Molecular rearrangements are ubiquitous in modern synthetic chemistry, providing a powerful strategy for reorganizing complex structures through one-step chemical transformations in atomic and step-economy 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 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 broad substrate cope, outstanding functional group tolerance and thus, a wide range of structurally diverse unsaturated ketones has been prepared in synthetically valuable yields.

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