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Bent Bonds and the Antiperiplanar Hypothesis. A Model To Account for Sigmatropic [1, n]-Hydrogen Shifts
Ghislain Deslongchamps1, Pierre Deslongchamps2
1Department of Chemistry , University of New Brunswick , Fredericton , New Brunswick E3B 5A3 , Canada.
Abstract:
The bent bond/antiperiplanar hypothesis (BBAH) is used to propose a mechanism-based orbital model for the facial selectivity of sigmatropic hydrogen shifts under both thermal and photochemical conditions. The BBAH analysis of these concerted rearrangements invokes transient vibrationally excited singlet diradicals in both 4 n and 4 n+2 polyenes.
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