Asymmetric hydroformylation of styrene using rhodium and platinum complexes of diphosphites containing atropisomeric backbones and chiral 1,3,2-dioxaphosphorinane moieties

Stefánia Cserépi-Szucs, Gottfried Huttner, László Zsolnai, J. Bakos

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Abstract

Diastereomers of 2,2′-bis[4,6-dimethyl-1,3,2-dioxaphosphorinan-2-yloxy]-1,1′- binaphthyl, R-bis(4R,6R)-1, and S-bis(4R,6R)-2, have been synthesized. The solid state structure of S-bis(4S,6S)-1 and the platinum complex [PtCl2(1)] (3) of its enantiomer pair have been determined. The structure of 3 shows a slightly distorted square-planar geometry. The dihedral angle defined by the naphthyl rings in 3 is smaller (77.6°(2)) than in the free ligand (103.0°(2)). In the platinum- and rhodium-catalyzed asymmetric hydroformylation of styrene, the axial chirality in the bridge has been found to be determinate for the product configuration with a cooperative effect from the terminal groups. The maximum enantioselectivity (39% ee) and a remarkable high regioselectivity (84%) towards branched aldehyde was obtained with platinum system of a matched constellation of the ligand (S-bis(4R,6R)-2).

Original languageEnglish
Pages (from-to)70-78
Number of pages9
JournalJournal of Organometallic Chemistry
Volume586
Issue number1
Publication statusPublished - Jul 31 1999

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Hydroformylation
Rhodium
Styrene
Platinum
rhodium
styrenes
platinum
Ligands
Regioselectivity
ligands
Enantiomers
constellations
Chirality
Enantioselectivity
enantiomers
Dihedral angle
Aldehydes
aldehydes
chirality
dihedral angle

Keywords

  • Catalysis
  • Diphosphite
  • Hydroformylation
  • Platinum
  • Rhodium

ASJC Scopus subject areas

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

Cite this

Asymmetric hydroformylation of styrene using rhodium and platinum complexes of diphosphites containing atropisomeric backbones and chiral 1,3,2-dioxaphosphorinane moieties. / Cserépi-Szucs, Stefánia; Huttner, Gottfried; Zsolnai, László; Bakos, J.

In: Journal of Organometallic Chemistry, Vol. 586, No. 1, 31.07.1999, p. 70-78.

Research output: Contribution to journalArticle

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abstract = "Diastereomers of 2,2′-bis[4,6-dimethyl-1,3,2-dioxaphosphorinan-2-yloxy]-1,1′- binaphthyl, R-bis(4R,6R)-1, and S-bis(4R,6R)-2, have been synthesized. The solid state structure of S-bis(4S,6S)-1 and the platinum complex [PtCl2(1)] (3) of its enantiomer pair have been determined. The structure of 3 shows a slightly distorted square-planar geometry. The dihedral angle defined by the naphthyl rings in 3 is smaller (77.6°(2)) than in the free ligand (103.0°(2)). In the platinum- and rhodium-catalyzed asymmetric hydroformylation of styrene, the axial chirality in the bridge has been found to be determinate for the product configuration with a cooperative effect from the terminal groups. The maximum enantioselectivity (39{\%} ee) and a remarkable high regioselectivity (84{\%}) towards branched aldehyde was obtained with platinum system of a matched constellation of the ligand (S-bis(4R,6R)-2).",
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T1 - Asymmetric hydroformylation of styrene using rhodium and platinum complexes of diphosphites containing atropisomeric backbones and chiral 1,3,2-dioxaphosphorinane moieties

AU - Cserépi-Szucs, Stefánia

AU - Huttner, Gottfried

AU - Zsolnai, László

AU - Bakos, J.

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N2 - Diastereomers of 2,2′-bis[4,6-dimethyl-1,3,2-dioxaphosphorinan-2-yloxy]-1,1′- binaphthyl, R-bis(4R,6R)-1, and S-bis(4R,6R)-2, have been synthesized. The solid state structure of S-bis(4S,6S)-1 and the platinum complex [PtCl2(1)] (3) of its enantiomer pair have been determined. The structure of 3 shows a slightly distorted square-planar geometry. The dihedral angle defined by the naphthyl rings in 3 is smaller (77.6°(2)) than in the free ligand (103.0°(2)). In the platinum- and rhodium-catalyzed asymmetric hydroformylation of styrene, the axial chirality in the bridge has been found to be determinate for the product configuration with a cooperative effect from the terminal groups. The maximum enantioselectivity (39% ee) and a remarkable high regioselectivity (84%) towards branched aldehyde was obtained with platinum system of a matched constellation of the ligand (S-bis(4R,6R)-2).

AB - Diastereomers of 2,2′-bis[4,6-dimethyl-1,3,2-dioxaphosphorinan-2-yloxy]-1,1′- binaphthyl, R-bis(4R,6R)-1, and S-bis(4R,6R)-2, have been synthesized. The solid state structure of S-bis(4S,6S)-1 and the platinum complex [PtCl2(1)] (3) of its enantiomer pair have been determined. The structure of 3 shows a slightly distorted square-planar geometry. The dihedral angle defined by the naphthyl rings in 3 is smaller (77.6°(2)) than in the free ligand (103.0°(2)). In the platinum- and rhodium-catalyzed asymmetric hydroformylation of styrene, the axial chirality in the bridge has been found to be determinate for the product configuration with a cooperative effect from the terminal groups. The maximum enantioselectivity (39% ee) and a remarkable high regioselectivity (84%) towards branched aldehyde was obtained with platinum system of a matched constellation of the ligand (S-bis(4R,6R)-2).

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