3 years ago

Intramolecular Thioether Migration in the Rhodium-Catalyzed Ene-Cycloisomerization of Alkenylidenecyclopropanes via a Metal-Mediated β-Sulfide Elimination

Phillip A. Inglesby, P. Andrew Evans, Yu Su
We report the first example of a rhodium-mediated β-sulfide elimination, which represents a new mode of reactivity for late transition metal chemistry. This serendipitous discovery facilitates an ene-cycloisomerization of allylic sulfide containing alkenylidenecyclopropanes (ACPs) to five-membered carbo- and heterocyclic rings with concomitant intramolecular thioether migration. Interestingly, similar selectivity is obtained with both E- and Z-allylic sulfides and the reaction is also feasible with an allylic selenide. Mechanistic studies are consistent with an inner-sphere transfer of the sulfide, which is remarkable given the propensity for sulfides to poison transition metal catalysts. Finally, we envision that this type of atom-economical rearrangement will prompt the development of related processes given the utility of sulfides in target directed synthesis

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201709059

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