Thermal and photochemical cycloaddition reactions of thiocarbonyls: A qualitative molecular orbital analysis

Varanasi Pushkara Rao, Jayaraman Chandrasekhar, Vaidhyanathan Ramamurthy

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

A comprehensive analysis of thermal and photochemical reactions of thiocarbonyls has been undertaken within the PMO framework employing MINDO/3 orbital energies and wavefunctions. The model is generally successful in rationalizing the observed regiochemistry of such reactions. In particular, the indicated regiochemistry for [4 + 2] thermal cycloadditions of saturated thiones to 2-substituted dienes, for the dimerization of α,β-unsaturated thiones, and for the photochemical cycloadditions of thioketones and thioenones are all in agreement with experimental observations. Interesting predictions are also made concerning cycloadditions of saturated, conjugated, and arylalkyl thiones which have not yet been studied experimentally. The analysis reveals the decisive role played by secondary orbital interactions in determining the observed product selectivity in the photochemical reactions between thioenone and olefins.

Original languageEnglish (US)
Pages (from-to)647-659
Number of pages13
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number5
DOIs
StatePublished - Jan 1 1988
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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