Optically active bidentate phosphine ligand palladium complex

Details Optically active bidentate phosphine ligand palladium complex Optically active bidentate phosphine ligand palladium complex

1997-09-16

1999-03-09

Nazario-Gonzalez, Porfirio

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

556 14, 556136, 502162, 548402, 549206, 549430, 568347, 568349, 568362, C07F 902, C07F 1500

Patent

active

058803017

DESCRIPTION:

BRIEF SUMMARY
This application was filed as a request for U.S. examination under 35 U.S.C. .sctn. 371 of International application No. PCT/JP96/00418 filed Feb. 23, 1996.


TECHNICAL FIELD

The present invention relates to a novel optically active bidentate phosphine ligand palladium complex and the use thereof.
The novel optically active bidentate phosphine ligand palladium complex of the present invention may be used as a catalyst in the preparation of optically active .beta.-hydroxyketones which are intermediates of medicines.


BACKGROUND ART

Recently, the organic synthesis reaction using a transition metal complex as a catalyst has been intensively developed, and especially, the asymmetric synthesis using an optically active bidentate phosphine ligand has been enthusiastically studied as a method of efficiently obtaining desired optically active substances. For instance, some reports disclose the development of the asymmetric catalyst using palladium as a transition metal, and there are known Pd(BINAP).sub.2 having the structure (A), (B) (Ozawa, F.; Kubo, A.; Matsumoto, Y.; Hayashi, T. Organometallics, 1993, 12, 4188), shown below, etc.; however, the palladium complex having the optically active bidentate phosphine as a ligand and coordinating with an water molecule or a hydroxyl group has not been known. ##STR3##
The catalytic asymmetric aldol reaction yielding an optically active .beta.-hydroxyketone is the condensation reaction of silyl enol ether, ketene silylacetal or ketene silylthioacetal and an aldehyde with an optically active Lewis acid catalyst. The examples are described in the literatures such as (a) Heathcock, C. H., In Asymmetric Synthesis; Morison, J. D., Ed.; Academic press: New York:, 1984; Vol. 3, Chapter 2, (b) Heathcock, C. H., In Comprehensive Organic Synthesis; Perganon Press: Oxford, 1991; Vol. 2, Chapter 1.5-1.9, and the like. In the aldol reaction with these asymmetric Lewis acid catalysts, although extremely high asymmetric yields are reported, in view of the nature of the Lewis acid, the catalyst is expected to have an affinity for various oxygen-functional groups and the like in the preparation of medicines, and therefore, the application of such a reaction to complicated compounds is expected to have difficulty.
On the other hand, although the literatures such as Reetz, M. T.; Vougioukas, A. E., Tetrahedron Lett., 1987, 28, 793; Roos, G. H. P.; Haines, R. J.; Raab, C. E., Synth. Commun., 1993, 23, 1251, and the like disclose the catalytic asymmetric aldol reaction via a transition metal enolate which is not expected to have an affinity for various oxygen-functionnal groups and the like, yet the asymmetric yields are not much more than 20%, and hence the development of the transition metal complex having a novel optically active ligand and the efficient asymmetric synthesis using the complex has been desired. Since the asymmetric aldol reaction is applicable to the asymmetric synthesis of the aglycon of polyoxomacrolides such as erythromycin A, erythromycin B and the like, stereochemistry in the aldol reaction has been enthusiastically studied. The compound having a .beta.-hydroxyketone as a moiety is exemplified by gingerol analogues. The gingerols are known as a compound which has cardiotonic activity (Japanese Patent Application Laid-open No. Sho 64-921 and Japanese Patent Application Laid-open No. Hei 6-40895), activity for platelet-aggregation (Japanese Patent Application Laid-open No. Sho 63-72625), analgesic activity (Japanese Patent Application No. Sho 59-1684), anti-inflammatory activity (Japanese Patent Application Laid-open No. Hei 3-90021), anti-parasitic activity (Japanese Patent Application Laid-open No. Hei 2-4711), and the like. Moreover, the mevalonic acid moiety of HMG-CoA reductase inhibitors has a .beta.-hydroxyester, and therefore, a method of efficiently obtaining an optically active .beta.-hydroxyketone is useful. However, the aldol reaction does not proceed and the .beta.-hydroxyketone is not obtained even if the known complex of (A) or (B) is used.


DISCLOSURE

REFERENCES:
Ozawa, F. et al., "Palladium-Catalyzed Asymmetric Arylation of 2,3-Dihydrofuran with Phenyl Triflate. A Novel Asymmetric Catalysis Involving a Kinetic Resolution Process," Organometallics, v. 12, pp. 4188-4196, 1993.
Reetz, M.T. et al., "Rhodium-Diphosphine Complexes as Catalysts in Aldol Additions," Tetrahedron Letters, v. 28, n. 7, pp. 793-796, 1987.
Heathcock, C.H. et al. Comprehensive Organic Synthesis, Pergamon Press: Oxford, v.2, ch. 1.5-1.9, 1991.
Heathcock, C.H., Asymmetric Synthesis, J.D. Morison, ed., Academic Press: New York, v.3, ch.2, 1984.
Roos, Gregory et al. "Enantioselective Approaches to Rhodium Catalysed Aldol-Type Reactions." Synthetic Communications, v. 23, n. 9, pp. 1251-1259, 1993.
Noyori, Ryoji. "BINAP: An Efficient Chiral Element for Asymmetric Catalysis." Acc. Chem. Res., v23 pp. 345-350,1990.
Hayashi, Tamio et al. "Asymmetric Catalytic Hydrosilylation of Ketones Preparation of Chiral Ferrocenylphosphines as Chiral Ligands." Tetrahedron Letters, No. 49-50, pp. 4405-4408, 1974.
Hayashi, Tamio et al. "Asymmetric Synthesis Catalyzed by Chiral Ferrocenylphsphine-Transition Metal Complexes. I. Preparation of Chiral Ferrocenylphophines." Bull. Chem. Soc. Jpn., v53, pp. 1138-1151, 1980.
Hayashi, Teruyuki et al. "Catalytic Asymmetric Hydroformylation by the Use of Rhodium-complexes of Chiral Bidentate Phosphorus Ligands Bearing Saturated Ring Skeletons." Bulletin of the Chemical Society of Japan, v. 52, n. 9, pp. 2605-2608, 1970.
Achiwa, Kazuo. "Asymmetric Hydrogenation with New Chiral Functionalized Bisphospine-Rhodium Complexes." Journal of the American Chemical Society, v98, No. 25, pp. 8265-8266, Dec. 8, 1976.
Achiwa, Kazuo. "New Chiral Phosphine-Rhodium Catalysts for Asymmetric Synthesis of .RTM.-and (S)-N-Benzyloxycarbonylalanine.sup.1)." Chemistry Letters, pp. 777-778, 1977.
Ojima, Iwao et al. "N-Carbamoyl-4-Diphenylphosphino-2-Diphenylphophinomethlypyrrolidines (CAPP). Efficient New Chiral Ligands for Asymmetric Hydrogenation." Tetrahedron Letters, v. 21, pp. 1051-1054, 1980.
Murrer, Barry A. et al. "Synthesis of Improved Preparation of its Phosphine Analogue (DIOP)." Synthesis, pp. 350-351, 1979.
Sodeoka, Mikiko et al. "Stable Diaqua Palladium (II) Complexes of BINAP and Tol-BINAP as Highly Efficient Catalysts for Asymmetric Aldol Reactions." Synlett, pp. 463-466, May 1997.
Hayashi, Tamio, et al., Palladium-Catalyzed Asymmetric 1,4-Disilylation of .alpha.,.beta.-Unsaturated Ketones: Catalytic Asymmetric Synthesis of .beta.-Hydroxy Ketones, Journal of the American Chemical Society, vol. 110, No. 16, pp. 5579-5581, 1988.
Matsumoto, Yonetatsu, et al., Catalytic Asymmetric Synthesis of .beta.-Hydroxy Ketones by Palladium-Catalyzed Asymmetric 1,4-Disilylation of .alpha.,.beta.-Unsaturated Ketones, Tetrahedron, vol. 50, No. 2, pp. 335-346, 1994.

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