Experimental and theoretical investigation on the cycloadditions of nitrile oxides, nitrones, and diazoalkanes with acyclic vinyl sulphones and thiet 1,1-dioxide
- 1 January 1982
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 2
- No. 1,p. 95-100
- https://doi.org/10.1039/p29820000095
Abstract
Diazoalkanes, nitrile oxides, and nitrones cycloadd thiet 1,1-dioxide showing regiochemical characteristics markedly different from those observed for acyclic vinyl sulphones. The charge-transfer stabilization energy, calculated according to the Klopman–Salem perturbational approach in the CNDO/2 approximation, is able to account for the experimental trends of the isomer ratios. An analysis of the calculations performed for cis-syn-vinyl sulphones explains the change of regiochemistry in the reactions of thiet 1,1 dioxide as due to its blocked cis-syn-structure which dues not happen in the ‘open’ vinyl sulphones. Unsuccessful predictions obtained with the frontier orbital approximation are discussed.Keywords
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