Density Functional Theory Mechanistic Study of Ni-Catalyzed Reductive Alkyne-Alkyne Cyclodimerization: Oxidative Cyclization versus Outer-Sphere Proton Transfer

Organic Letters
Xiaojian RenZhi-Xiang Wang

Abstract

Density functional theory mechanistic study of the nickel-catalyzed reductive alkyne-alkyne cyclodimerization with CH3OH/BEt3 unveils that, after forming a nickel-alkyne π complex, the reaction prefers outer-sphere proton transfer rather than the common alkyne-alkyne oxidative cyclization. The outperformance of aminophosphine ligand (L1) is attributed to its bidentate coordination that favors the proton transfer, the labile -NH2 and strong electron-donating -PPh2 arms and adequate Ni-P distance that allow the hydrogen transfer of the ethyl group of MeO-BEt3-.

References

Nov 10, 2000·Chemistry : a European Journal·D J HuangC H Cheng
Apr 10, 2003·Chemical Reviews·Jan C Namyslo, Dieter E Kaufmann
Apr 9, 2004·Journal of the American Chemical Society·Hisanaka ItoKazuo Iguchi
Jun 17, 2004·Journal of the American Chemical Society·Randy F SweisSergey A Kozmin
May 25, 2007·Journal of the American Chemical Society·Tülay A AteşinWilliam D Jones
Sep 12, 2012·Angewandte Chemie·Karin RadkowskiAlois Fürstner
Sep 13, 2012·Journal of the American Chemical Society·Akira NishimuraSensuke Ogoshi
Sep 21, 2013·Journal of the American Chemical Society·Shinsuke KomagawaMasanobu Uchiyama
Feb 5, 2015·Angewandte Chemie·Michael Fuchs, Alois Fürstner
Mar 12, 2015·Angewandte Chemie·Njamkou N Noucti, Erik J Alexanian
Jun 10, 2015·Journal of the American Chemical Society·Alex J NettJohn Montgomery
Feb 9, 2016·Journal of the American Chemical Society·Li-Jun XiaoQi-Lin Zhou
Feb 13, 2018·Journal of the American Chemical Society·Alexandre GuthertzAlois Fürstner
Aug 29, 2018·Frontiers in Chemistry·Wen-Jie ChenXin Huang
Oct 4, 2018·Journal of the American Chemical Society·Can ZhuJan-E Bäckvall
Dec 6, 2018·Journal of the American Chemical Society·Santiago CañellasMiquel À Pericàs
Sep 3, 2019·Journal of the American Chemical Society·Mahesh M ParsutkarT V RajanBabu

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