Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1999-05-21
2001-03-13
McKane, Joseph K. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C548S341100, C568S009000, C568S367000, C568S382000, C568S717000, C502S302000, C502S303000, C502S304000
Reexamination Certificate
active
06201123
ABSTRACT:
BACKGROUND OF THE INVENTION
(1) Field of the Invention
This invention relates to a catalyst composition for organic asymmetric synthesis, a catalyst solution comprising the catalyst composition, and a process for preparing an optically active epoxide by catalytic asymmetric epoxidation.
The catalyst composition of the present invention is useful for various organic asymmetric syntheses. For example, it exhibits a high catalytic activity for asymmetric epoxidation of enones and gives epoxides having an enhanced optical purity.
(2) Description of the Related Art
As for catalysts for organic asymmetric syntheses, a catalyst solution has been heretofore proposed for asymmetric epoxidation in Japanese Unexamined Patent Publication No. H10-120668, which comprises (A) lanthanum isopropoxide, (B) a binaphthol derivative represented by the following general formula (6):
wherein R
14
is hydrogen or a hydroxymethyl group, and * signifies that the carbon atom adjacent thereto is optically active, (C) a molecular sieve 4A, and (D) tetrahydrofuran.
However, when the catalytic asymmetric epoxidation is conducted by using tert-butylhydroperoxide (hereinafter abbreviated to “TBHP”) as an oxidizing agent and, for example, at room temperature for 30 minutes, an epoxide with a low optical purity of 73% is obtained in a low yield of 86%. If the catalytic asymmetric epoxidation is conducted by using a special oxidizing agent, i.e., cumene hydroperoxide (hereinafter abbreviated to “CMHP”) and, for example, for at least 6 hours, then, epoxides with an optical purity of 83 to 94% are obtained in a yield of 78 to 98% (J. Am. Chem. Soc. Vol. 119, No. 9, 1997, p2329-2330).
SUMMARY OF THE INVENTION
A primary object of the present invention is to provide a catalyst composition exhibiting an enhanced catalytic activity for organic asymmetric synthesis and giving a reaction product with a high optical purity.
In accordance with the present invention, there is provided a catalyst composition for organic asymmetric synthesis comprising:
(A) a lanthanoid element ion;
(B) a binaphthol represented by the following general formula (1):
wherein R
1
, R
2
, R
3
and R
4
independently represent a hydrogen atom, a straight chain, branched chain or cyclic alkyl group having 1 to 10 carbon atoms, a straight chain, branched chain or cyclic alkoxy group having 1 to 10 carbon atoms, a straight chain, branched chain or cyclic alkyloxyalkyl group having 2 to 10 carbon atoms, a straight chain, branched chain or cyclic alkyloxyalkoxy group having 2 to 10 carbon atoms, a straight chain, branched chain or cyclic alkylamino group having 1 to 10 carbon atoms, an aromatic group having 5 to 14 carbon atoms, an aromatic group having 5 to 14 carbon atoms and having a substituent which is an alkyl group having 1 to 5 carbon atoms, or a halogen atom; and * signifies that the carbon atom adjacent thereto is optically active; and
(C) at least one compound selected from the group consisting of:
(i) compounds represented by the following general formula (2):
wherein R
5
, R
6
and R
7
independently represent a straight chain, branched chain or cyclic alkyl group having 1 to 10 carbon atoms, an aromatic group having 5 to 14 carbon atoms, an aromatic group having 5 to 14 carbon atoms and having a substituent which is an alkyl group with 1 to 5 carbon atoms, or a group represented by the following formula:
wherein R
8
and R
9
independently represent a straight chain, branched chain or cyclic alkyl group having 1 to 10 carbon atoms, an aromatic group having 5 to 14 carbon atoms, a straight chain, branched chain or cyclic alkyl group having 1 to 5 carbon atoms and having a substituent which is an aromatic group with 5 to 14 carbon atoms, or an aromatic group having a substituent which is an aromatic group with 5 to 14 carbon atoms, and R
8
and R
9
may be combined together to form an alkylene group having 2 to 6 carbon atoms; and
(ii) compounds represented by the following general formula (3):
wherein A represents a carbon or nitrogen atom; and, when A is a carbon atom, R
10
and R
11
independently represent an amino group having two substituents each of which is a straight chain, branched chain or cyclic alkyl group having 1 to 10 carbon atoms, wherein R
10
and R
11
may be combined together with A to form a nitrogen-containing ring, or R
10
and R
11
independently represent an amino group having two substituents each of which is an aromatic group having 5 to 14 carbon atoms, and the bond between A and O is a double bond; and, when A is a nitrogen atom, R
10 and R
11
are combined together with A to form a nitrogen-containing aromatic ring, and the bond between A and O is a single bond.
In accordance with the present invention, there is further provided a catalyst solution for organic asymmetric synthesis comprising the above-mentioned catalyst composition and an ether solvent.
In accordance with the present invention, there is further provided a process for preparing an optically active epoxide represented by the following general formula (5):
wherein R
12
and R
13
independently represent a straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, an aromatic group having 5 to 14 carbon atoms, an aromatic group having 5 to 14 carbon atoms and having one to five substituents which are an alkyl group having 1 to 5 carbon atoms, an aromatic group having 5 to 14 carbon atoms and having one to five substituents which are an alkoxy group having 1 to 5 carbon atoms, an aromatic group having 5 to 14 carbon atoms and having one to five substituents which are a halogen atom, a straight chain, branched chain or cyclic alkly group having 1 to 6 carbon atoms and having a substituent which is an aromatic group having 5 to 14 carbon atoms, or a straight chain, branched chain or cyclic alkyl group having 1 to 5 carbon atoms and having a substituent which is a halogenated aromatic group having 5 to 14 carbon atoms, and * signifies that the carbon atom adjacent thereto is optically active,
which comprises comprising allowing an enone represented by the following general formula (4) to react with an oxidizing agent in the presence of the above-mentioned catalyst composition or the above-mentioned catalyst solution,
wherein R
12
and R
13
are as defined above for the formula (5).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The catalyst composition of the present invention comprises (A) a lanthanoid element ion, (B) a binaphthol of the above formula (1), and (C) at least one compound selected from compounds of the above general formula (2) and compounds of the above general formula (3). The catalyst composition broadly includes various types of compositions, which include compositions, the ingredients of which are bound together not only through an ionic bonding-coordinate bond, but also through a covalent bonding-coordinate bond. To make the following explanation short and clear, the respective ingredients will be explained on an ionic form.
The lanthanoid element ion (A) used is not particularly limited, and usually includes ions of elements selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutecium.
The lanthanoid element ions can be obtained from, for example, their alkoxides prepared from the corresponding aliphatic alcohols, such as methoxide, ethoxide, n-propoxide, isopropoxide and n-propoxide; their sulfonates such as trifluoromethane sulfonate and pentafluoroethane sulfonate; and their halides such as chloride, bromide and iodide.
The binaphthol of the formula (1), i.e., ingredient (B) in the catalyst composition of the invention, is not particularly limited. As specific examples of the binaphthol, there can be mentioned (R) compounds such as (R)-binaphthol, (R)-3,3′-dimethoxyblnaphthol, (R)-3,3′-methoxyethoxybinaphthol, (R)-6,6′-diphenylbnaphthol, (R)-6,6′-dibromobinaphthol, (R)-6,6′-dinaphthylbinaphthol and (R)-6,6′-dimethoxybinaphthol; and (S) compou
Daikai Kazuhiro
Hanamoto Takeshi
Inanaga Junji
Kamaura Masahiro
McKane Joseph K.
Nixon & Vanderhye
Solola Taofiq A.
Techno Polymer Co., Ltd.
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