Rhodium-catalyzed 1,4-hydroxyl migration of alkenyl alcohols

Abstract

Molecular rearrangements are ubiquitous in modern synthetic chemistry, providing a powerful strategy for reorganizing complex structures through one-step chemical transformations in atom- and step-economic processes. Herein, we report a rhodium-catalyzed intramolecular 1,4-hydroxyl migration of alkenyl alcohols, which is, to the best of our knowledge, the first metal-catalyzed 1,4-hydroxyl migration without the presence of a radical initiator. The key to this transformation is the selective breaking of C(sp³)–O bonds. The reaction is also characterized by the migration of the hydroxyl group from the stable tertiary carbocation to the secondary carbocation. This procedure features a broad substrate scope and outstanding functional group tolerance, and thus, a wide range of structurally diverse unsaturated ketones has been prepared in synthetically valuable yields.