Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations
Type
ArticleAuthors
Vummaleti, Sai V. C.
Alghamdi, Miasser

Poater, Albert

Falivene, Laura

Scaranto, Jessica
Beetstra, Dirk J.
Morton, Jason G.
Cavallo, Luigi

KAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
SABIC - Corporate Research and Innovation Center (CRI) at KAUST
Date
2015-11-13Online Publication Date
2015-11-13Print Publication Date
2015-12-14Permanent link to this record
http://hdl.handle.net/10754/621702
Metadata
Show full item recordAbstract
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 center. © 2015 American Chemical Society.Citation
Vummaleti SVC, Al-Ghamdi M, Poater A, Falivene L, Scaranto J, et al. (2015) Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations. Organometallics 34: 5549–5554. Available: http://dx.doi.org/10.1021/acs.organomet.5b00749.Sponsors
European Commission[CIG09-GA-2011-293900]Ministerio de Economía y Competitividad[CTQ2014-59832-JIN]
King Abdullah University of Science and Technology
Publisher
American Chemical Society (ACS)Journal
OrganometallicsAdditional Links
http://pubs.acs.org/doi/abs/10.1021/acs.organomet.5b00749ae974a485f413a2113503eed53cd6c53
10.1021/acs.organomet.5b00749