Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2003-06-03
2004-09-21
Vollano, Jean F. (Department: 1621)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S166000, C549S206000, C549S208000, C549S216000
Reexamination Certificate
active
06794328
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a novel 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 for various asymmetric syntheses.
BACKGROUND OF THE INVENTION
Hitherto, many reports have been made on transition metal complexes capable of being utilized in asymmetric syntheses such as asymmetric hydrogenation, asymmetric isomerization, and asymmetric hydrosilylation. Particularly, a complex where an optically active tertiary phosphine coordinates to a transition metal such as ruthenium, rhodium, iridium, or palladium exhibits excellent performance as a catalyst for asymmetric synthetic reactions.
In order to further enhance the performance, a large number of phosphine compounds having various structures have been hitherto developed (The Chemical Society of Japan ed., Kagaku Sosetsu (Chemical Review) 32 Yuki Kinzoku Sakutai no Kagaku (Chemistry of Organic Metal Complexes), pp. 237-238, 1982;
Asymmetric Catalysts In Organic Synthesis
, written by Ryoji Noyori, A Wiley-Interscience Publication). In particular, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (hereinafter referred to as “BINAP”) is one of excellent optically active phosphines, and there have been already reported a rhodium complex (JP-A-55-61937) and a ruthenium complex (JP-B-4-81596 corresponding to U.S. Pat. No. 4,691,037) containing the BINAP as a ligand. Moreover, it has been also reported that a rhodium complex (JP-B-1-42959 corresponding to U.S. Pat. No. 4,604,474) and a ruthenium complex (JP-B-4-81596 corresponding to U.S. Pat. No. 4,691,037) containing 2,2′-bis(di-(p-tolyl)phosphino)-1,1′-binaphthyl (hereinafter referred to as “p-TolBINAP”) as a ligand affords good results in asymmetric hydrogenation and asymmetric isomerization. Furthermore, JP-B-7-68260 corresponding to U.S. Pat. No. 5,223,632 reports that a ruthenium complex of 2,2′-bis(di-(3,5-dialkylphenyl)phosphino)-1,1′-binaphthyl affords excellent results in asymmetric hydrogenation of &bgr;-ketoesters.
However, since selectivity (chemical selectivity, enantio-selectivity) and catalytic activity are not always satisfactory depending on objective reaction or its reaction substrate, improvement of the catalysts are sometimes required.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a novel phosphine compound and specifically, it is an object to provide a novel phosphine compound useful as a ligand for the above catalysts. Moreover, it is another object to provide a novel catalyst having an excellent performance (chemical selectivity, enantio-selectivity, catalytic activity) as a catalyst for asymmetric synthetic reactions, particularly asymmetric hydrogenation.
As a result of extensive studies for solving the above problems, the present inventors have found that a transition metal complex containing an optically active isomer of a diphosphine compound having a specific structure as a ligand is effective as a catalyst component which participates in asymmetric hydrogenation. In addition, they have found that the transition metal complex exhibits excellent catalytic activity and enantio-selectivity in asymmetric hydrogenation. Based on the findings and further investigation, they have accomplished the invention.
Thus, the present invention provides:
(i) A diphosphine compound represented by the general formula (1):
wherein R
1
and R
2
each independently represents a lower alkyl group, a cycloalkyl group, an unsubstituted or substituted phenyl group, or a five-membered heteroaromatic ring residue.
(ii) A compound represented by the general formula (2):
wherein n is an integer of 1 to 3.
(iii) A compound represented by the general formula (3):
wherein R
3
and R
4
each independently represents a hydroxy group, a protected hydroxy group, a lower alkoxy group, a chlorine atom, or a bromine atom.
(iv) A transition metal complex containing an optically active compound of the compound according to (i) above and a transition metal selected from the group consisting of rhodium, ruthenium, iridium, palladium, and nickel.
(v) A catalyst containing a transition metal complex represented by the general formula (4):
M
m
L
n
X
p
Q
q
(4)
wherein M is a transition metal selected from rhodium, ruthenium, iridium, palladium, and nickel and L represents an optically active diphosphine compound of the compound according to (i) above; X is selected from the group consisting of Cl, Br, I, an acetoxy group, a methallyl group, and a &pgr;-allyl group; and Q is selected from the group consisting of NEt
3
(wherein Et represents an ethyl group) and an dialkylammonium ion,
provided that
when M=Rh, X=Cl, Br, or I and m=2, n=2, p=2, and q=0,
when M=Ru and X=an acetoxy group, m=1, n=1, p=2 and q=0,
when M=Ru and X=a methallyl group, m=1, n=1, p=2 and q=0,
when M=Ru, X=Cl, Br, or I, and Q=NEt
3
, m=2, n=2, p=4, and q=1,
when M=Ru, X=Cl, Br, or I, and Q=an dialkylammonium ion, m=n=2, p=5, and q=1,
when M=Ir, X=Cl, Br, or I and m=2, n=2, p=2, and q=0,
when M=Pd and X=Cl, Br, or I, m=1, n=1, p=2, and q=0,
when M=Pd and X=a &pgr;-allyl group, m=2, n=2, p=2, and q=0, and
when M=Ni, X=Cl, Br, or I and m=1, n=1, p=2, and q=0.
(vi) A catalyst containing a transition metal complex represented by the general formula (5):
[M
m
L
n
X
p
Z
q
]Y
r
(5)
wherein M is a transition metal selected from rhodium, ruthenium, iridium, palladium, and nickel and L represents an optically active diphosphine compound of the compound according to (i) above; X is selected from the group consisting of a &pgr;-allyl group, cod, nbd, Cl, Br, and I; Z represents benzene or p-cymene; and Y is selected from the group consisting of BF
4
, ClO
4
, PF
6
, BPh
4
, Cl, Br, and I, and cod represents 1,5-cyclooctadiene, nbd represents norbornadiene, and Ph represents a phenyl group, provided that
when M=Rh, X=cod or nbd, Y=BF
4
, ClO
4
, PF
6
, or BPh
4
, and m=1, n=1, p=1, q=0, and r=1,
when M=Ru and Y=Cl, Br, or I, X=Cl, Br, or I, Z=benzene or p-cymene, and m=1, n=1, p=1, q=1, and r=1,
when M=Ru and Y=BF
4
, ClO
4
, PF
6
, or BPh
4
, m=1, n=1, p=0, q=0, and r=2,
when M=Ir, X=cod or nbd, Y=BF
4
, ClO
4
, PF
6
, or BPh
4
, and m=1, n=1, p=1, q=0, and r=1,
when M=Pd and X=a &pgr;-allyl group, Y=Cl, Br, I, BF
4
, ClO
4
, PF
6
, or BPh
4
and m=1, n=1, p=1, q=0, and r=1,
when M=Pd and p=0, Y=BF
4
, ClO
4
, PF
6
, or BPh
4
and m=1, n=1, q=0, and r=1, and
when M=Ni, X=Cl, Br, or I and m=1, n=1, p=2, q=0, and r=0.
(vii) A catalyst for asymmetric hydrogenation, which contains the transition metal complex according to (iv) above.
DETAILED DESCRIPTION OF THE INVENTION
The following will explain the invention in detail.
The diphosphine compound of the invention is a compound represented by the following general formula (1):
wherein R
1
and R
2
each independently represents a lower alkyl group, a cycloalkyl group, an unsubstituted or substituted phenyl group, or a five-membered heteroaromatic ring residue.
The lower alkyl group for the above R
1
and R
2
is an alkyl group having 1 to 5 carbon atoms, which includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a se
Saito Takao
Yokozawa Tohru
Sughrue & Mion, PLLC
Takasago International Corporation
Vollano Jean F.
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