Rhodium/tris-binaphthyl chiral monophosphite complexes: Efficient catalysts for the hydroformylation of disubstituted aryl olefins
authors Carrilho, RMB; Neves, ACB; Lourenco, MAO; Abreu, AR; Rosado, MTS; Abreu, PE; Eusebio, MES; Kollar, L; Bayon, JC; Pereira, MM
journal JOURNAL OF ORGANOMETALLIC CHEMISTRY
author keywords Tris-binaphthyl monophosphite; Cone angle; Rhodium complexes; Hydroformylation; Hindered olefins; Kinetics
keywords ASYMMETRIC HYDROFORMYLATION; PHOSPHORUS LIGANDS; PHOSPHITE LIGANDS; BULKY PHOSPHITE; KINETICS; STYRENE; SYSTEM; REGIOSELECTIVITY; TRANSFORMATIONS; 1-HEXENE
abstract A family of threefold symmetry phosphite ligands, P(O-BIN-OR)(3) (BIN = 2,2'-binaphthyl; R = Me, Bn, CHPh2, 1-adamantyl), derived from enantiomerically pure (R)-BINOL, was developed. Cone angles within the range 240-270 degrees 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. (C) 2011 Elsevier B. V. All rights reserved.
publisher ELSEVIER SCIENCE SA
issn 0022-328X
year published 2012
volume 698
beginning page 28
ending page 34
digital object identifier (doi) 10.1016/j.jorganchem.2011.10.007
web of science category Chemistry, Inorganic & Nuclear; Chemistry, Organic
subject category Chemistry
unique article identifier WOS:000298142800005
  ciceco authors
  impact metrics
journal analysis (jcr 2019):
journal impact factor 2.304
5 year journal impact factor 1.963
category normalized journal impact factor percentile 55.965
dimensions (citation analysis):
altmetrics (social interaction):



 


Sponsors

1suponsers_list_ciceco.jpg