US 12,168,224 B2
Optically pure enantiomers of ruthenium complexes and uses thereof
Rodolphe Jazzar, La Jolla, CA (US); Guy Bertrand, Solana Beach, CA (US); François Vermersch, San Diego, CA (US); Nicolas Vanthuyne, Marseilles (FR); Jennifer Morvan, Pluméliau (FR); and Marc Mauduit, Vitre (FR)
Assigned to CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, Paris (FR); UNIVERSITÉ D'AIX-MARSEILLE, Marseilles (FR); UNIVERSITE DE RENNES 1, Rennes (FR); INSTITUT NATIONAL DES SCIENCES APPLIQUÉES, Rennes (FR); ECOLE NATIONALE SUPÉRIEURE DE CHIMIE DE RENNES, Rennes (FR); and UNIVERSITY OF CALIFORNIA, SAN DIEGO, La Jolla, CA (US)
Appl. No. 18/004,341
Filed by CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, Paris (FR); UNIVERSITÉ D'AIX-MARSEILLE, Marseilles (FR); UNIVERSITE DE RENNES 1, Rennes (FR); INSTITUT NATIONAL DES SCIENCES APPLIQUÉES, Rennes (FR); ECOLE NATIONALE SUPÉRIEURE DE CHIMIE DE RENNES, Rennes (FR); and UNIVERSITY OF CALIFORNIA, SAN DIEGO, La Jolla, CA (US)
PCT Filed Jul. 8, 2021, PCT No. PCT/EP2021/068995
§ 371(c)(1), (2) Date Jan. 5, 2023,
PCT Pub. No. WO2022/008656, PCT Pub. Date Jan. 13, 2022.
Claims priority of application No. PCT/IB2020/000920 (WO), filed on Jul. 8, 2020.
Prior Publication US 2024/0198321 A1, Jun. 20, 2024
Int. Cl. B01J 31/22 (2006.01); B01J 37/00 (2006.01); C07C 6/04 (2006.01); C07F 15/00 (2006.01)
CPC B01J 31/2291 (2013.01) [B01J 31/2226 (2013.01); B01J 31/226 (2013.01); B01J 31/2273 (2013.01); B01J 37/009 (2013.01); C07C 6/04 (2013.01); C07F 15/0046 (2013.01); B01J 2231/543 (2013.01); B01J 2531/821 (2013.01); C07C 2531/22 (2013.01)] 14 Claims
 
1. An optically pure (+) or (−) enantiomer of a ruthenium complex having the following formula (I):

OG Complex Work Unit Chemistry
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):

OG Complex Work Unit Chemistry
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.