Understanding the nature of the molecular mechanisms associated with the competitive Lewis acid catalyzed [4+2] and [4+3] cycloadditions between arylidenoxazolone systems and cyclopentadiene: a DFT analysis

Chemistry : a European Journal
Manuel ArnóJuan Andrés

Abstract

The molecular mechanisms of the reactions between aryliden-5(4H)-oxazolone 1, and cyclopentadiene (Cp), in presence of Lewis acid (LA) catalyst to obtain the corresponding [4+2] and [4+3] cycloadducts are examined through density functional theory (DFT) calculations at the B3LYP/6-31G* level. The activation effect of LA catalyst can be reached by two ways, that is, interaction of LA either with carbonyl or carboxyl oxygen atoms of 1 to render [4+2] or [4+3] cycloadducts. The endo and exo [4+2] cycloadducts are formed through a highly asynchronous concerted mechanism associated to a Michael-type addition of Cp to the beta-conjugated position of alpha,beta-unsaturated carbonyl framework of 1. Coordination of LA catalyst to the carboxyl oxygen yields a highly functionalized compound, 3, through a domino reaction. For this process, the first reaction is a stepwise [4+3] cycloaddition which is initiated by a Friedel-Crafts-type addition of the electrophilically activated carbonyl group of 1 to Cp and subsequent cyclization of the corresponding zwitterionic intermediate to yield the corresponding [4+3] cycloadduct. The next rearrangement is the nucleophilic trapping of this cycloadduct by a second molecule of Cp to yield the final ad...Continue Reading

Citations

May 24, 2014·Journal of the American Chemical Society·Damien F P CrépinPiotr Raubo
Aug 14, 2009·Organic & Biomolecular Chemistry·Luis R Domingo, José A Sáez
Oct 20, 2006·The Journal of Physical Chemistry. a·Gang-Long CuiJian-Guo Yu
May 4, 2011·Journal of the American Chemical Society·Christopher S JeffreyChristopher R Carson
Jun 15, 2006·Chemical Reviews·Pratim Kumar ChattarajDebesh Ranjan Roy
May 12, 2006·The Journal of Physical Chemistry. a·Shogo Sakai

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