Influence of Alkyne and Azide Substituents on the Choice of the Reaction Mechanism of the Cu+ -Catalyzed Addition of Azides to Iodoalkynes

The Journal of Physical Chemistry. a
Pedro J Silva, Carlos E P Bernardo

Abstract

The cycloaddition of azides to iodoalkynes is strongly enhanced by some Cu+-complexes. We have studied computationally six reaction pathways for the cycloaddition of 24 combinations of azide and iodoalkyne to identify the dominant pathways and the influence of reactant structure on the evolution of the reaction. Two pathways were found to be operating for distinct sets of reactants. In the first pathway, initial complexation of iodoalkyne by Cu+ is followed by the binding of the azide to the metal through its substituted nitrogen atom, followed by attack of the nonhalogenated alkyne carbon by the terminal nitrogen atom. This pathway is generally followed by aromatic or electron-deficient azides, unless the iodoalkyne bears an electron-withdrawing group. The second pathway is a single-step mechanism similar (apart from the alkyne bond weakening caused by complexation) to that observed in the absence of catalyst. Electron-deficient iodoalkynes and methyl azides strongly prefer this mechanism, regardless of the identity of the reaction partners. The catalytic gain obtained through the use of Cu+ depends only partially on its direct effect on the energy of the transition state (relative to that of the infinitely separated reactants...Continue Reading

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Dec 18, 2003·Drug Discovery Today·Hartmuth C Kolb, K Barry Sharpless
Jan 6, 2005·Journal of the American Chemical Society·Fahmi HimoValery V Fokin
Feb 5, 2005·Angewandte Chemie·Valentin O RodionovM G Finn
Jul 15, 2006·The Journal of Physical Chemistry. a·Christophe MorellAlejandro Toro-Labbé
Sep 14, 2006·Chemistry : a European Journal·Silvia Díez-GonzálezSteven P Nolan
Feb 16, 2007·Angewandte Chemie·Christoph NolteBernd F Straub
Oct 5, 2007·Journal of the American Chemical Society·Valentin O RodionovM G Finn
Jan 26, 2008·Chemical Communications : Chem Comm·Bernd F Straub
May 20, 2008·The Journal of Organic Chemistry·Luis R DomingoPatricia Pérez
May 30, 2008·Pharmaceutical Research·Christopher D HeinDong Wang
Aug 14, 2009·Organic & Biomolecular Chemistry·Luis R Domingo, José A Sáez
Sep 24, 2009·Angewandte Chemie·Jason E HeinValery V Fokin
Apr 17, 2010·Chemistry : a European Journal·Benjamin R BuckleyHarry Heaney
Jun 18, 2010·The Journal of Physical Chemistry. a·Marcel SwartMiquel Solà
Jul 5, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Trevor J Del CastilloAdam S Veige
Jul 13, 2011·Organic & Biomolecular Chemistry·Ilaria Proietti SilvestriSpencer J Williams
Dec 14, 2011·Journal of Computational Chemistry·Tian Lu, Feiwu Chen
Sep 1, 1986·Journal of the American Chemical Society·W Yang, W J Mortier
Dec 25, 2013·Beilstein Journal of Organic Chemistry·Regina Berg, Bernd F Straub
Sep 10, 2015·The Journal of Organic Chemistry·David N BarsoumLei Zhu
May 25, 2016·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Lei ZhuRonald J Clark

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