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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-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

Financial support fro m the Spanish Ministry of Educatio n and Science (MINECO) (Project No. CTQ2014-54306-P and CTQ2015-64436-P), the DIUE of the Generalitat de Catalunya (Project No.: 2014SGR931, pre-doctoral grant to D.C. and ICREA Academia 2014 prize to MS), and the FEDER fund (European Fund for Regional Development) for grant UNGI08-4E-801 is gratefully acknowledged

Wiley

Director: Ministerio de Economía y Competitividad (Espanya)
Autor: Cassú Ponsatí, Daniel
Parella Coll, Teodor
Solà i Puig, Miquel
Pla i Quintana, Anna
Roglans i Ribas, Anna
Data: 5 juny 2018
Resum: 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
Financial support fro m the Spanish Ministry of Educatio n and Science (MINECO) (Project No. CTQ2014-54306-P and CTQ2015-64436-P), the DIUE of the Generalitat de Catalunya (Project No.: 2014SGR931, pre-doctoral grant to D.C. and ICREA Academia 2014 prize to MS), and the FEDER fund (European Fund for Regional Development) for grant UNGI08-4E-801 is gratefully acknowledged
Accés al document: http://hdl.handle.net/2072/319884
Llenguatge: eng
Editor: Wiley
Drets: Tots els drets reservats
Matèria: Reaccions d’addició
Addition reactions
Funcional de densitat, Teoria del
Density functionals
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Rodi
Rhodium
Títol: Rhodium-Catalyzed [2+2+2] Cycloaddition Reactions of Linear Allene–Ene–Ynes to afford Fused Tricyclic Scaffolds: Insights into the Mechanism
Tipus: info:eu-repo/semantics/article
Repositori: Recercat

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