Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru-based Catalyst and Alcohols

Handle URI:
http://hdl.handle.net/10754/625015
Title:
Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru-based Catalyst and Alcohols
Authors:
Poater, Albert; Vummaleti, Sai V. C. ( 0000-0001-7276-2475 ) ; Polo, Alfonso; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
Density functional theory calculations have been used to investigate the reaction mechanism for [(C6H6)(PCy3)(CO) RuH](+) (1; Cy, cyclohexyl) mediated alkylation of indene substrate using ethanol as solvent. According to Yi et al. [ Science 2011, 333, 1613] the plausible reaction mechanism involves a cationic Rualkenyl species, which is initially formed from 1 with two equivalents of the olefin substrate via the vinylic C-H activation and an alkane elimination step. Once the active catalytic species is achieved the oxidative addition step is faced. The latter step together with the next C-C bond formation might display the upper barrier of the catalytic cycle. Having these experimental insights at hand, we investigated in detail the whole reaction pathway using several computational DFT approaches including alternative pathways, higher in energy.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Poater A, Vummaleti SVC, Polo A, Cavallo L (2016) Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru-based Catalyst and Alcohols. ChemistrySelect 1: 4218–4228. Available: http://dx.doi.org/10.1002/slct.201600860.
Publisher:
Wiley-Blackwell
Journal:
ChemistrySelect
Issue Date:
11-Sep-2016
DOI:
10.1002/slct.201600860
Type:
Article
ISSN:
2365-6549
Sponsors:
A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN. We thank King Abdullah University of Science and Technology (CFF project) for support.
Additional Links:
http://onlinelibrary.wiley.com/wol1/doi/10.1002/slct.201600860/abstract
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPoater, Alberten
dc.contributor.authorVummaleti, Sai V. C.en
dc.contributor.authorPolo, Alfonsoen
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2017-06-14T12:17:34Z-
dc.date.available2017-06-14T12:17:34Z-
dc.date.issued2016-09-11en
dc.identifier.citationPoater A, Vummaleti SVC, Polo A, Cavallo L (2016) Mechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru-based Catalyst and Alcohols. ChemistrySelect 1: 4218–4228. Available: http://dx.doi.org/10.1002/slct.201600860.en
dc.identifier.issn2365-6549en
dc.identifier.doi10.1002/slct.201600860en
dc.identifier.urihttp://hdl.handle.net/10754/625015-
dc.description.abstractDensity functional theory calculations have been used to investigate the reaction mechanism for [(C6H6)(PCy3)(CO) RuH](+) (1; Cy, cyclohexyl) mediated alkylation of indene substrate using ethanol as solvent. According to Yi et al. [ Science 2011, 333, 1613] the plausible reaction mechanism involves a cationic Rualkenyl species, which is initially formed from 1 with two equivalents of the olefin substrate via the vinylic C-H activation and an alkane elimination step. Once the active catalytic species is achieved the oxidative addition step is faced. The latter step together with the next C-C bond formation might display the upper barrier of the catalytic cycle. Having these experimental insights at hand, we investigated in detail the whole reaction pathway using several computational DFT approaches including alternative pathways, higher in energy.en
dc.description.sponsorshipA.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN. We thank King Abdullah University of Science and Technology (CFF project) for support.en
dc.publisherWiley-Blackwellen
dc.relation.urlhttp://onlinelibrary.wiley.com/wol1/doi/10.1002/slct.201600860/abstracten
dc.subjectruthenium catalysten
dc.subjectalcoholen
dc.subjectDFT calculationsen
dc.subjectC-C bond formationen
dc.subjectC-H alkylationen
dc.titleMechanistic Insights of a Selective C-H Alkylation of Alkenes by a Ru-based Catalyst and Alcoholsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalChemistrySelecten
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química; Universitat de Girona, Campus Montilivi; 17003 Girona, Catalonia Spainen
kaust.authorVummaleti, Sai V. C.en
kaust.authorCavallo, Luigien
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