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

Rao, Varanasi Pushkara and Chandrasekhar, Jayaraman and Ramamurthy, Vaidhyanathan (1988) Thermal and photochemical cycloaddition reactions of thiocarbonyls: a qualitative molecular orbital analysis. In: Perkin Transactions 2 (5). pp. 647-659.

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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.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to Royal Society of Chemistry.
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Date Deposited: 11 Oct 2010 09:23
Last Modified: 11 Oct 2010 09:23
URI: http://eprints.iisc.ernet.in/id/eprint/33035

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