Molecular weight-enlarged ligands for asymmetric,...

Details Molecular weight-enlarged ligands for asymmetric,... Molecular weight-enlarged ligands for asymmetric,...

2001-01-24

2003-09-09

Dawson, Robert (Department: 1712)

Chemistry of hydrocarbon compounds

Adding hydrogen to unsaturated bond of hydrocarbon, i.e.,...

Using transition metal-containing catalyst

C556S136000, C556S137000, C556S144000, C525S326100, C525S327600, C525S329800, C525S329700, C525S340000, C525S341000, C525S360000, C525S370000, C502S155000, C502S158000, C502S159000, C502S162000, C502S167000, C502S171000, C502S313000

Reexamination Certificate

active

06617480

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to molecular weight-enlarged ligands for catalysts and their use for the asymmetric, homogeneous hydrogenation of double bonds.
2. Discussion of the Background
Catalytically active species for the asymmetric, homogeneous hydrogenation of double bonds are extremely advantageous for the industrial synthesis of organic substances. This is particularly the case due to their improved recyclability, which helps keep manufacturing costs low for synthetically produced products.
Molecular weight-enlarged catalysts for homogeneous enantioselective hydrogenation are known in the literature. J. Am. Chem. Soc. (1998), 120, 9481 et seq. addresses the problem of producing soluble molecular weight enlargements, inter alia, for hydrogenation catalysts. Wandrey et al have also reported the use of a molecular weight-enlarged hydrogenation catalyst in a membrane reactor (Angew. Chem. (1990), 102, 445 et seq.). U.S. Pat. No. 5,777,062 describes homogeneously soluble polymer-enlarged ligands for hydrogenation catalysts. The monomeric ligands are bound in this case to the polymer backbone via urethane or urea linkers.
The catalysts described above have problems, for example, in that it is difficult to separate the catalysts from the product with regard to the membrane used, and the catalysts become inactivated over the course of the reaction. These and other problems associated with the catalysts described above have not been adequately been resolved to date, and thus there is still a requirement for novel catalyst systems which make it possible to perform continuous processes catalytically.
SUMMARY OF THE INVENTION
Accordingly, one object of the present invention is to provide a homogenous soluble hydrogenation catalyst that is readily separable from the product of the hydrogenation.
Another object of the present invention is to provide a molecular weight-enlarged ligand for preparing such a catalyst.
Another object of the present invention is to provide a method for preparing such ligands and catalysts.
Another object of the invention is to provide a method for the asymmetric, homogenous hydrogenation of unsaturated compounds using such catalysts.
These and other objects have been achieved by the present invention, the first embodiment of which provides a molecular weight-enlarged, homogeneously soluble ligand, which includes:
an average molecular weight of at least 1000 g/mol;
a molecular weight-enlarging polymer;
optionally, a polymer linker; and
at least one homochiral active center;
wherein the active center is bound to the molecular weight-enlarging polymer through the polymer linker or is bound directly to the molecular weight-enlarging polymer; and
wherein the active center is selected from the group including compounds having the formulas in the following table, and combinations thereof:
n = 0-5

n = 0-5


R = cyclohexyl or (C
6
-C
18
) aryl R′ = H or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer X = PR
2
or OMe

R = cyclohexyl or (C
6
-C
18
) aryl R′ = CH
3
, OMe, CF
3
, H or tert. Bu

R = H, CF
3
, OMe or CH
3


R = H, (C
1
-C
8
) alkyl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer

R = H, (C
1
-C
8
) alkyl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer

R = cyclohexyl or (C
6
-C
18
) aryl

R = cyclohexyl or (C
6
-C
18
) aryl R′ = (C
1
-C
8
) alkyl, (C
7
-C
19
) aralkyl or (C
6
-C
18
) aryl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer R″ = (C
1
-C
8
) alkyl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer





R = H or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer R′ = (C
1
-C
8
) alkyl, (C
7
-C
19
) aralkyl or (C
6
-C
18
) aryl

R = cyclohexyl or (C
6
-C
18
) aryl R′ = (C
1
-C
8
) alkyl, H or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer R″ = H or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer X = NR′
2
, NR′H, OMe or OAc Y = Pr
2
or H

R = cyclohexyl or (C
6
-C
18
) aryl R′ = (C
1
-C
8
) alkyl, (C
6
-C
18
) aryl or H R″ = polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer n = 0, 1 or 2

R = H, (C
1
-C
8
) alkyl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer


R = cyclohexyl or (C
6
-C
18
) aryl R′ = H, (C
1
-C
8
) alkyl or (C
6
-C
18
) aryl

R = (C
1
-C
8
) alkyl R′ = H, O-(C
1
-C
8
) alkyl, O-(C
7
-C
19
) aralkyl, O-(C
6
C
18
aryl or OH

R = cyclohexyl or (C
6
-C
18
) aryl R′ = H or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer

R = cyclohexyl or (C
6
-C
18
) aryl R′ = H or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer

R = H, (C
1
-C
8
) alkyl, (C
7
-C
19
) aralkyl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer

R = cyclohexyl or (C
6
-C
18
) aryl R′ = H, (C
1
-C
8
) alkyl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer R″= H, (C
1
-C
8
) alkyl, (C
7
-C
19
) aralkyl, (C
6
-C
18
) aryl, polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer

R = cyclohexyl or (C
6
-C
18
) aryl R′ = H, (C
1
-C
8
) alkyl, (C
7
-C
19
) aralkyl, (C
6
-C
18
) aryl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer

R = cyclohexyl or (C
6
-C
18
) aryl X = CH
2
, O, S, PR or NH



R = H or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer

R = H, polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer


(n = 1-6)

R = (C
1
-C
8
) alkyl, (C
7
-C
19
) aralkyl, (C
6
-C
18
) aryl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer

R = cyclohexyl or (C
6
-C
18
) aryl R′ = H, (C
1
-C
8
) alkyl, (C
7
-C
19
) aralkyl, (C
6
-C
18
) aryl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer n = 0-5

n = 0 or 1 R = (C
1
-C
8
) alkyl or H R′ = H, (C
1
-C
8
) alkyl, (C
7
-C
19
) aralkyl, (C
6
-C
18
) aryl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer





R = (C
1
-C
8
) alkyl or (C
6
-C
18
) aryl, n = 0-5

R = (C
1
-C
8
) alkyl, (C
7
-C
19
) aralkyl or (C
6
-C
18
) aryl


R = cyclohexyl, (C
6
-C
18
) aryl R′ = (C
1
-C
8
) alkyl, (C
6
-C
18
) aryl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer R″ = H, (C
1
-C
8
) alkyl, (C
7
-C
19
) aralkyl, (C
6
-C
18
) aryl, polymer linkage through said polymer linker or directly to said molecular weight enlarging
polymer OR′, OAc, NR′
2
or NH
2

R = cyclohexyl or (C
6
-C
18
) aryl R′ = (C
1
-C
8
) alkyl, (C
6
-C
18
) aryl or polymer linkage through said polymer linker or directly to said molecular weight enlarging polymer R″ = H, (C
1
-C
8
) alkyl, (C
6
-C
18
) aryl, OR′, OAc, NR′
2
, NH
2
, polymer linkage through said polymer

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