Method for generating secondary phosphines

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

Reexamination Certificate

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C568S008000, C568S009000

Reexamination Certificate

active

07491851

ABSTRACT:
This invention provides a method for generating secondary phosphines from secondary phosphine oxides in the presence of a reducing agent, such as diisobutylaluminum hydride (DIBAL-H), triisobutyldialuminoxane, triisobutylaluminum, tetraisobutyldialuminoxane, or another reducing agent comprising: (i) an R1R2AlH moiety, wherein R1and R2are each an alkyl species or oxygen, and wherein at least one of R1or R2comprises at least 2 carbon atoms, or (ii) an R1R2R3Al moiety, wherein R1, R2, and R3are not hydrogen, and wherein at least one of R1, R2, and R3is an alkyl species comprising a β-hydrogen, not including triethylaluminum. Preferred reducing agents for the present invention include: diisobutylaluminum hydride, triisobutyldialiuminoxane, triisobutylaluminum, tetraisobutyldialuminoxane, and combinations thereof.

REFERENCES:
patent: 4113783 (1978-09-01), Malpass et al.
patent: 5648549 (1997-07-01), Kleiner
Million et al., The Mechanism of the Reduction of Diphenylphosphinic acid and its Ethyl Ester by Lithium Aluminum halide, J. Chem. Soc., Suppl. (1964) 6121-6130.
Senda, T., et al. Rhodium-Catalyzed Asymmetric 1, 4 Addition of Organoboron Reagents to 5, 6-Dihydro-2(1H)-pyridinones, Asymmetric Synthesis of 4 Aryl-2 piperidinones, J. Org. Chem. 2001, 66, 6852-6856, XP-002977097.
Kapoor, P.N., et al; Synthesis of Three New Ditertiary Phosphines: 1-Diphenylophospino-2-BIS(m-Fluorophenyl) Phosphinoethane, 1 Diphenylphosphino-2-BIS(p-Fluorophenyl) Phosphinoethane and 1 Diphenylphosphino-2-m BIS Journal of Organometallic Chemistry (1984), 276 (2) 167-170.
(Trifluoromethyl)Phenyl-phosphinoethane: Journal of Organometallic Chemistry, 276 (1984) 167-170 XP 002327624.
McKinstry, L., et al.: On the Asymmetric Rh(1) Catalyzed [4+2] Cycloisomerization Reaction. Electronic and Torsional Ligand Control of Absolute Stereoselection. Tetrahedron vol. 50, No. 21, pp. 6145-6154, 1994 XP-002327625.

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