Observation of a Tricyclic[4.1.0.02,4 ]heptane During a Michael Addition-Ring Closure Reaction and a Computational Study on Its Mechanism of Formation

The Journal of Organic Chemistry
Marco Farren-DaiAndrew J Bennet

Abstract

We describe the formation of a bis-cyclopropane product, a tricyclic[4.1.0.02,4]heptane, that is formed during a Johnson-Corey-Chaykovsky reaction on a cyclopentenone. Two (of four possible) bicyclic products are selectively formed by addition of a COOEt-stabilized sulfur ylide onto the Michael acceptor. The tricyclic product is formed subsequently via a retro Michael elimination of a hindered ether followed by addition of a further cyclopropyl moiety, affecting only one of the two bicyclic products initially formed. The experimental reaction outcome was rationalized using density functional theory (DFT), investigating the different Michael-addition approaches of the sulfur ylide, the transition state (TS) energies for the formation of possible zwitterionic intermediates and subsequent reactions that give rise to cyclopropanation. Selective formation of only two of the four possible products occurs due to the epimerization of unreactive intermediates from the other two pathways, as revealed by energy barrier calculations. The formation of the tricyclic product was rationalized by evaluation of energy barriers for proton abstraction required to form the intermediate undergoing the second cyclopropanation. The selectivity-guiding...Continue Reading

References

Feb 19, 2002·Chemical Reviews·Michael P. Doyle, David C. Forbes
Apr 10, 2003·Chemical Reviews·Hélène LebelAndré B Charette
Apr 13, 2005·The Journal of Organic Chemistry·Makoto ItagakiYohsuke Yamamoto
Sep 28, 2005·Chemistry : a European Journal·Varinder K Aggarwal, Emma Grange
Dec 2, 2006·The Journal of Organic Chemistry·Michael P Doyle
Jul 29, 2008·Accounts of Chemical Research·Xiu-Li Sun, Yong Tang
Jun 3, 2010·Journal of the American Chemical Society·Samantha L RichesVarinder K Aggarwal
May 18, 2012·Chemical Society Reviews·David Y-K ChenJean-Alexandre Richard

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