Controlled Payne rearrangements of 2,3-epoxy alcohols in aprotic media: an enantioselective total synthesis of (+)-exo-brevicomin

Abstract
The catalysis of the isomerisation of primary cis-2,3-epoxy alcohols to threo-1,2-epoxy alcohols by lithium chloride in tetrahydrofuran solution is described; the more reactive terminal epoxides may be selectively trapped in situ by reaction with nucleophiles, and this methodology is used in an enantioselective synthesis of (+)-exo-brevicomin.

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