Regio- and stereo-selectivity of alkenyl radical ring closure: A theoretical study

A theoretical study has been undertaken of the relative rates and the regio- and stereo-chemistry of ring closure of a variety of alkenyl, alkenylaryl, alkenylvinyl and similar radicals. The method involves the application of MM2 force-field calculations to model transition structures for which the dimensions of the arrays of reactive centres have been obtained by MNDO-UHF techniques. The results, which generally accord with guidelines based on stereochemical considerations, show excellent qualitative and satisfactory quantitative agreement with experimental data. The method has been successfully applied to complex systems including ring closure of alkylperoxy radicals, and formation of the triquinane system by three consecutive cyclisations.