Jump to main content
Jump to site search


External electric field control: driving the reactivity of metal-free azide–alkyne click reactions

Author affiliations

Abstract

Recent reports have suggested that an external electric field (EEF) can assist and even control product selectivity. In this work, we have shown that the barrier for the Huisgen reaction between alkyl (aryl) azide and cyclooctyne(biflurocyclooctyne) is reduced by ∼3–4 kcal mol−1 when an oriented EEF is applied along the reaction axis. As a consequence of their inherently polar transition-states (TSs), a parallel orientation of the EEF results in enhancement of the charge transfer (CT) between the fragments and concomitant increase in the dipole moment along the reaction axes. This leads to an increase in the reaction rate for moderate EEFs in the range of 0.3–0.5 V Å−1. Since highly polar and directional environments are omnipresent in biological environments, metal-free click reactions can be further accelerated for non-invasive imaging of live-cells. Conceptually, electric field control appears to be a novel tool (catalyst) to drive, and possibly even tune, the reactivity of organic molecules.

Graphical abstract: External electric field control: driving the reactivity of metal-free azide–alkyne click reactions

Back to tab navigation

Supplementary files

Publication details

The article was received on 22 Jun 2017, accepted on 07 Aug 2017 and first published on 07 Aug 2017


Article type: Paper
DOI: 10.1039/C7CP04202G
Citation: Phys. Chem. Chem. Phys., 2017, Advance Article
  •   Request permissions

    External electric field control: driving the reactivity of metal-free azide–alkyne click reactions

    K. Bhattacharyya, S. Karmakar and A. Datta, Phys. Chem. Chem. Phys., 2017, Advance Article , DOI: 10.1039/C7CP04202G

Search articles by author

Spotlight

Advertisements