Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2000-10-30
2001-12-25
Vollano, Jean F. (Department: 1621)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C568S014000, C568S017000, C549S218000, C556S013000, C556S021000
Reexamination Certificate
active
06333291
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a novel optically active diphosphine compound, a production intermediate thereof, a transition metal complex containing the diphosphine compound as a ligand and a transition metal complex catalyst useful as a catalyst of various asymmetric synthesis reactions.
BACKGROUND OF THE INVENTION
A large number of transition metal complexes have been reported, which can be used in asymmetric syntheses such as asymmetric hydrogenation reaction, asymmetric isomerization reaction and asymmetric hydrosilylation reaction. Particularly, a complex in which an optically active tertiary phosphine compound is coordinated to a transition metal complex such as of ruthenium, rhodium, iridium or palladium has excellent performance as a catalyst of asymmetric synthesis reactions.
In order to further improve this performance, a large number of phosphine compounds having various structures have so far been developed (Chemical Review 32 “Chemistry of Organic Metal Complex”, pp. 237-238, 1982, edited by The Chemical Society of Japan; “Asymmetric Catalysis In Organic Synthesis”, edited by R. Noyori, A Wiley-Interscience Publication).
Particularly, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (to be referred to as “BINAP” hereinafter) is one of the excellent optically active phosphine compounds, and a rhodium complex (JP-A-55-61973; the term “JP-A” as used herein means an “unexamined published Japanese patent application”) and a ruthenium complex (JP-A-61-63690), which contain the BINAP as a ligand, have already been reported.
Also, it has been reported that a rhodium complex (JP-A-60-199898) and a ruthenium complex (JP-A-61-63690), which contain 2,2′-bis(di-(p-tolyl)phosphino)-1,1′-binaphthyl (to be referred to as “p-TolBINAP” hereinafter) as a ligand, give good results in asymmetric hydrogenation reaction and asymmetric isomerization reaction. In addition, it has been reported in JP-A-3-255090 that a ruthenium complex of 2,2′-bis(di-(3,5-dialkylphenyl)phosphino)-1,1′-binaphthyl gives excellent results in asymmetric hydrogenation of &bgr;-ketoesters.
However, since their selectivity (chemical selectivity or enantio-selectivity) and catalytic activities are not sufficient depending on the intended reactions or reaction substrates thereof, there are cases in which these catalysts have to be improved.
SUMMARY OF THE INVENTION
In view of the above, it therefore becomes an object of the invention to provide a novel catalyst which has excellent performance (chemical selectivity, enantio-selectivity and catalytic activity) as a catalyst of asymmetric synthesis reactions, particularly asymmetric hydrogenation reaction.
The invention also contemplates providing a novel phosphine compound and further providing a novel phosphine compound which is useful as a ligand of the catalyst.
With the aim of achieving these objects, the present inventors have conducted intensive studies and found as a result of the efforts that a transition metal complex of an optically active diphosphine compound represented by the following formula (6) (to be referred sometimes to as 7,8-dihydro-6H-dibenzo[f,h][1,5]dioxonine-1,13-diyl-bis(diphenylphosphine) hereinafter) is effective as a catalyst component which is concerned in the asymmetric hydrogenation reaction, and that this transition metal complex exerts excellent catalytic activity and enantio-selectivity in the asymmetric hydrogenation reaction of benzoylacetic acid esters. Thereafter, the invention has been established by further conducting evaluations.
In this connection, the inventors have already developed a transition metal complex of ((5,6), (5′,6′)-bis-(methylenedioxy)biphenyl-2,2′-diyl)bis(diphenylphosphine) (to be referred to as “SEGPHOS” hereinafter), but effects of the transition metal complex of diphenylphosphine compound of the invention are equal to or higher than those of the above transition metal complex.
Other objects and advantages of the invention will be made apparent as the description progresses.
DETAILED DESCRIPTION OF THE INVENTION
One of the diphosphine compounds of the invention is a compound represented by the following general formula (1):
wherein R
1
and R
2
each independently represents a cycloalkyl group, an unsubstituted or substituted phenyl group or a five-membered aromatic heterocycle residue.
The cycloalkyl group is preferably cyclopentyl group, cyclohexyl group or cycloheptyl group, the five-membered aromatic heterocycle residue is preferably 2-furyl group, 3-furyl group, 2-benzofuryl group or 3-benzofuryl group, and the substituent group of the substituted phenyl group is preferably an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, a di(lower alkyl)amino group or a halogen atom. The term “lower alkyl” as used herein means an alkyl group having from 1 to 5 carbon atoms.
Preferred among these compounds is a compound of a formula (7):
wherein R
5
and R
6
each independently represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms or an alkoxy group having from 1 to 4 carbon atoms, and R represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, an alkoxyl group having from 1 to 4 carbon atoms or a di (lower alkyl)aminogroup. The term “lower alkyl” as used here in means an alkyl group having from 1 to 5 carbon atoms.
More preferred is a compound in which R
5
and R
6
are the same and selected from the group consisting of hydrogen atom, t-butyl group, n-butyl group, n-propyl group, isopropyl group, ethyl group and methyl group, and R
7
is selected from the group consisting of hydrogen atom, t-butoxy group, isopropoxy group, ethoxy group and methoxy group.
A diphosphine oxide compound represented by the following formula (2) is also a compound which belongs to the invention:
wherein R
1
and R
2
are as defined in the foregoing.
The compound of formula (2) is a production intermediate of the diphosphine compounds of formulae (1) and (7).
A compound represented by the following formula (3) is also a compound which belongs to the invention:
wherein R
3
and R
4
each independently represents a cycloalkyl group, an unsubstituted or substituted phenyl group, a five-membered aromatic heterocycle residue, an alkoxyl group having from 1 to 4 carbon atoms, phenoxy group, benzyloxy group, chlorine atom or bromine atom.
In this connection, the compound represented by formula (3) can be divided into a compound in which R
3
and R
4
each independently represents a cycloalkyl group, an unsubstituted or substituted phenyl group or a five-membered aromatic heterocycle residue and a compound in which R
3
and R
4
each independently represents an alkoxyl group having from 1 to 4 carbon atoms, phenoxy group, benzyloxy group, chlorine atom or bromine atom.
Of these two compounds, the former is a production intermediate of the compound of formula (2) and the latter is a production intermediate of the former compound.
In addition, racemic modifications and optically active compounds of the above compounds are also the compounds which belong to the invention.
Methods for the production of these compounds are described in the following.
For the sake of avoiding complexity, production methods of the compounds of the invention are illustratively described using an optically active (−)-form of a compound represented by the following formula (8), ((−)-7,8-dihydro-6H-dibenzo[f,h][1,5]dioxonine-1,13-diyl-bis(diphenylphosphine)), as an example of the compounds included in the invention. However, the invention is not limited to this example.
That is, 3,3′-dibromo-1,1′-trimethylenedioxydibenzene (10) is prepared by allowing sodium hydride and trimethylene dibromide to react with 3-bromophenol (11). The compound (10) is allowed to react with magnesium pieces to obtain a Grignard's reagent which is then allowed to react with diphenylphosphinyl chloride to obtain 1,1′-trimethylenedioxydibenzene-3,3′-diyl-bis(di
Ishizaki Takero
Saito Takao
Sayo Noboru
Yokozawa Tohru
Sughrue Mion Zinn Macpeak & Seas, PLLC
Takasago International Corporation
Vollano Jean F.
LandOfFree
Optically active diphosphine compound, production... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Optically active diphosphine compound, production..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Optically active diphosphine compound, production... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2564168