Degenerate thermal rearrangement of 1, 3-dimethylenecyclopentane. Evidence for partially stereospecific biradical formation and closure in a 1, 3 shift

JJ Gajewski, JDC Salazar

Index: Gajewski, Joseph J.; Salazar, Jose Del C. Journal of the American Chemical Society, 1981 , vol. 103, # 14 p. 4145 - 4154

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Citation Number: 8

Abstract

Abstract: Pyrolysis of 1, 3-bis (dideuteriomethylene) cyclopentane at 370 OC resulted in a first-order degenerate rearrangement in which the 1, 3-and 3, 3-shift products were formed in a 2: l ratio, respectively, indicating the intermediacy of an effectively orthogonal 2, 2'-bis (allylmethane) biradical. Pyrolysis of trans-and cis-4, 5-dimethyl-1, 3- dimethyIenecyclopentane (T and C) gave 1, 3-and 3, 3-shift products with stereochemistry ...