Transition metal-catalyzed ene-cycloisomerization reactions represent an important class of reaction because of their ability to construct complex carbo- and heterocyclic scaffolds in an atom-economical manner. In a program directed towards the development of metal-catalyzed carbocyclization reactions, with alkenylidenecyclopropanes (ACPs), we recently reported a novel rhodium-catalyzed ene-cycloisomerization, which generates products with two stereogenic centers. This seminar will outline the development of a novel intramolecular rhodium-catalyzed ene-cycloisomerization of thioether containing alkenylidenecyclopropanes, in which an allylic sulfide undergoes a unprecedented chemoselective metal-mediated β-sulfide migration to provide 5-membered carbo- and heterocyclic rings with a new allylic sulfide. Furthermore, the reaction occurs with equal efficiency for both the E- and Z-allylic sulfides and includes an example of an allylic selenide with similar efficiency and selectivity.

Chemo- and stereoselective rhodium-catalyzed ene-cycloisomerization of thioether-substituted alkenylidenecyclopropanes: Metal-mediated β-sulfide migration

254th National Meeting (2017)

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