Intramolecular Thioether Migration in the Rhodium‐Catalyzed Ene‐Cycloisomerization of Alkenylidenecyclopropanes by a Metal‐Mediated β‐Sulfide Elimination |
| |
| Authors: | Yu Su Dr. Phillip A. Inglesby Prof. P. Andrew Evans |
| |
| Affiliation: | 1. http://faculty.chem.queensu.ca/people/faculty/evans/index.htm;2. Department of Chemistry, Queen's University, Kingston, ON, Canada;3. Department of Chemistry, University of Liverpool, Liverpool, UK |
| |
| Abstract: | Reported is 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 afford 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, this type of atom‐economical rearrangement is envisioned to prompt the development of related processes given the utility of sulfides in target‐directed synthesis. |
| |
| Keywords: | cyclization heterocyles isomerization rhodium sulfur |
|
|
