Cp*RuCl-Vinyl Carbenes: Two Faces and the Bifunctional Role in Catalytic Processes

Chemistry : a European Journal
Damián PadínCarlos Saá

Abstract

Ruthenium vinyl carbenes derived from Cp/Cp*RuCl-based complexes have been routinely invoked as key intermediates in tandem reactions involving a carbene/alkyne metathesis (CAM). A priori, these intermediates resemble the Grubbs-type family of catalysts, but they exhibit a completely different reactivity pattern that few, if any, other catalytic system can reproduce so far. The reactivity of these species with α-unsubstituted and α-substituted alkynals showcases the peculiarities of these intermediates. While Z-vinyl dihydrooxazines are preferentially obtained with the former, Z-vinyl epoxypyrrolidines are obtained with the latter. A combination of spectroscopic and computational data now prove that a η3-coordination mode of the ruthenium vinyl carbene and the presence of a Lewis basic chloride ligand give rise to two markedly different stereoelectronic faces that are responsible for the unconventional reactivity of these species.

References

Mar 27, 2001·Organic Letters·M P DoyleD J Timmons
Feb 1, 1996·Chemical Reviews·Albert Padwa, M. David Weingarten
Apr 10, 2003·Chemical Reviews·Hélène LebelAndré B Charette
Mar 11, 2004·Chemical Reviews·Steven T Diver, Anthony J Giessert
Jun 25, 2004·Chemical Communications : Chem Comm·Yajun Wang, Frank Caruso
Sep 10, 2004·Journal of the American Chemical Society·Yike Ni, John Montgomery
May 19, 2005·Journal of the American Chemical Society·Jörg J Lippstreu, Bernd F Straub
Feb 24, 2006·Journal of the American Chemical Society·Yike Ni, John Montgomery
Dec 19, 2006·Chemical Society Reviews·Hélène VillarCarsten Bolm
Apr 7, 2007·The Journal of Chemical Physics·Kirk A PetersonHermann Stoll
Apr 14, 2007·Journal of the American Chemical Society·Florian MonnierCarlo Mealli
Nov 13, 2007·Nature·Amir H Hoveyda, Adil R Zhugralin
Jan 25, 2008·Nature·Huw M L Davies, James R Manning
Mar 5, 2008·The Journal of Chemical Physics·Jeng-Da Chai, Martin Head-Gordon
Nov 8, 2008·Physical Chemistry Chemical Physics : PCCP·Jeng-Da Chai, Martin Head-Gordon
Mar 1, 2007·Coordination Chemistry Reviews·Steven T Diver
Sep 30, 2009·Chemical Reviews·Michael P DoyleLei Zhou
Oct 23, 2009·Chemical Society Reviews·Albert Padwa
Oct 23, 2009·Chemical Society Reviews·Alois Fürstner
Dec 17, 2009·Chemical Reviews·Georgios C Vougioukalakis, Robert H Grubbs
May 13, 2010·Journal of the American Chemical Society·Jacques Le PaihPierre H Dixneuf
Mar 30, 2011·Beilstein Journal of Organic Chemistry·Cédric Fischmeister, Christian Bruneau
Dec 2, 2011·Angewandte Chemie·Fermín CambeiroCarlos Saá
Oct 23, 2012·Journal of the American Chemical Society·Santa Jansone-Popova, Jeremy A May
Apr 15, 2016·Journal of the American Chemical Society·Justin R GriffithsSteven T Diver
Feb 9, 2017·Journal of the American Chemical Society·Dragoş-Adrian RoşcaAlois Fürstner
Feb 13, 2018·Journal of the American Chemical Society·Alexandre GuthertzAlois Fürstner
Nov 6, 2018·Organic & Biomolecular Chemistry·Chao PeiXinfang Xu

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Citations

Oct 20, 2020·Journal of the American Chemical Society·Sebastian PeilAlois Fürstner

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