Abstract
Studies of product compositions and deuterium-label rearrangements at various concentrations of tri-n-butyltin hydride in the reductions of exo-and endo-5-bromonorbornene and 2-bromonortricyclcne to mixtures of norbornene and nortricyclene lead to three main conclusions: (i) at least two radical intermediates contribute to product formation; (ii) each intermediate yields predominantly (80% or more) one product; and (iii) nortricyclene is predominantly derived from a symmetrical intermediate. This constitutes strong evidence for hydrogen abstraction by classical (i.e., single-product) norbornenyl and nortricyclyl radicals. It is argued that the norbornenyl-nortricyclyl system is exceptionally well suited for the generation of a nonclassical (dual-product) radical; hence, the existence of a nonclassical radical in any other system is rather unlikely.
Keywords: free radical rearrangement, symmetrical intermediates, mechanism
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