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US 12,168,224 B2Granted
Optically pure enantiomers of ruthenium complexes and uses thereof
AssigneesCentre National De La Recherche Scientifique, Universite D'Aix-Marseille, Universite De Rennes 1, Institut National Des Sciences Appliquees, Ecole Nationale Superieure De Chimie De Rennes, University of California, San Diego
InventorsRodolphe Jazzar, Guy Bertrand, François Vermersch, Nicolas Vanthuyne, Jennifer Morvan, Marc Mauduit
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Abstract
The present invention relates to an optically pure (+) or (−) enantiomer of a ruthenium complex having formula (I) as well as the preparation method of said enantiomer, and uses thereof as catalyst, in particular in asymmetric olefin metathesis.
Claims14
An optically pure (+) or (−) enantiomer of a ruthenium complex having the following formula (I):
- wherein:
- R1 is a (C6-C14)aryl group, a (C1-C6)alkyl group or a (C8-C20)cycloalkyl group, said aryl group being optionally substituted with at least one substituent chosen from the group consisting of:
- halogen, (C6-C10)aryl group, and (C1-C6)alkyl group, said alkyl group being optionally substituted with one or several phenyl group(s);
- or R1 is a —NR′aR′b group, R′a and R′b being independently from each other selected from the group consisting of:
- H, (C1-C6)alkyl, and (C6-C10)aryl;
- R2 is H, a (C6-C10)aryl group or a (C1-C6)alkyl group;
- R3 is a (C1-C6)alkyl group;
- or R2 and R3 may together form, with the carbon atom carrying them, a (C3-C6)cycloalkyl;
- R4 is selected from the following groups:
- (C6-C20)aryl, (C1-C10)alkyl, and (C3-C12)cycloalkyl group, said aryl group being optionally substituted with at least one substituent chosen from the group consisting of:
- (C1-C6)alkyl, optionally substituted with one or several phenyl group(s), (C6-C10)aryl(C1-C6)alkyl, and (C6-C10)aryl, optionally substituted with one or several substituents;
- R5 is selected from the following groups:
- (C6-C20)aryl, (C1-C10)alkyl, (C3-C12)cycloalkyl, heteroaryl, (C6-C10)aryl(C1-C6)alkyl, and heteroaryl(C1-C6)alkyl, said aryl group being optionally substituted with at least one substituent chosen from the group consisting of:
- (C1-C6)alkyl, optionally substituted with one or several phenyl group(s), (C6-C10)aryl(C1-C6)alkyl, and (C6-C10)aryl, optionally substituted with one or several substituents;
- with the proviso that R5 is different from R4;
- A is either a group of formula (1) or a group of formula (2):
- wherein:
- X1 is an halogen atom, a (C1-C6)alkoxy group or a —S—(C6-C10)aryl group;
- X2 is an halogen atom or a (C1-C6)alkoxy group;
- or X1 and X2 may form together with the ruthenium atom carrying them a heterocycloalkyl group fused with a phenyl group, said phenyl group being possibly optionally substituted with at least one halogen atom,
- R6 is H or is selected from the following groups:
- nitro, cyano, (C1-C6)alkyl, cycloalkyl, (C1-C6)alkoxy, cycloalkyloxy, (C6-C10)aryl, heteroaryl, (C6-C10)aryloxy, heteroaryloxy, (C1-C6)alkylcarbonyl, arylcarbonyl, (C1-C6)alkoxycarbonyl, aryloxycarbonyl, carboxyl, amido, (C1-C6)alkylsulfonyl, arylsulfonyl, (C1-C6)alkylsulfinyl, arylsulfinyl, (C1-C6)alkylthio, arylthio, sulfonamide, halogen, —NRaRb, —SO2—NRR′, and —N(Rc)—C(═O)—Rc,
- Ra and Rb being independently selected from H and (C1-C6)alkyl,
- R and R′ being selected from the following groups:
- (C1-C6)alkyl, (C6-C10)aryl, heteroaryl, and halo(C1-C6)alkyl,
- Rc being H or being selected from the following groups:
- (C1-C6)alkyl, (C6-C10)aryl, and heteroaryl,
- Rd being H or selected from the following groups:
- (C1-C6)alkyl, halo(C1-C6)alkyl, cycloalkyl, (C6-C10)aryl, heteroaryl, (C1-C6)alkoxy, cycloalkyloxy, (C6-C10)aryloxy, and heteroaryloxy;
- R7 is a (C1-C6)alkyl group;
- R9 is a (C1-C6)alkyl group;
- and
- R8 is H, a (C6-C10)aryl group or a (C1-C6)alkyl group;
- and
- Y− is a non-coordinating inorganic anion.
32 more elements
A ruthenium complex having the following formula (I′):
- wherein:
- R1 is a —NR′aR′b group, R′a and R′b being independently from each other selected from the group consisting of:
- H, (C1-C6)alkyl, and (C6-C10)aryl;
- R2 is H, a (C6-C10)aryl group or a (C1-C6)alkyl group;
- R3 is a (C1-C6)alkyl group;
- or R2 and R3 may together form, with the carbon atom carrying them, a (C3-C6)cycloalkyl;
- R4 is selected from the following groups:
- (C6-C20)aryl, (C1-C10)alkyl, and (C3-C12)cycloalkyl group, said aryl group being optionally substituted with at least one substituent chosen from the group consisting of:
- (C1-C6)alkyl, optionally substituted with one or several phenyl group(s), (C6-C10)aryl(C1-C6)alkyl, and (C6-C10)aryl, optionally substituted with one or several substituents, in particular selected in from the group consisting of:
- (C1-C6)alkylamino, di(C1-C6)alkylamino, (C1-C6) alcoxy, and (C1-C6)alkyl;
- R5 is selected from the following groups:
- (C6-C20)aryl, (C1-C10)alkyl, (C3-C12)cycloalkyl, heteroaryl, (C6-C10)aryl(C1-C6)alkyl, and heteroaryl(C1-C6)alkyl, said aryl group being optionally substituted with at least one substituent chosen from the group consisting of:
- (C1-C6)alkyl, optionally substituted with one or several phenyl group(s), (C6-C10)aryl(C1-C6)alkyl, and (C6-C10)aryl, optionally substituted with one or several substituents, in particular selected in from the group consisting of:
- (C1-C6)alkylamino, di(C1-C6)alkylamino, (C1-C6) alcoxy, and (C1-C6)alkyl;
- with the proviso that R5 is different from R4;
- A is either a group of formula (1) or a group of formula (2):
- wherein:
- X1 is an halogen atom, a (C1-C6)alkoxy group or a —S—(C6-C10)aryl group;
- X2 is an halogen atom or a (C1-C6)alkoxy group;
- or X1 and X2 may form together with the ruthenium atom carrying them a heterocycloalkyl group fused with a phenyl group, said phenyl group being possibly optionally substituted with at least one halogen atom,
- R6 is H or is selected from the following groups:
- nitro, cyano, (C1-C6)alkyl, cycloalkyl, (C1-C6)alkoxy, cycloalkyloxy, (C6-C10)aryl, heteroaryl, (C6-C10)aryloxy, heteroaryloxy, (C1-C6)alkylcarbonyl, arylcarbonyl, (C1-C6)alkoxycarbonyl, aryloxycarbonyl, carboxyl, amido, (C1-C6)alkylsulfonyl, arylsulfonyl, (C1-C6)alkylsulfinyl, arylsulfinyl, (C1-C6)alkylthio, arylthio, sulfonamide, halogen, —NRaRb, —SO2—NRR′, and —N(Rc)—C(═O)—Rc,
- Ra and Rb being independently selected from H and (C1-C6)alkyl,
- R and R′ being selected from the following groups:
- (C1-C6)alkyl, (C6-C10)aryl, heteroaryl, and halo(C1-C6)alkyl,
- Rc being H or being selected from the following groups:
- (C1-C6)alkyl, (C6-C10)aryl, and heteroaryl,
- Rd being H or selected from the following groups:
- (C1-C6)alkyl, halo(C1-C6)alkyl, cycloalkyl, (C6-C10)aryl, heteroaryl, (C1-C6)alkoxy, cycloalkyloxy, (C6-C10)aryloxy, and heteroaryloxy;
- R7 is a (C1-C6)alkyl group;
- R9 is a (C1-C6)alkyl group;
- and
- R8 is H, a (C6-C10)aryl group or a (C1-C6)alkyl group;
- and
- Y− is a non-coordinating inorganic anion,
- said complex being in the form of a racemic mixture, or in the form of an optically pure (+) or (−) enantiomer.
33 more elements
Dependencies are inferred from the claim text.