Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2000-09-19
2003-02-18
Shaver, Paul F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S419000, C556S479000, C556S405000, C556S001000, C556S051000, C556S045000, C556S136000, C556S137000, C562S106000, C562S106000, C562S106000, C562S106000, C562S106000, C540S132000, C540S542000, C540S544000, C540S547000, C540S548000, C549S349000, C549S232000, C549S012000, C549S016000, C549S017000
Reexamination Certificate
active
06521769
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel chiral biaryl phosphines and chelating phosphines with tunable bite angles for applications in asymmetric catalysis. More particularly, the present invention relates to transition metal complexes of these ligands, which are useful as catalysts in asymmetric reactions.
2. Description of the Prior Art
Discovery of new chiral ligands is crucial in developing highly enantioselective transition metal-catalyzed reactions. Despite the large number of chiral ligands that have been made for applications in asymmetric catalysis, only few chiral ligands or synthetic routes or motifs have been commonly used in the synthesis of chiral molecules by the chemical industry or academic laboratories.
Among these ligands, BINAP is one of frequently used chiral ligands. The axially dissymmetric, fully aromatic BINAP have demonstrated to be highly effective for many asymmetric reactions (Noyori, R; Takaya, H.
Acc. Chem. Res
. 1990, 23, 345; Olkuma, T.; Koizumi, M.; Doucet, H.; Pham, T.; Kozawa, M.; Murata, K.; Katayama, E.; Yokozawa, T.; Ikariya, T.; Noyori, R
J. Am. Chem. Soc
. 1998, 120, 13529). Related axially dissymmetric ligands such as MeO-BIPHEP and BIPHEMP were made and used for a number of asymmetric reactions (Schmid, R. et al.
Pure & Appl. Chem
. 1996, 68, 131; Foricher, J.: Heiser, B.; Schmid, R. U.S. Pat. No. 5,302,738; Michel, L.; European Patent Application 0667350A1; Broger, E. A.; Foricher, J.; Heiser, B.; Schmid, R. PCT WO 92/16536). Several chiral biaryl phosphines known in the literature are depicted below.
Despite the extensive research in this area, there are still a variety of reactions in which only modest enantioselectivity has been achieved with these ligands. Specially, the free rotation in certain degrees makes BINAP as a conformationally flexible ligand. Recent results suggest that partially hydrogenated BINAP with a bigger bite angle, i.e., H8-BINAP, may be a better ligand in certain asymmetric reactions.
For example, restricting conformational flexibility can enhance enantioselectivity (Uemura, T.; Zhang, X.; Matsumura, K.; Sayo, N.; Kumobayashi, H.; Ohta, T.; Nozaii, K.; Takaya, H.
J. Org Chem
. 1996, 61, 5510). For most chiral axially dissymmetric phosphine ligands, there is a low energy bite angle dictated by the metal species and a large degree of free rotation. The bite angle of chelating chiral phosphines is difficult to fine-tune. Change of ligand electronic properties can also contribute to the activity as well as to the enantioselectivity of a reaction. Because different substrates require different size of chiral pockets, it is important to have a tunable chiral ligand system to achieve high enantioselectivity.
The present invention includes tunable chiral biaryl phosphine ligands with a variety of bite angles by lining two aryl groups with a variety of bridges. Several new chiral biaryl phosphines are disclosed. To achieve heterogenous and supported catalysts, a number of approaches to ligand systems have been developed. These include linking these ligands to a polymer chain, organic or inorganic supports such as dendrimers, silica gel and molecular sieves. Water-soluble groups can be easily introduced into the ligands and fluorocarbon chains can be introduced to promote phase separation.
Catalysts derived from the ligands of the present invention are employed in a variety of asymmetric reactions such as hydrogenation, hydride transfer reaction, hydrosilylation, hydroboration, hydrovinylation, hydroformylation, hydrocarboxylation, isomerization, allylic alkylation, cyclopropanation, Diels-Alder reaction, Aldol reaction, Heck reaction and Michael addition to prepare asymmetric compounds having high enantiomeric purity.
SUMMARY OF THE INVENTION
The present invention includes a ligand selected from the group consisting of compounds represented by A through Z, AA, BB and CC:
wherein “bridge 1” is selected from the group consisting of: C═O, C═S, SO
2
, PO(OR
1
), PO(NHR
1
), PO(NR
1
R
2
), divalent phenyl, substituted divalent phenyl, 2,2′-divalent-1,1′-biphenyl, substituted 2,2′-divalent-1,1′-biphenyl, 2,2′-divalent-1,1′-binaphthyl, substituted 2,2′-divatent-1,1′-binaphthyl, 1,1′-ferrocene, substituted 1,1′-ferrocene, SiR
1
2
(CH
2
)
n
where n is an integer ranging from 1 to 8, and (CR
2
2
)
n
X
1
(CR
2
2
)
m
wherein each n, m is independently an integer from 1 to 8, wherein X
1
is selected from the group consisting of O, S, NR
3
, PR
3
2
,
+
NR
3
2
,
+
PR
3
2
, divalent aryl, divalent fused aryl, divalent 5-membered ring heterocyclic group and divalent fused heterocyclic group;
wherein “bridge 2” is selected from the group consisting of: NH, O, a single bond, (CH
2
)
n
, O(CH
2
)
n
O, NH(CH
2
)
n
NKn wherein each n is independently an integer from 1 to 8, divalent phenyl, substituted divalent phenyl, divalent phenyl amine, substituted divalent phenyl amine, 2,2′-divalent-1,1′-biphenyl, substituted 2,2′-divalent-1,1′-biphenyl, 2,2′-divalent-1,1′-binaphthyl, substituted 2,2′-divalent-1,1′-binaphthyl, 1,1′-ferrocene, substituted 1,1′-ferrocene, O(CR
2
2
)
n
X
1
(CR
2
2
)
m
O, NH(CR
2
2
)
n
X
1
(CR
2
2
)
m
NH and (CR
2
2
)
n
X
1
(CR
2
2
)
m
wherein each n, m is independently an integer from 1 to 8, wherein X
1
is selected from the group consisting of: O, S, NR
3
, PR
3
2
,
+
NR
3
2
,
+
PR
3
2
, divalent aryl, divalent fused aryl, divalent 5-membered ring heterocyclic group and divalent fused heterocyclic group;
wherein “bridge 3” is selected from the group consisting of: SO
2
, CO, COCO, OC(CH
2
)
n
CO, (CH
2
)
n
wherein n is an integer ranging from 1 to 8, COArCO, wherein Ar is selected from the group consisting of: divalent phenyl, substituted divalent phenyl, 2,2′-divalent-1,1′-biphenyl, substituted 2,2′-divalent-1,1′-biphenyl, 2,2′-divalent-1,1′-binaphthyl, substituted 2,2′-divalent-1,1′-binaphthyl, 1,1′-ferrocene, substituted 1,1′-ferrocene and CO(CR
2
2
)
n
X
1
(CR
2
2
)
m
CO wherein each n, m is independently an integer from 1 to 8, wherein X
1
is selected from the group consisting of: O, S, NR
3
, PR
3
2
,
+
NR
3
2
,
+
PR
3
2
, divalent aryl, divalent fused aryl, divalent 5-membered ring heterocyclic group and divalent fused heterocyclic group;
wherein each R
1
is independently selected from the group consisting of: aryl, alkyl, alkaryl, araly and substituted derivatives thereof wherein the substituent in said substituted derivatives is selected from the group consisting of: carboxylic acid, alkoxy, hydroxy, alkylthio, thiol and dialkylamino;
wherein each R
2
and R
3
is independently selected from the group consisting of: aryl, alkyl, substituted aryl and substituted alkyl group;
wherein each said substituted divalent phenyl, divalent phenyl amine, biphenyl, binaphthyl and ferrocene derivative comprises at least one substituent selected from the group consisting of aryl, substituted aryl, alkyl, heteroatom, F, Cl, Br, I, COOR
1
, SO
3
R
1
, PO
3
R
1
2
, OR
1
, SR
1
, PR
1
2
, AsR
1
2
, SbR
1
2
, OAr, nitro, amino, vinyl, substituted vinyl and sulfonic acid;
wherein each R and R′ is independently selected from the group consisting of: aryl, alkyl, alkaryl, arallkyl and substituted derivatives thereof, wherein the substituent in said substituted derivatives is selected from the group consisting of: carboxylic acid, alkoxy, hydroxy, alkylthio, thiol, dialkyl amino groups;
wherein each X and X′ is independently selected from the group consisting of aryl, alkyl, alkaryl, aralkyl, alkoxy, alkoxy, hydroxy, alkylthio, thiol, primary amine, secondary amine and ArNH;
wherein each Z and Z′ is independently selected from the group consisting of: halogen, alkyl, aryl, aryloxy, nitro, amino, vinyl, substituted vinyl and sulfonic acid; and
wherein each Q, Q′, Y, Y′, T and T′ is independently selected from
Ohlandt Greeley Ruggiero & Perle L.L.P.
Shaver Paul F.
The Penn State Research Foundation
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