EXTRAORDINARY PHOTOREARRANGEMENT OF SILYFURANS AND SUBSEQUENT THERMAL REARRANGEMENTS.

Article abstract of DOI:10.1021/ja00358a025

A report is made on the fact that silyl substitution allows remarkably clean photoisomerization of furans, in contrast to the complex product mixtures and low yields of the photolyses of furans. Experiments were performed to determine whether the silicon substitution was the controlling factor in changing the course of furan photochemistry. The ability of silicon to stabilize a polar excited state (and ground state) through inclusion of resonance structures in the resonance hybrid is offered as an explanation. Refs.