TY - JOUR
T1 - Thermal and photochemical cycloaddition reactions of thiocarbonyls
T2 - A qualitative molecular orbital analysis
AU - Rao, Varanasi Pushkara
AU - Chandrasekhar, Jayaraman
AU - Ramamurthy, Vaidhyanathan
PY - 1988/1/1
Y1 - 1988/1/1
N2 - 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.
AB - 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.
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U2 - 10.1039/P29880000647
DO - 10.1039/P29880000647
M3 - Article
AN - SCOPUS:37049087223
SP - 647
EP - 659
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
SN - 1472-779X
IS - 5
ER -