Item


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

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Cassú Ponsatí, Daniel
Parella Coll, Teodor
Solà i Puig, Miquel
Pla i Quintana, Anna
Roglans i Ribas, Anna
Date: 2020 February 15
Abstract: 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
Document access: http://hdl.handle.net/2072/372845
Language: eng
Publisher: Wiley
Rights: Tots els drets reservats
Subject: Reaccions d’addició
Addition reactions
Funcional de densitat, Teoria del
Density functionals
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Rodi
Rhodium
Title: Rhodium-Catalyzed [2+2+2] Cycloaddition Reactions of Linear Allene–Ene–Ynes to afford Fused Tricyclic Scaffolds: Insights into the Mechanism
Type: info:eu-repo/semantics/article
Repository: Recercat

Subjects

Authors


Warning: Unknown: write failed: No space left on device (28) in Unknown on line 0

Warning: Unknown: Failed to write session data (files). Please verify that the current setting of session.save_path is correct (/var/lib/php5) in Unknown on line 0