Pseudopericyclic reactions, a subset of pericyclic reactions, are concerted with one or more orbital disconnections in a cyclic array of overlapping orbitals. These reactions exhibit planar or almost planar transition states that have very low energy barriers. Based on computational analysis at B3LYP/cc-pVDZ level for the trichloacetimidate [2a-b  ], thiocarbamate [3a-b  ], acetate [4a-b  ] and xanthate [5a-b  ], we propose a series of [3,3]- and [3,5]-sigmatropic rearrangements that will that allows substrates [2-5  ] to undergo the transformation by bringing the lone pair electrons on X closer to the single cis double bond. Steric hindrance between the allylic and methylene protons in the 5-membered ring substrates [2a-5a  ] is expected to be less than the 6-membered ring substrates [2b-5b  ], making the transition states more planar and susceptible to a [3,5]- sigmatropic shift via a pseudopericyclic pathway. The synthetic scheme for the synthesis of the substrates and the corresponding [3,3]- and [3,5]-sigmatropic rearrangements are shown

Pseudopericyclic nature of [3,3]- and [3,5]-sigmatropic rearrangements

246th National Meeting (2013)

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