Transition-Metal Catalysis of Triene 6π Electrocyclization: The π-Complexation Strategy Realized

Angewandte Chemie
Pengjin QinArnold L Rheingold

Abstract

Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal-alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C5 H5 )Ru(NCMe)3 ]PF6 as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations.

References

Oct 5, 2001·Journal of the American Chemical Society·D J Tantillo, R Hoffmann
Apr 4, 2002·Journal of the American Chemical Society·Joseph M O'ConnorMark Tichenor
Jun 21, 2002·Organic Letters·Christopher M Beaudry, Dirk Trauner
Jul 3, 2004·Proceedings of the National Academy of Sciences of the United States of America·Lucy M StarkErik J Sorensen
Jun 30, 2005·Journal of the American Chemical Society·Joseph M O'connorLev Zakharov
Sep 24, 2005·Organic Letters·Christopher M Beaudry, Dirk Trauner
Nov 25, 2005·Journal of the American Chemical Society·Joseph M O'ConnorBetsy L Rodgers
Dec 15, 2005·Chemical Reviews·Christopher M BeaudryDirk Trauner
Jul 29, 2006·The Journal of Organic Chemistry·Tang-Qing YuQing-Xiang Guo
Apr 20, 2007·Proceedings of the National Academy of Sciences of the United States of America·Maurice BrookhartGerard Parkin
Mar 12, 1993·Science·C P Casey
Sep 12, 2008·Angewandte Chemie·Lee M BishopDirk Trauner
Aug 14, 2010·Organic Letters·Aurélie LeverrierMarc Litaudon
Jan 25, 2011·Nature Chemistry·Ritu AhujaAlan S Goldman
Jun 2, 2011·Organic Letters·Takumi AbeMinoru Ishikura
Apr 28, 2012·Journal of the American Chemical Society·Ming BianAng Li
Jun 20, 2012·Journal of the American Chemical Society·Sang Young YunDaesung Lee
Oct 9, 2012·Organic Letters·Gregg A BarcanOhyun Kwon
Jan 1, 2013·Organic Letters·Hee Nam Lim, Kathlyn A Parker
Feb 21, 2013·Angewandte Chemie·Marko Hapke, C Christoph Tzschucke
Mar 19, 2014·Chemical Society Reviews·Paul von Ragué SchleyerIsrael Fernández
Nov 2, 2014·Journal of the American Chemical Society·Jian LiAng Li
Dec 17, 2014·Nature·Kyle W Quasdorf, Larry E Overman
Jan 9, 2015·The Journal of Organic Chemistry·Christine HofmannPeter R Schreiner
Feb 11, 2016·Journal of the American Chemical Society·Christopher G NewtonNicolai Cramer
Apr 29, 2016·Angewandte Chemie·Peng YangAng Li
Dec 10, 2016·Journal of the American Chemical Society·Hailong LiAng Li
Aug 31, 2017·The Journal of Antibiotics·Yike Zou, Amos B Smith
Aug 23, 2019·Journal of the American Chemical Society·Vignesh PalaniRichmond Sarpong
Dec 24, 2019·Chemical Reviews·Damien DattlerNicolas Giuseppone
Mar 17, 2020·The Journal of Organic Chemistry·Xuchen ZhaoJon D Rainier

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