Rearrangement of alkylchlorocarbenes: 1, 2-H shift in free carbene, carbene-olefin complex, and excited states of carbene precursors

…, MTH Liu, KC Kim, JL Goodman

Index: Bonneau, Roland; Liu, Michael T. H.; Kim, Kyu Chul; Goodman, Joshua L. Journal of the American Chemical Society, 1996 , vol. 118, # 16 p. 3829 - 3837

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Citation Number: 57

Abstract

Photolysis of alkylchlorodiazirines (1) in the presence of olefins gives a cyclopropane (3) by addition of the generated carbene to the olefin and a vinyl chloride derivative (2) resulting from a 1, 2-H shift rearrangement. This rearrangement may occur either in the carbene or in some excited state, precursor of the carbene (RIES mechanism), or in a “carbene+ olefin complex” on the way to the formation of 3 (COC mechanism). Results obtained by time- ...

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