Chiral ligands used in transition metal catalysts for...

Organic compounds -- part of the class 532-570 series – Organic compounds – Phosphorus containing

Reexamination Certificate

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C556S021000, C560S190000, C502S162000, C502S166000, C502S167000

Reexamination Certificate

active

08008529

ABSTRACT:
Ligands of the formula (I) secondary phosphine-Q-P(═O)HR1(I) in the form of mixtures of diastereomers or pure diastereomers, in which secondary phosphine is a secondary phosphine group with hydrocarbon radicals or heterohydrocarbon radicals as substituents; Q is a bivalent bisaryl or bisheteroaryl radical with an axial chiral centre to which the two phosphorus atoms are bonded in the ortho positions to the bisaryl or bisheteroaryl bridge bond, or Q is a bivalent ferrocenyl radical with a planar chiral centre or without a planar chiral centre, to which the phosphorus atom of the secondary phosphine is bonded directly or via a C1-C4-carbon chain to a cyclopentadienyl ring, the —P*(═O)HR1group is bonded either on the same cyclopentadienyl ring in ortho position to the bonded secondary phosphine or on the other cyclopentadienyl ring; P* is a chiral phosphorus atom, and R1is a hydrocarbon radical, a heterohydrocarbon radical or a ferrocenyl radical, where R1is a ferrocenyl radical with a planar chiral centre when Q is a ferrocenyl radical without a planar chiral centre. Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

REFERENCES:
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International Search Report issued Oct. 25, 2007 in the International (PCT) Application PCT/EP2007/055026 of which the present application is the U.S. National Stage.
Written Opinion issued Oct. 25, 2007 in the International (PCT) Application PCT/EP2007/055026 of which the present application is the U.S. National Stage.
Xiao-bin Jiang et al., “The application of monodentate secondary phosphine oxide ligands in rhodium- and iridium-catalyzed asymmetric hydrogenation”, Tetrahedron: Asymmetry, vol. 15, No. 14, pp. 2223-2229, XP004523712, ISSN: 0957-4166, Jul. 26, 2004.
P. Gary Eller et al., “Syntheses of New Tetrafluoroaryl Derivatives of Phosphorus and Sulfur”, Journal of Organometallic Chemistry, vol. 22, No. 3, pp. 631-636, XP009090293, ISSN: 0022-328X, May 1970.
Xiao-bin Jiang et al., “Application of Monodentate Secondary Phosphine Oxides, a New Class of Chiral Ligands, in Ir(I)-Catalyzed Asymmetric Imine Hydrogenation”, Organic Letters, vol. 5, No. 9, pp. 1503-1506, XP009090287, ISSN: 1523-7060, May 1, 2003.
X. Jiang, “Monodentate secondary phosphine oxides (SPO's), Synthesis and application in asymmetric catalysis”, pp. 1-173, XP007903156, 2004.

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