Dyotropic rearrangement of bridgehead substituents in closed dithienylethenes; conjugated verses non-conjugated analogues

Abstract

Type I dyotropic rearrangement reactions of halogen and methyl substituents at the bridgehead position of diarylethenes and dihydroarylethenes have been studied through density functional theory at B3LYP/6-31+G(d) level. The calculations have been performed to explore the dyotropic rearrangement as a possible factor for the elusive nature of halogenated dithienylethenes (closed). The dyotropic rearrangement process in closed dithienylethenes is then compared with the dihydro analogues. Moreover, the effect of hetero atom and conjugation is also explored through quantum mechanical calculations.

Type-I dyotropic rearrangement for 1,2-disubstituted cyclohexanes: substitution effect on activation energy

“…32 Application of computational investigations in synthesis has emerged as an indispensable research element and indeed, is a time and cost effective approach. It has been eloquently applied to dyotropic rearrangement and is reported for several structural units such as dithienylethenes, 33 arene/allene cycloadducts, 34 phosphate and sulphate anions, 35 azines, 36 pentalenene, 37 vicinal dibromides, 38 b-lactones, 39 dimethylaurate, 40 organocuprates and organoargentates, 41 and nitroso acetals. 42 Undoubtedly, cyclohexane is regarded as one of the most privileged cycloalkane due to associated structural features.…”