Catalytic Cleavage of C(sp2)−C(sp2) Bonds with Rh-Carbynoids
We report a catalytic strategy that generates rhodium-carbynoids by selective diazo activation of designed carbyne sources. We found that rhodium-carbynoid species provoke C(sp2)–C(sp2) bond scission in alkenes by inserting a monovalent carbon unit between both sp2-hybridized carbons. This skeletal...
| Autores: | , , , |
|---|---|
| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2019 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2072/363718 |
| Acceso en línea: | http://hdl.handle.net/2072/363718 https://doi.org/10.1021/jacs.9b08632 |
| Access Level: | acceso abierto |
| Palabra clave: | 54 |
| Sumario: | We report a catalytic strategy that generates rhodium-carbynoids by selective diazo activation of designed carbyne sources. We found that rhodium-carbynoid species provoke C(sp2)–C(sp2) bond scission in alkenes by inserting a monovalent carbon unit between both sp2-hybridized carbons. This skeletal remodeling process accesses synthetically useful allyl cation intermediates that conduct to valuable allylic building blocks upon nucleophile attack. Our results rely on the formation of cyclopropyl-I(III) intermediates able to undergo electrocyclic ring-opening, following the Woodward–Hoffmann–DePuy rules. |
|---|