Experimental and computational studies have shown that  acetoxycyclohexadienone analogues undergo both [3,3]- and [3,5]-sigmatropic rearrangements. The [3,5]-sigmatropic rearrangement which is thermally forbidden according to Woodward-Hoffmann rules, occurs via a facile  pseudopericyclic 8-centered transition state. To further extend the scope of pseudopericyclic reactions, coumarin based structures were designed and synthesized. Based on initial orbital analysis both [3,3]- and [3,5]-sigmatropic rearrangements can be predicted.  Detailed thermal and computational studies for the newly designed coumarin derivatives will be discussed.

Pseudopericyclic reactions: Extension to coumarin derivatives

247th National Meeting (2014)

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