Rhodium-Catalyzed [2+2+2] Cycloaddition Reactions of Linear Allene–Ene–Ynes to afford Fused Tricyclic Scaffolds: Insights into the Mechanism
Allene-(E)-ene-yne N-tosyl-tethered substrates 3 a–3 h were efficiently prepared and their rhodium-catalyzed [2+2+2] cycloaddition reactions were evaluated. The cycloadditions are chemoselective as only the proximal double bond of the allene reacted to afford exocyclic double bonds in the fused-tric...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2017 |
| 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:10256/14776 |
| Acceso en línea: | http://hdl.handle.net/10256/14776 |
| Access Level: | acceso abierto |
| Palabra clave: | Reaccions d'addició Addition reactions Funcional de densitat, Teoria del Density functionals Mecanismes de reacció (Química) Reaction mechanisms (Chemistry) Rodi Rhodium |
| Sumario: | Allene-(E)-ene-yne N-tosyl-tethered substrates 3 a–3 h were efficiently prepared and their rhodium-catalyzed [2+2+2] cycloaddition reactions were evaluated. The cycloadditions are chemoselective as only the proximal double bond of the allene reacted to afford exocyclic double bonds in the fused-tricyclic scaffolds. The stereoselectivity depended on the catalytic system used. Reactivity between allene, alkene, and alkyne was studied for the first time by density functional theory calculations. This mechanistic study determines the order in which the unsaturated groups take part in the catalytic cycle |
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