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Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd cente

A.P. thanks the Spanish MINECO for project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)

American Chemical Society (ACS)

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Vummaleti, Sai Vikrama Chaitanya
Al-Ghamdi, Miasser
Poater Teixidor, Albert
Falivene, Laura
Scaranto, Jessica
Beetstra, Dirk J.
Morton, Jason G.
Cavallo, Luigi
Abstract: Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd cente
A.P. thanks the Spanish MINECO for project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)
Document access: http://hdl.handle.net/2072/298695
Language: eng
Publisher: American Chemical Society (ACS)
Rights: Tots els drets reservats
Subject: Funcional de densitat, Teoria del
Density functionals
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Title: Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations
Type: info:eu-repo/semantics/article
Repository: Recercat

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