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US 2006/0135804 A1Published application
Tetradentate ligands and metal complexes thereof for asymmetric catalysis
OwnerNeil Boazinventor
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Abstract
This invention relates to novel, substantially enantiomerically pure tetradentate ligands comprised of two phosphines and two secondary amines. These species have been used as ligands for metal catalysts for asymmetric reactions and have demonstrated good enantioselectivity, in particular as ruthenium complexes for asymmetric hydrogenation. Also disclosed are methods for making the ligands, corresponding catalyst complexes, and processes employing the ligands and catalysts. The ligands may be described by the general formula 1: R2P-L1-NH-L2-NH-L3-PR12 1
Claims52
A substantially enantiomerically pure compound having the general formula 1:
- R2P-L1-NH-L2-NH-L3-PR12 1
- wherein R and R1 are, independently, branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or a C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- L1, L2, and L3 may be the same or different, and are divalent radicals selected from branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, a C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen, or metallocenylalkyl and wherein L1, L3 and, optionally, L2 are substantially enantiomerically pure.
A compound having formula 7
- wherein
- R2 is a branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or a C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, or oxygen;
- R3, R4, and R5 are independently hydrogen, branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having one to three heteroatoms wherein the heteroatoms are selected from sulfur, nitrogen, and oxygen;
- L2 is an achiral, racemic, enantiomerically enriched or substantially enantiomerically pure C1-C20 alkylene, C3-C8 cycloalkylene, or 1,1′-biaryl-2,2′-diyl;
- n is 0 to 3;
- m is 0 to 5;
- and
- M is selected from the metals of Groups IVB, VB, VIB, VIIB and VIII.
5 more elements
A compound having formula 11
- wherein
- R2 is a branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or a C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, or oxygen;
- R3, R4, and R5 are independently hydrogen, branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having one to three heteroatoms wherein the heteroatoms are selected from sulfur, nitrogen, and oxygen;
- L2 is an achiral, racemic, enantiomerically enriched or substantially enantiomerically pure C1-C20 alkylene, C3-C8 cycloalkylene, or 1,1′-biaryl-2,2′-diyl;
- n is 0 to 3;
- m is 0 to 5;
- and
- M is selected from the metals of Groups IVB, VB, VIB, VIIB and VIII.
5 more elements
A process for preparing a compound having formula 4
- which comprises the steps of:
- (1) contacting a dialkyl amine having formula 5:
- with a carboxylic anhydride having the formula (R10CO)2O to obtain a first ester having formula 6:
- (2) contacting the ester produced in step (1) with a diamine having the formula H2N-L2-NH2 to obtain a phosphine-diamine 7
- and (3) contacting the phosphine-diamine produced in step (2) with a second ester having formula 6 to afford diphosphine-diamine 4,
- wherein each R2 is independently a branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or a C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, or oxygen;
- each R3, R4, and R5 is independently selected from hydrogen, branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- R8 and R9 are independently branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- each R10 is independently a C1 to C4 alkyl radical;
- L2 is an achiral, racemic, or enantiomerically enriched C1-C20 alkylene, C3-C8 cycloalkylene, or 1,1′-biaryl-2,2′-diyl;
- n is 0 to 3;
- m is 0 to 5;
- and
- M is selected from the metals of Groups IVB, VB, VIB, VIIB and VIII.
11 more elements
A process for preparing a compound having formula 8
- which comprises the steps of:
- (1) contacting a dialkyl amine having formula 9:
- with a carboxylic anhydride having the formula (R10CO)2O to obtain a first ester having formula 10:
- (2) contacting the ester produced in step (1) with a diamine having the formula H2N-L2-NH2 to obtain a phosphine-diamine 11
- and (3) contacting the phosphine-diamine produced in step (2) with a second ester having formula 10 to afford diphosphine-diamine 8,
- wherein each R2 is independently a branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or a C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, or oxygen;
- each R3, R4, and R5 is independently selected from hydrogen, branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- R8 and R9 are independently branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- each R10 is independently a C1 to C4 alkyl radical:
- L2 is an achiral, racemic, or enantiomerically enriched C1-C20 alkylene, C3-C8 cycloalkylene, or 1,1′-biaryl-2,2′-diyl;
- n is 0 to 3;
- m is 0 to 5;
- and
- M is selected from the metals of Groups IVB, VB, VIB, VIIB and VIII.
11 more elements
A process for preparing a compound having formula 4
- which comprises the steps of:
- (1) contacting a dialkyl amine having formula 5:
- with a carboxylic anhydride having the formula (R10CO)2O to obtain an ester having formula 6:
- and (2) contacting the ester produced in step (1) with a diamine having the formula H2N-L2-NH2 to obtain diphosphine-diamine 4,
- wherein R2 is a branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or a C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, or oxygen;
- R3, R4, and R5 are independently selected from hydrogen, branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- R8 and R9 are independently branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- R10 is a C1 to C4 alkyl radical:
- L2 is an achiral, racemic, enantiomerically enriched or substantially enantiomerically pure C1-C20 alkylene, C3-C8 cycloalkylene, or 1,1′-biaryl-2,2′-diyl;
- n is 0 to 3;
- m is 0 to 5;
- and
- M is selected from the metals of Groups IVB, VB, VIB, VIIB and VIII.
10 more elements
A process for preparing a compound having formula 8
- which comprises the steps of:
- (1) contacting a dialkyl amine having formula 9:
- with a carboxylic anhydride having the formula (R10CO)2O to obtain an ester having formula 10:
- and (2) contacting the ester produced in step (1) with a diamine having the formula H2N-L2-NH2 to obtain diphosphine-diamine 8,
- wherein R2 is a branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or a C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, or oxygen;
- R3, R4, and R5 are independently selected from hydrogen, branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- R8 and R9 are independently branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- R10 is a C1 to C4 alkyl radical:
- L2 is an achiral, racemic, enantiomerically enriched or substantially enantiomerically pure C1-C20 alkylene, C3-C8 cycloalkylene, or 1,1′-biaryl-2,2′-diyl;
- n is 0 to 3;
- m is 0 to 5;
- and
- M is selected from the metals of Groups IVB, VB, VIB, VIIB and VIII.
10 more elements
A process which comprises contacting a dialkyl amine having formula 5:
- with a carboxylic anhydride having the formula (R10CO)2O to obtain an ester having formula 6:
- and contacting the ester 6 with a diamine having the formula H2N-L2-NH2 to obtain a phosphine-diamine 7
- wherein R2 is a branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or a C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, or oxygen;
- R3, R4, and R5 are independently selected from hydrogen, branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- R8 and R9 are independently branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- R10 is a C1 to C4 alkyl radical:
- L2 is an achiral, racemic, enantiomerically enriched or substantially enantiomerically pure C1-C20 alkylene, C3-C8 cycloalkylene, or 1,1′-biaryl-2,2′-diyl;
- n is 0 to 3;
- m is 0 to 5;
- and
- M is selected from the metals of Groups IVB, VB, VIB, VIIB and VIII.
8 more elements
A process which comprises contacting a dialkyl amine having formula 9
- with a carboxylic anhydride having the formula (R10CO)2O to obtain an ester having formula 10
- and contacting ester 10 with a diamine having the formula H2N-L2-NH2 to obtain a phosphine-diamine 11
- wherein R2 is a branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or a C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, or oxygen;
- R3, R4, and R5 are independently selected from hydrogen, branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- R8 and R9 are independently branched- or straight-chain C1-C20 alkyl, C3-C8 cycloalkyl, C6-C20 carbocyclic aryl, or C4-C20 heteroaryl having from one to three heteroatoms selected from sulfur, nitrogen, and oxygen;
- R10 is a C1 to C4 alkyl radical:
- L2 is an achiral, racemic, enantiomerically enriched or substantially enantiomerically pure C1-C20 alkylene, C3-C8 cycloalkylene, or 1,1′-biaryl-2,2′-diyl;
- n is 0 to 3;
- m is 0 to 5;
- and
- M is selected from the metals of Groups IVB, VB, VIB, VIIB and VIII.
8 more elements
Dependencies are inferred from the claim text.