Ruthenium complexes and process for preparing alcoholic...

Details Ruthenium complexes and process for preparing alcoholic... Ruthenium complexes and process for preparing alcoholic...

2002-12-27

2004-09-14

Nazario-Gonzalez, Porfirio (Department: 1621)

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

Organic compounds

Heavy metal containing

C568S881000

Reexamination Certificate

active

06790973

ABSTRACT:

FIELD OF THE INVENTION
The invention relates to a novel ruthenium complex and a process using said complex as a catalyst for preparing an optically active alcoholic compound. More particularly, the invention relates to a ruthenium complex, which is a highly efficient catalyst useful for preparing an optically active alcoholic compound as an intermediate or the like of pharmaceuticals, agricultural chemicals or commodity chemicals, and a process using said complex as a catalyst for preparing an optically active alcoholic compound.
BACKGROUND OF THE INVENTION
Transition metal complexes having optically active diphosphine compounds as the ligands are extremely useful as catalysts for asymmetric reactions and a large number of catalysts have been developed so far. Since the optically active diphosphine compounds give a great effect to a catalyst performance, a variety of optically active diphosphine compounds have been developed. For example, an axially chiral diphosphine compound represented by BINAP or a diphosphine compound having asymmetry on carbon such as DIOP are known. However, although asymmetric hydrogenation or asymmetric reduction catalysts, which have been examined in a large number, are useful as catalysts for olefins or carbonyl compounds having a functional group, they have not shown either a sufficient efficiency or a sufficient enatioselection for the reactions of carbonyl compounds having no functional group.
In order to solve these problems, optically active ruthenium metal complexes having as the ligand an axially chiral diphosphine compound and an optically active diamine compound have recently been developed and a highly efficient as well as highly stereoselective hydrogenation or reduction of carbonyl compounds have become possible. For example, as described in JP, A, 8-225466 and J. Am. Chem. Soc. 1995, 117, 2675, a process for carrying out the asymmetric hydrogenation of a carbonyl compound using a three-component catalyst system consisting of “ruthenium complex having as the ligand an optically active diphosphine compound”, “optically active diamine compound” and “base” has been developed. Also, as described in JP, A, 11-189600, J. Am. Chem. Soc. 1998, 120, 13529 and Angew. Chem. Int. Ed. 1998, 37, 1703, a process for carrying out the asymmetric hydrogenation of a carbonyl compound using a two-component system catalyst consisting of “ruthenium complex having as the ligands a diphosphine compound and a vdiamine compound” and “base”, improving complexity of the reaction using the three-component system has been reported.
In the above patents and reports, although the use of catalysts having as the ligand BINAPs (hereinafter BINAP, TolBINAP and XylBINAP generically are referred to as BINAPs) is reported, reporting examples of catalysts having as the ligands other axially chiral diphosphine compounds are not abundant. As for an example of the asymmetric hydrogenation of carbonyl compounds using a ruthenium metal complex having as the ligand an axially chiral diphosphine compound except BINAP, as described in WO 01/74829 and Org. Lett. 2000, 2, 26, 4173, catalysts consisting of two components of a ruthenium complex having as the ligands an optically active PHANEPHOS and an optically active diamine compound and a base have been reported. Further, in J. Org. Chem. 1999, 64, 2127, the asymmetric hydrogenation of carbonyl compounds using a three-component system catalyst consisting of a ruthenium complex having the optically active BICP as the ligand, an optically active diamine compound and a base has been reported. By the catalyst of WO 01/74829 and Org. Lett. 2000, 2, 26, 4173 the symmetric hydrogenation of acetophenone gives an optically active phenethyl alcohol of the optical purity 99% ee. The catalyst of J. Org. Chem. 1999, 64, 2127 gives an optically active phenethyl alcohol of the optical purity 76% ee by the asymmetric hydrogenation of acetophenone.
On the other hand, there are fewer examples of the asymmetric hydrogenation of carbonyl compounds by a ruthenium metal complex having an optically active diphosphine compound with asymmetry on carbon as the ligand, and an effective catalyst has not been found. For example, in CHIRALITY 2000, 12, 514 the asymmetric hydrogenation of acetophenone using a two-component system catalyst consisting of a ruthenium complex having the optically active SKEWPHOS and the optically active DPEN as the ligands and a base has been reported, achieving phenethyl alcohol of the optical purity 84% ee. In JP, A, 8-225466 one example of the symmetric hydrogenation of &bgr;-ionone using a catalyst consisting of three components of a ruthenium complex having the optically active CHIRAPHOS as the ligand, an optically active diamine compound and a base has been reported, and the corresponding optically active alcohol is obtained in the optical purity 53% ee. In both CHIRALITY 2000, 12, 514 and JP, A, 8-225466 the optical purity is lower compared with the case using a ruthenium complex having the above BINAPs as the ligand. Although in Angew. Chem. Int. Ed. 1998, 37, 1703 the synthesis of ruthenium complexes having the optically active DIOP or the optically active CHIRAPHOS as the ligand is reported, examination as a catalyst for the asymmetric hydrogenation of a carbonyl compound is not carried out.
As described above, since a catalyst consisting of a ruthenium metal complex having an axially chiral diphosphine compound represented by BINAPs and a chiral diamine compound as the ligand and a base enables the asymmetric hydrogenation of a wide range of carbonyl compounds and shows a high reactivity and a high enantioselectivity, giving an optically active alcohol with a high optical purity and therefore, it is of high utility value. However, since said catalyst does not necessarily show a high performance with respect to all the carbonyl compounds, development of a catalyst having an optically active diphosphine ligand other than BINAPs is desired.
Further, there are drawbacks in the synthesist of axially chiral diphosphine compounds. For example, the optically active BINAP is synthesized from binaphthol, which is obtained by the optical resolution, by methods shown in the following.
In J. Org. Chem. 1993, 58, 1945 the reaction of 2,2′-bis-(trifuluoromethanesulfonyl)oxy-1,1′-binaphthyl derivatized from the optically active binaphthol and in J. Org. Chem. 1994, 59, 7180 the synthesis by the reaction of 2,2′-bis-(trifuluoromethanesulfonyl)oxy-1,1′-binaphthyl and diphenylphosphine are reported.
However, the above synthetic methods require beforehand obtain the optically active binaphthol by the optical resolution from racemic binaphthol and further derivatize this optically active binaphthol to an optically active diphosphine compound of axial chirality.
As described above, in the process for obtaining axially chiral diphosphine compounds in many cases the steps are generally tedious since 1) the synthesis is multi-steps, 2) the optical resolution step is required.
As described above, with respect to the asymmetric hydrogenation by a three-component catalyst system consisting of a ruthenium complex having an optically active diphosphine compound with asymmetry on carbon as the ligand, an optically active diamine compound and a base, or by a two-component system catalyst consisting of a ruthenium complex having an optically active diphosphine compound with asymmetry on carbon and an optically active diamine compound as the ligands and a base, the reported examples are extremely few, and complexes satisfying a catalytic performance have not yet been developed.
SUMMARY OF THE INVENTION
Consequently, the invention solves the foregoing problems in the art and provides novel ruthenium complexes having an optically active diphosphine compound, which has asymmetry on carbon and is easy to synthesize, as the ligand and a process for preparing optically active alcoholic compounds using said complex as the catalyst, wherein said process is for preparing optically active alcoholic compounds, which are excellent in terms of rea

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