Catalytic 1,4‐Rhodium(III) Migration Enables 1,3‐Enynes to Function as One‐Carbon Oxidative Annulation Partners in CH Functionalizations

Abstract

Abstract1,3‐Enynes containing allylic hydrogens cis to the alkyne are shown to act as one‐carbon partners, rather than two‐carbon partners, in various rhodium‐catalyzed oxidative annulations. The mechanism of these unexpected transformations is proposed to occur through double CH activation, involving a hitherto rare example of the 1,4‐migration of a RhIII species. This phenomenon is general across a variety of substrates, and provides a diverse range of heterocyclic products.