Three concomitant C-C dissociation pathways during the mechanical activation of an N-heterocyclic carbene precursor.

Nature Chemistry
Robert Nixon, Guillaume De Bo

Abstract

Chemical reactions usually proceed through a radical, concerted or ionic mechanism; transformations in which all three mechanisms occur are rare. In polymer mechanochemistry, a mechanical force, transduced along polymer chains, is used to activate covalent bonds in mechanosensitive molecules (mechanophores). Cleavage of a C-C bond often follows a homolytic pathway, but some mechanophores have also been designed that react in a concerted or, more rarely, a heterolytic manner. Here, using 1H- and 19F-nuclear magnetic resonance spectroscopy in combination with deuterium labelling, we show that the dissociation of a mechanophore built around an N-heterocyclic carbene precursor proceeds with the rupture of a C-C bond through concomitant heterolytic, concerted and homolytic pathways. The distribution of products probably arises from a post-transition-state bifurcation in the reaction pathway, and their relative proportion is dictated by the polarization of the scissile C-C bond.

References

Aug 19, 2004·Chemistry : a European Journal·Gregory W NyceJames L Hedrick
Aug 12, 2005·Chemical Reviews·Martin K Beyer, Hauke Clausen-Schaumann
Mar 23, 2007·Nature·Charles R HickenbothScott R Wilson
Aug 14, 2008·Chemical Reviews·Morten Meldal, Christian Wenzel Tornøe
Sep 4, 2008·Angewandte Chemie·Daniel H EssKendall N Houk
Oct 22, 2008·Journal of the American Chemical Society·S KarthikeyanRint P Sijbesma
Oct 16, 2009·Chemical Reviews·Mary M CarusoJeffrey S Moore
Aug 28, 2010·Science·Jeremy M LenhardtStephen L Craig
May 1, 2009·Nature Chemistry·Alessio PiermatteiRint P Sijbesma
Jun 1, 2009·Nature Chemistry·Sergi Garcia-ManyesJulio M Fernández
Jun 2, 2012·Journal of the American Chemical Society·Hope M KlukovichStephen L Craig
Oct 1, 2013·Nature Communications·Yancong TianRoman Boulatov
Jun 21, 2014·Nature Chemistry·Charles E DiesendruckJeffrey S Moore
Jun 27, 2014·Nature·Matthew N HopkinsonFrank Glorius
Aug 13, 2014·Macromolecular Rapid Communications·Gregory I Peterson, Andrew J Boydston
Nov 20, 2014·Faraday Discussions·Tomohiro ShirakiJeffrey S Moore
May 21, 2015·Chemical Reviews·Darrin M FlaniganTomislav Rovis
Sep 4, 2015·Journal of the American Chemical Society·Junpeng WangStephen L Craig
Oct 1, 2015·Angewandte Chemie·Philipp Michael, Wolfgang H Binder
Dec 15, 2015·Angewandte Chemie·Jess M CloughRint P Sijbesma
Dec 13, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Miriam WollenhauptDominik Marx
Jun 14, 2018·Angewandte Chemie·Michela Di GiannantonioKatharina M Fromm
May 18, 2019·ACS Macro Letters·Ye ShaChuanbing Tang
May 22, 2019·Angewandte Chemie·Michael F PillHauke Clausen-Schaumann
Jun 12, 2019·Chemical Science·Ye ShaChuanbing Tang

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Citations

Jan 1, 2021·Journal of the American Chemical Society·Robert Nixon, Guillaume De Bo
Mar 6, 2021·Journal of the American Chemical Society·Cameron L BrownStephen L Craig
Mar 31, 2021·Journal of the American Chemical Society·Brandon H BowserStephen L Craig
Apr 8, 2021·Angewandte Chemie·Hang ShenAndrew J Boydston
Jul 21, 2021·Journal of the American Chemical Society·Yujin ChaChuanbing Tang
Sep 23, 2020·Journal of the American Chemical Society·Liqi WangRoss A Widenhoefer
Sep 10, 2020·Journal of the American Chemical Society·Isabel M KleinMaxwell J Robb
Sep 30, 2021·Journal of the American Chemical Society·Qingkai QiXiaocun Lu
Sep 10, 2021·Angewandte Chemie·Sangmin Jung, Hyo Jae Yoon
Nov 5, 2021·Journal of the American Chemical Society·James R HemmerJosé Augusto Berrocal

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Methods Mentioned

BETA
NMR

Software Mentioned

MMFF
CoGEF
Spartan

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