ion, enhances the production and activity of the catalyst.

Original languageEnglish
Pages (from-to)10221-10232
Number of pages12
JournalJournal of the American Chemical Society
Volume140
Issue number32
DOIs
Publication statusPublished - 15 Aug 2018

Funding

Publisher Copyright: © Copyright 2018 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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