US 6,855,657 B2Granted

Ortho substituted chiral phosphines and phosphinites and their use in asymmetric catalytic reactions

AssigneeThe Penn State Research Foundation

InventorXumu Zhang

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Abstract

3,3′-Substituted chiral biaryl phosphine and phosphinite ligands and metal complexes based on such chiral ligands useful in asymmetric catalysis are disclosed. 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.

Claims55

Dependent claims

A catalyst prepared by a process comprising:

contacting a transition metal salt, or a complex thereof, and a ligand selected from the group consisting of compounds 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, NR2, COOR, halide, SiR3, P(O)R2, P(O)(OR)2 and P(OR)2;
wherein each Z and Z1 is independently selected from the group consisting of:
alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR2, COOR, halide, SiR3, P(O)R2, P(O)(OR)2 and P(OR)2;
or wherein Z and Z1 together form the bridging group A-B-A1;
wherein each Z′, Z″, Z1′ and Z1′ is independently selected from the group consisting of:
H, alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR2, COOR, halide, SiR3, P(O)R2, 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;
Z1 and Z1′ together form the bridging group A1-B1-A1′;
and/or Z1 and Z1′ together form a fused cycloaliphatic or aromatic group;
wherein each A, A′, A1 and A1′ is independently selected from the group consisting of:
O, CH2, NH, NR, S, CO and a bond;
wherein each B and B1 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, CH2, NH, NR, S, CO, SO2, P(O)R, P(O)OR, POR, SiR2 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 arylene group;
wherein each Y, Y′ and Y″ is independently selected from the group consisting of:
O, CH2, 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 and wherein each Y is independently selected from the group consisting of:
CH2 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.

27 more elements

A process for preparation of an asymmetric compound comprising:

contacting a substrate capable of forming an asymmetric product by an asymmetric reaction and a catalyst prepared by a process comprising:
contacting a transition metal salt, or a complex thereof, and a ligand selected from the group consisting of compounds 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, NR2, COOR, and halide;
wherein each Z and Z1 is independently selected from the group consisting of:
alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR2, COOR and halide;
or wherein Z and Z1 together form the bridging group A-B-A1;
wherein each Z′, Z″, Z1′ and Z1″ is independently selected from the group consisting of:
H, alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR2, COOR, and halide;
or wherein Z and Z together form the bridging group A′-B-A;
Z′ and Z together form a fused cycloaliphatic or aromatic group;
Z1, and Z1′ together form the bridging group A1-B1-A1′;
and/or Z1 and Z1′ together form a fused cycloaliphatic or aromatic group;
wherein each A, A′, A1 and A1′ is independently selected from the group consisting of:
O, CH2, NH, NR, S, CO and a bond;
wherein each B and B1 is independently selected from the group consisting of:
O, CH2, NH, NR, S, CO, SO2, and a bond;
wherein each T is independently selected from the group consisting of:
alkyl, substituted alkyl, aryl, substituted aryl, alkoxide, aryloxide, R, R′, and R″;
or wherein two T groups together form an alkylene or arylene;
wherein each T′ is independently selected from the group consisting of:
alkyl, substituted alkyl, aryl, substituted aryl, alkoxide, aryloxide, R, R′, and R″;
or wherein two T′ groups together form an alkylene or arylene;
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, arylene or substituted arylene group;
and
wherein each Y, Y′ and Y″ is independently selected from the group consisting of:
CH2 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;
wherein said asymmetric reaction is selected from the group consisting of:
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 wherein m=3 to 6 and n=2.

29 more elements

Dependencies are inferred from the claim text.

Facts

Application: 10/660,350Filed 11 Sep 2003 · division
Priority: 17 Nov 2000
Published: US 2004/0068126 A18 Apr 2004
Granted: 15 Feb 2005
Term ends: Not estimatedThe source records don’t support an estimate.

Classification32 codes

C07F 9/65848
Having one phosphorus atom as ring hetero atom: cyclic amide derivatives of acids of phosphorus, in which two nitrogen atoms belong to the ring
B01J 31/1875
The ligands containing phosphorus: phosphinites
B01J 31/2409
Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring: with more…
B01J 31/2452
And phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring: with more than one complexing phosphine-P atom

Family

Application60/249,537Us provisional application · filed 17 Nov 2000
Application60/301,221Us provisional application · filed 27 Jun 2001
Application09/991,261Parent of this division · filed 16 Nov 2001
US 6,653,485 B2Parent of this division · filed 25 Nov 2003
US 2004/0068126 A1Pre-grant publication · published 8 Apr 2004
US 2002/0128501 A1Published application
US 6,855,657 B2This patent

From the US filing history. Foreign family members aren’t listed.