Phosphoramidites: Novel modifying ligands in rhodium catalysed hydroformylation

The phosphoramidites 2–9 have been applied as modifying ligands in rhodium-catalysed hydroformylation of oct-1-ene and styrene. Monodentate phosphoramidites 2–5 gave rise to catalysts with average rates of 1000 mol [mol Rh]−1 h−1 and maximum selectivities of 65% to the linear product nonanal for the hydroformylation of oct-1-ene (P 20 bar CO/H2, T 80°C, [oct-1-ene] ≈ 1 M). Styrene was hydroformylated (T 40°C, P 20 bar CO/H2) at rates up to 150 mol [mol Rh]−1 h−1 and a selectivity for the branched 2-phenylpropanal of 93%. Using diphosphoramidite modified catalysts a maximum rate of 1200 mol.[mol Rh]−1.h−1 for oct-1-ene was observed for 9, with 91% regioselectivity for the linear product. At 40°C styrene was hydroformylated at rates up to 25 mol [mol Rh]−1 h−1 and with selectivities for the branched aldehyde of 89%. Characterization of the rhodium complexes showed that formation of rhodium hydride complexes is slow and incomplete under the conditions applied for the monophosphoramidites. The diphosphoramidite ligands all form bidentate hydrido-rhodium complexes. The diphosphoramidite ligands 6–9 coordinate bis-equatorially in the trigonal bipyramidal rhodium complexes, which accounts for the high regioselectivities.

[1]  N. Veldman,et al.  Bulky diphosphite modified rhodium catalyst; Hydroformylation and characterization , 1996 .

[2]  Y. V. D. van der Burgt,et al.  New Diphosphine Ligands Based on Heterocyclic Aromatics Inducing Very High Regioselectivity in Rhodium-Catalyzed Hydroformylation: Effect of the Bite Angle , 1995 .

[3]  N. Veldman,et al.  NMR spectra and crystal structure of a regioselective hydroformylation catalyst complex RhH(diphosphite)(CO)2 , 1995 .

[4]  P. V. Leeuwen,et al.  Hydridorhodium diphosphite catalysts in the asymmetric hydroformylation of styrene , 1995 .

[5]  P. V. Leeuwen,et al.  Hydroformylation with a rhodium/bulky phosphite modified catalyst. A comparison of the catlyst behaviour for oct-1-ene, cyclohexene and styrene , 1995 .

[6]  M. LeeuwenvanP.W.N.,et al.  Solution structures of hydrido rhodium diphosphite hydroformylation catalysts , 2010 .

[7]  T. A. Ayers,et al.  Electronic effects in asymmetric catalysis: Hydroformylation of olefins , 1994 .

[8]  A. T. Teleshev,et al.  Complexation of rhodium(I) with hydrophosphorane derivatives of bicyclo[3.3.0]-1-phospha-2,8-dioxa-5-aza-octane , 1993 .

[9]  P. V. Leeuwen,et al.  Rhodium catalysed asymmetric hydroformylation with chiral diphosphite ligands , 1993 .

[10]  R. Rodebaugh,et al.  Sterically Congested Phosphite Ligands: Synthesis, crystallographic characterization, and observation of unprecedented eight-Bond 31P,31P coupling in the 31P-NMR spectra , 1993 .

[11]  D. Powell,et al.  Diphosphines with natural bite angles near 120.degree. increase selectivity for n-aldehyde formation in rhodium-catalyzed hydroformylation , 1992 .

[12]  G. Challa,et al.  A NEW TYPE OF HIGHLY-ACTIVE POLYMER-BOUND RHODIUM HYDROFORMYLATION CATALYST , 1992 .

[13]  G. Challa,et al.  A mechanistic study of rhodium tri(o-t-butylphenyl)phosphite complexes as hydroformylation catalysts , 1991 .

[14]  P. V. Leeuwen,et al.  Hydroformylation of oct-1-ene with extremely high rates using rhodium catalysts containing bulky phosphites , 1991 .

[15]  R. Lazzaroni,et al.  Reversibility of metal-alkyl intermediate formation in the rhodium-catalyzed deuterioformylation of 1-hexene , 1989 .

[16]  A. Mortreux,et al.  Utilisation des ligands aminophosphinephosphinites en hydroformylation catalysée par le rhodium: amélioration de l'énantioselectivité par synthèse selective des hydrures RhH(CO)2L★2 , 1989 .

[17]  R. Lazzaroni,et al.  Regioselectivity in the rhodium-catalyzed hydroformylation of styrene as a function of reaction temperature and gas pressure , 1989 .

[18]  R. Rodebaugh,et al.  Sterically congested molecules: synthesis, characterization, and unique spectral characteristics of hexa-tert-butyl-substituted biaryl bis(1,3,2-oxazaphospholidines) , 1988 .

[19]  A. Trzeciak,et al.  Homogeneous rhodium complex-catalyzed hydroformylation and related reactions of functionally substituted olefins , 1987 .

[20]  A. Trzeciak,et al.  New synthesis of [RhH{P(OPh)3}4] and related reactions , 1987 .

[21]  W. R. Moser,et al.  The mechanism of phosphine-modified rhodium-catalyzed hydroformylation studied by CIR-FTIR , 1987 .

[22]  John M. Brown,et al.  Structural characterisation in solution of intermediates in rhodium-catalysed hydroformylation and their interconversion pathways , 1987 .

[23]  R. Eldik,et al.  Reactions of Rh(acac)[P(OPh)3]2 with H2, CO and olefins , 1986 .

[24]  A. Trzeciak,et al.  Low pressure, highly active rhodium catalyst for the homogeneous hydroformylation of olefins , 1986 .

[25]  A. Trzeciak,et al.  New rhodium complexes as low pressure hydroformylation catalysts: effect of ligand on catalyst activity and selectivity , 1984 .

[26]  A. Trzeciak,et al.  Synthesis of rhodium(I) acetylacetonato-bistriphenylphosphite complex and its reactivity towards carbon monoxide , 1982 .

[27]  C. A. Tolman,et al.  Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis , 1977 .

[28]  R. Pruett,et al.  Low-pressure system for producing normal aldehydes by hydroformylation of .alpha.-olefins , 1969 .

[29]  R. D. Mullineaux,et al.  Novel Hydroformylation catalysts , 1968 .

[30]  J. Osborn,et al.  Hydroformylation of alkenes by use of rhodium complex catalysts , 1968 .

[31]  A. Wilkinson.  SPOKEN ENGLISH IN SCHOOL , 1965 .