Rhodium/tris-binaphthyl chiral monophosphite complexes: Efficient catalysts for the hydroformylation of disubstituted aryl olefins

Rui M.B. Carrilho, A. C.B. Neves, Mirtha A.O. Loureno, Artur R. Abreu, Mário T.S. Rosado, Paulo E. Abreu, M. Ermelinda S. Eusébio, László Kollár, J. Carles Bayón, Mariette M. Pereira

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Abstract

A family of threefold symmetry phosphite ligands, P(O-BIN-OR) 3 (BIN = 2,2′-binaphthyl; R = Me, Bn, CHPh 2, 1-adamantyl), derived from enantiomerically pure (R)-BINOL, was developed. Cone angles within the range 240-270° were calculated for the phosphite ligands, using the computational PM6 Hamiltonian. Their rhodium complexes formed in situ showed remarkable catalytic activity in the hydroformylation of hindered phenylpropenes, under relatively mild reaction conditions, with full chemoselectivity for aldehydes, high regioselectivity, however with low enantioselectivity. The ether substituents at the ligand affected considerably the catalytic activity on the hydroformylation of 1,1- and 1,2-disubstituted aryl olefins. The kinetics of the hydroformylation of trans-1-phenyl-1-propene, using tris[(R)-2′-benzyloxy-1,1′-binaphthyl-2-yl]phosphite as model ligand, was investigated. A first order dependence in the hydroformylation initial rate with respect to substrate and catalyst concentrations was found, as well as a positive order with respect to the partial pressure of H 2, and a slightly negative order with respect to phosphite concentration and CO partial pressure.

Original languageEnglish
Pages (from-to)28-34
Number of pages7
JournalJournal of Organometallic Chemistry
Volume698
DOIs
Publication statusPublished - Feb 1 2012

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Keywords

  • Cone angle
  • Hindered olefins
  • Hydroformylation
  • Kinetics
  • Rhodium complexes
  • Tris-binaphthyl monophosphite

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Carrilho, R. M. B., Neves, A. C. B., Loureno, M. A. O., Abreu, A. R., Rosado, M. T. S., Abreu, P. E., Eusébio, M. E. S., Kollár, L., Bayón, J. C., & Pereira, M. M. (2012). Rhodium/tris-binaphthyl chiral monophosphite complexes: Efficient catalysts for the hydroformylation of disubstituted aryl olefins. Journal of Organometallic Chemistry, 698, 28-34. https://doi.org/10.1016/j.jorganchem.2011.10.007