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Catalytic role of nickel in the decarbonylative addition of phthalimides to alkynes

Density functional theory calculations have been used to investigate the catalytic role of nickel(0) in the decarbonylative addition of phthalimides to alkynes. According to Kurahashi et al. the plausible reaction mechanism involves a nucleophilic attack of nickel at an imide group, giving a six-membered metallacycle, followed by a decarbonylation and insertion of an alkyne leading to a seven-membered metallacycle. Finally a reductive elimination process produces the desired product and regenerates the nickel(0) catalyst. In this paper, we present a full description of the complete reaction pathway along with possible alternative pathways, which are predicted to display higher upper barriers. Our computational results substantially confirm the proposed mechanism, offering a detailed geometrical and energetical understanding of all the elementary steps

A.P. and L.C. thank the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226), European Commission for a Career Integration Grant (CIG09-GA-2011-293900), and Generalitat de Catalunya (2012BE100824)

漏 Organometallics, 2013, vol. 32, p. 6330-6336

American Chemical Society (ACS)

Author: Poater Teixidor, Albert
Vummaleti, Sai Vikrama Chaitanya
Cavallo, Luigi
Date: 2013
Abstract: Density functional theory calculations have been used to investigate the catalytic role of nickel(0) in the decarbonylative addition of phthalimides to alkynes. According to Kurahashi et al. the plausible reaction mechanism involves a nucleophilic attack of nickel at an imide group, giving a six-membered metallacycle, followed by a decarbonylation and insertion of an alkyne leading to a seven-membered metallacycle. Finally a reductive elimination process produces the desired product and regenerates the nickel(0) catalyst. In this paper, we present a full description of the complete reaction pathway along with possible alternative pathways, which are predicted to display higher upper barriers. Our computational results substantially confirm the proposed mechanism, offering a detailed geometrical and energetical understanding of all the elementary steps
A.P. and L.C. thank the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226), European Commission for a Career Integration Grant (CIG09-GA-2011-293900), and Generalitat de Catalunya (2012BE100824)
Format: application/pdf
ISSN: 0276-7333 (versi贸 paper)
1520-6041 (versi贸 electr貌nica)
Document access: http://hdl.handle.net/10256/10340
Language: eng
Publisher: American Chemical Society (ACS)
Collection: MICINN/PN 2012-2015/RYC-2009-05226
AGAUR/2012BE100824
Reproducci贸 digital del document publicat a: http://dx.doi.org/10.1021/om400693v
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: 漏 Organometallics, 2013, vol. 32, p. 6330-6336
Rights: Tots els drets reservats
Subject: Funcional de densitat, Teoria del
Density functionals
Catalitzadors de n铆quel
Nickel catalysts
Title: Catalytic role of nickel in the decarbonylative addition of phthalimides to alkynes
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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