Concepedia

Mechanistic Aspects of Alkyne Migration in Alkylidene Carbenoid Rearrangements

Paul Bichler, Wesley A. Chalifoux, Sara Eisler, Annabelle L. K. Shi Shun, Erin T. Chernick, Rik R. Tykwinski

Organic Letters · 2009 · 33 citations · 38 references

DOI

Concepts

Abstract

The mechanism of the Fritsch-Buttenberg-Wiechell rearrangement of (13)C labeled precursors has been examined to determine the propensity of the alkynyl (R-CC-) group to migrate in an alkylidene carbenoid species. Reaction of dibromoolefins with n-BuLi and ketones with Me(3)SiC(Li)N(2) both demonstrate that the alkynyl moiety readily undergoes 1,2-migration from carbenoid intermediates.

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