Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

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 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.

Acknowledgements
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
Organometallics

DOI
10.1021/acs.organomet.5b00749

Additional Links
http://pubs.acs.org/doi/abs/10.1021/acs.organomet.5b00749

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