Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-11-16
2003-11-25
Vollano, Jean F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C568S017000, C568S012000, C568S013000, C548S112000, C546S022000, C544S171000, C556S013000
Reexamination Certificate
active
06653485
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel chiral ligands derived from 3,3′-substituted biaryl phosphines and phosphinites. More particularly, the present invention relates to transition metal complexes of these chiral phosphine ligands. The transition metal complexes are useful as catalysts in asymmetric reactions, such as, hydrogenation, hydride transfer, allylic alkylation, hydrosilylation, hydroboration, hydrovinylation, hydroformylation, olefin metathesis, hydrocarboxylation, isomerization, cyclopropanation, Diels-Alder reaction, Heck reaction, isomerization, Aldol reaction, Michael addition, epoxidation, kinetic resolution and [m+n] cycloaddition.
2. Description of the Prior Art
Discovery of new chiral ligands is crucial in developing highly enantioselective transition metal-catalyzed reactions. Many chiral ligands have been made for applications in asymmetric catalysis, however, relatively few of these chiral ligands are commonly used in industry for the synthesis of chiral molecules.
Several chiral ligands having a biaryl backbone are known in the prior art. These are summarized below:
Among these ligands, BINAP (1) is one of the most frequently used chiral ligands. The axially dissymmetric, fully aromatic BINAP has demonstrated to be highly effective for many asymmetric reactions (Noyori, R. et al.
Acc. Chem. Res.
1990, 23, 345, Ohkuma, T. et al.
J. Am. Chem. Soc.
1998, 120, 13529). Recent results show that partially hydrogenated BINAP with a larger bite angle, H8-BINAP (2), is a better ligand for certain asymmetric reactions due to restriction of conformational flexibility (Zhang X. et al.
Synlett
1994, 501). Chiral BINAPO (3) was made and it was not effective due to the conformational flexibility (Grubbs, R. et al.
Tetrahedron Lett.
1977, 1879). Other axially dissymmetric ligands such as BIPHEMP (4) and MeO-BIPHEP (5) were developed and used for a number of asymmetric reactions (Schmid, R. et al.
Pure
&
Appl. Chem.
1996, 68, 131; Schmide, R. et al.
Helv. Chim. Acta,
1988, 71, 897). However, the present inventor is not aware of any examples of related 3,3′ substituted chiral biaryl phosphines, the subject of the present invention, being disclosed in the prior art (Broger, E. A. et al., WO 92/16536 and Broger, E. A. et al., WO93/15089). NAPHOS (6), another example of a prior art compound has been prepared (Tamao, K. et al.
Tetrahedron Lett.
1977, 1389) and was found to be not effective for asymmetric hydrogenation reaction. The corresponding ligands with the N linker, BDPAB (7) and H8-BDPAB (8) have also been made and tested for asymmetric hydrogenation reactions (Zhang, F. et al.
J. Am. Chem. Soc.
1998, 120, 5808).
SUMMARY OF THE INVENTION
The present invention includes a ligand represented by the formula or its enantiomer:
wherein each X and X′ is independently selected from the group consisting of: alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR
2
, COOR, halide, SiR
3
, P(O)R
2
, P(O)(OR)
2
and P(OR)
2
;
wherein each Z and Z
1
is independently selected from the group consisting of: alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR
2
, COOR, halide, SiR
3
, P(O)R
2
, P(O)(OR)
2
and P(OR)
2
; or wherein Z and Z
1
together form the bridging group A-B-A
1
;
wherein each Z′, Z″, Z
1
′ and Z
1
″ is independently selected from the group consisting of: H, alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR
2
, COOR, halide, SiR
3
, P(O)R
2
, P(O)(OR)
2
and P(OR)
2
, or wherein Z′ and Z together form the bridging group A′-B-A; Z′ and Z together form a fused cycloaliphatic or aromatic group; Z
1
and Z
1
′ together form the bridging group A
1
-B
1
-A
1
′; and/or Z
1
and Z
1
′ together form a fused cycloaliphatic or aromatic group;
wherein each A, A′, A
1
and A
1
′ is independently selected from the group consisting of: O, CH
2
, NH, NR, S, CO and a bond;
wherein each B and B
1
is independently selected from the group consisting of: linear, branched or cyclic alkylene of 1 to 6 carbon atoms, arylene of 6 to 12 carbon atoms, O, CH
2
, NH, NR, S, CO, SO
2
, P(O)R, P(O)OR, POR, SiR
2
and a bond;
wherein each T is independently selected from the group consisting of: alkyl, substituted alkyl, aryl, substituted aryl, alkoxide, aryloxide, R, R′, R″, YR′, YR″, Y′R′ and Y″R″; or wherein two T groups together form an alkylene, arylene, alkylenediamino, arylenediamino, alkelenedioxyl or arylenedioxyl;
wherein each T′ is independently selected from the group consisting of: alkyl, substituted alkyl, aryl, substituted aryl, alkoxide, aryloxide, R, R′, R″, YR′, YR″, Y′R′ and Y″R″; or wherein two T′ groups together form an alkylene, arylene, alkylenediamino, arylenediamino, alkelenedioxyl or arylenedioxyl;
wherein each R, R′ and R″ is independently selected from the group consisting of: alkyl, substituted alkyl, aryl, aralkyl and alkaryl of 1 to 22 carbon atoms; or wherein two R groups, two R′ groups or two R″ group together form an alkylene or arelene group; and
wherein each Y, Y′ and Y″ is independently selected from the group consisting of: O, CH
2
, NH, S and a bond between carbon and phosphorus; with the proviso that when the Y group at the 2′ position is a bond between carbon and phosphorus, X′ is hydrogen.
The present invention further includes a catalyst prepared by a process, which includes: contacting a transition metal salt, or a complex thereof, and a ligand according to the present invention.
The present invention still further includes a process for preparation of an asymmetric compound including: contacting a substrate capable of forming an asymmetric product by an asymmetric reaction and a catalyst prepared by a process including: contacting a transition metal salt, or a complex thereof, and a ligand according to the present invention.
The metal complexes are useful as catalysts in asymmetric reactions, such as, hydrogenation, hydride transfer, allylic alkylation, hydrosilylation, hydroboration, hydrovinylation, hydroformylation, olefin metathesis, hydrocarboxylation, isomerization, cyclopropanation, Diels-Alder reaction, Heck reaction, isomerization, Aldol reaction, Michael addition, epoxidation, kinetic resolution and [m+n] cycloaddition. The metal complexes are particularly effective in Ru-catalyzed asymmetric hydrogenation of beta-ketoesters to beta-hydroxyesters and Ru-catalyzed asymmetric hydrogenation of enamides to beta amino acids.
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patent: 5710339 (1998-01-01), Laue et al.
patent: 5728886 (1998-03-01), Naumann et al.
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patent: 5872273 (1999-02-01), Saito et al.
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patent: WO 92/16536 (1992-10-01), None
patent: WO 93/15089 (1993-08-01), None
CA:134:326631 abs of EP 1095946 May 2001.*
Simonsen et al., “A simple synthetic approach to 3,3′-diaryl BINOLs.”J. Org. Chem. 1998, 63, 7536-7538.
Xiao et al. “Synthesis of a novel chiral binaphthyl phospholane and its application in the highly enantioselective dydrogenation of enamides.”Organic Letters. 1999, vol. 1, No. 10, 1679-1681.
Zhu et al. “Highly efficient asymmetric synthesis of &bgr;-amino acid derivatives via rhodium-catalyzed hydrogenation of &bgr;-(acylamino)acrylates.”J. Org. Chem. 1999, 64, 6907-6910.
Tschaen et al. “Asymmetric synthesis of MK-0499.”J. Org. Chem. 1995, 60, 4324-4330.
Lubell et al. “Enantioselevtive synthesis of &bgr;-amino acids based on BINAP-ruthenium (II) catalyzed hydrogenation.”Tetrahedron Asymmetry. vol. 2, No. 7, 543-554, 1991.
Tamao et al. “Optically active 2,2′-bis(diphenylphosphinomethyl)-1,1'-binaphthyl: A new chiral bidentate phosphine Ligand for transition-metal
Ohlandt, Greeley, Ruggiero & Perle L.L.P
The Penn State Research Foundation
Vollano Jean F.
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