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

Handle URI:
http://hdl.handle.net/10754/563083
Title:
Catalytic role of nickel in the decarbonylative addition of phthalimides to alkynes
Authors:
Poater, Albert; Vummaleti, Sai V. C. ( 0000-0001-7276-2475 ) ; Cavallo, Luigi ( 0000-0002-1398-338X )
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. © 2013 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
Issue Date:
11-Nov-2013
DOI:
10.1021/om400693v
Type:
Article
ISSN:
02767333
Sponsors:
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).
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPoater, Alberten
dc.contributor.authorVummaleti, Sai V. C.en
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-08-03T11:35:23Zen
dc.date.available2015-08-03T11:35:23Zen
dc.date.issued2013-11-11en
dc.identifier.issn02767333en
dc.identifier.doi10.1021/om400693ven
dc.identifier.urihttp://hdl.handle.net/10754/563083en
dc.description.abstractDensity 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. © 2013 American Chemical Society.en
dc.description.sponsorshipA.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).en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleCatalytic role of nickel in the decarbonylative addition of phthalimides to alkynesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalOrganometallicsen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi, Departament de Química, Universitat de Girona, E-17071 Girona, Catalonia, Spainen
kaust.authorVummaleti, Sai V. C.en
kaust.authorCavallo, Luigien
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.