US 11,999,754 B2
Ruthenium complexes and their use in olefin metathesis reactions
Rafal Gawin, Warsaw (PL); Patryk Krajczy, Glogowek (PL); Anna Gawin, Warsaw (PL); and Krzysztof Skowerski, Jablonowo Pomorskie (PL)
Assigned to APEIRON SYNTHESIS S.A., Wroclaw (PL)
Appl. No. 17/048,092
Filed by APEIRON SYNTHESIS S.A., Wroclaw (PL)
PCT Filed Apr. 16, 2019, PCT No. PCT/IB2019/053138
§ 371(c)(1), (2) Date Oct. 15, 2020,
PCT Pub. No. WO2019/202509, PCT Pub. Date Oct. 24, 2019.
Claims priority of application No. 425237 (PL), filed on Apr. 16, 2018.
Prior Publication US 2021/0101922 A1, Apr. 8, 2021
Int. Cl. C07F 15/00 (2006.01); B01J 31/18 (2006.01); C07C 6/04 (2006.01)
CPC C07F 15/0046 (2013.01) [B01J 31/1825 (2013.01); C07C 6/04 (2013.01); C07C 2531/22 (2013.01)] 15 Claims
 
1. A ruthenium complex of formula 1

OG Complex Work Unit Chemistry
wherein:
X1, X2 are each independently an anionic ligand selected from such as halogen atom, —OR, —SR, —C(C═O)R, where R is C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, which are optionally substituted with at least one C1-C12 alkyl, optionally C1-C12 perhalogenalkyl, optionally C1-C12 alkoxy, optionally a halogen atom;
R1 is a hydrogen atom or C5-C24 aryl, C1-C25 alkyl, C5-C25 heteroaryl, C7-C24 aralkyl, which are optionally substituted by at least one C1-C12 alkyl, optionally C1-C12 perhalogenalkyl, optionally C1-C12 alkoxy, optionally a halogen atom, wherein the alkyl groups may be interconnected to form a ring;
R2 is C5-C24 aryl, C5-C25 heteroaryl, C7-C24 aralkyl, which are optionally substituted by at least one C1-C12 alkyl, optionally C1-C12 perhalogenalkyl, optionally C1-C12 alkoxy, optionally a halogen atom, wherein the alkyl groups may be interconnected to form a ring;
R3 is C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl, or C5-C20 heteroaryl, which is optionally substituted by at least one C1-C12 alkyl, C1-C12 perhalogenalkyl, C2-C12 alkoxy or a halogen atom;
R4, R5, R6, R7, R8, R9 are each independently a hydrogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl, or C5-C20 heteroaryl, which is optionally substituted by at least one C1-C12 alkyl, C1-C12 perhalogenalkyl, C1-C12 alkoxy or a halogen atom, and the R4 and R5 and/or R8 and R9 groups may optionally be interconnected to form a cyclic system C4-C10; and
a, b, c, d—are each independently a hydrogen atom, a halogen atom, C1-C25 alkyl, C1-C25 perfluoroalkyl, C3-C7 cycloalkyl, C1-C25 alkoxy, C5-C24 aryl, C7-C24 aralkyl, C5-C25 heteroaryl, 3-12-membered heterocycle, wherein the alkyl groups may be interconnected to form a ring; also, each of them can be independently an ether (—OR′), thioether (—SR′), nitro (—NO2), cyano (—CN), amide (—CONR′R″), carboxy and ester (—COOR′), sulfa (—SO2R′), sulfonamide (SO2NR′R″), formyl and ketone (—COR′) group, in which groups R′ and R″ are each C1-C25 alkyl, C1-C25 perfluoroalkyl, C5-C24 aryl, C5-C25 heteroaryl, C5-C24 perfluoroaryl.