Abstract
Abstract Deuterium isotope effects on the efficiencies of light-induced rearrangements of 2,5-dimethyl- and 2,5-di- tert -butylhexatrienes are reported. The 4π electrocyclizations show an inverse secondary isotope effect, in agreement with the existence of the theoretically predicted barrier on the potential energy surface of the excited state. In the formation of allylcyclopropene derivatives isotope effects provide evidence for a mechanism involving a biradical intermediate. The surprisingly large decrease in the efficiency of E — Z isomerizations in E - and Z -2,5-di- tert -butyl-1,3,5-hexatrienes after deuteration of the central double bond is ascribed to a reduced frequency of the hydrogen out-of-plane deformation which initiates the reaction.
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