Process for producing ruthenium complexes and intermediates thereof and their use in olefin metathesis

A process for producing a compound represented by the Formula 1,

• wherein:
• X1 and X2 are each independently an anionic ligand selected from halogen, —CN, —SCN, —OR′, —SR′, —O(C═O)R′, —O(SO2)R′, and —OSi(R′)3 group, wherein R′ is C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, each of which is optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or halogen;
• Z is selected from the group consisting of O, S, NR′, wherein 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, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or halogen;
• Ar is an aryl group substituted with hydrogen atoms or optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, and C5-C20 heteroaryloxy group, or halogen;
• R1 and R2 are each independently hydrogen, C1-C25 alkyl group, C1-C25 alkoxy group, C2-C25 alkenyl group, C1-C12 perfluoroalkyl, C5-C20 aryl, C5-C24 aryloxy, C5-C20 heteroaryloxy;
• or R1 and R2 are combined together to form substituted or unsubstituted C4-C10 cyclic or C4-C12 polycyclic system;
• or an ester (—COOR′), amide (—CONR′2), formyl (—CHO), ketone (—COR′), and hydroxamic (—CON(OR′)(R′)) group, in which R′ is C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, each of which is optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or halogen;
• R3, R4, R5, R6 are each independently hydrogen, C1-C25 alkyl group, C1-C25 alkoxy group, or C2-C25 alkenyl group;
• or R3, R4, R5, R6 substituents can be combined together to form a substituted or unsubstituted C4-C10 cyclic or C4-C12 polycyclic system;
• or an alkoxy (—OR′), sulfide (—SR′), sulfoxide (—S(O)R′), sulfonium (—S+R′2), sulfone (—SO2R′), sulfonamide (—SO2NR′2), amine (—NR′2), ammonium (—N+R′3), nitro (—NO2), cyano (—CN), phosphonate (—P(O)(OR′)2), phosphinate (—P(O)R′(OR′)), phosphoninum (—P(OR′)2), phosphine (—PR′2), phosphine oxide (—P(O)R′2), phosphonium (—P+R′3), carboxy (—COOH), ester (—COOR′), amide (—CONR′2, or —NR′C(O)R′), formyl (—CHO), or ketone (—COR′) group, wherein R′ is C1-C5 alkyl, C1-C5 perfluoroalkyl, C5-C24 aryl, C7-C24 aralkyl, or C5-C24 perfluoroaryl;
• and
• R7, R8, R9, and R10 are each independently hydrogen atom, or C1-C25 alkyl group;
• or R7 and R8, R7 and R9, R8 and R10, or R9 and R10 are combined to form a cyclic system;
• or independently C1-C12 alkyl group, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, C5-C24 perfluoroaryl, each of which is optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or halogen;
• characterized in that an alkylidene ruthenium complex represented by the Formula 2
• wherein:
• L1 and L2 are each a neutral phosphine ligand P(R′)3, wherein each R′ is independently C1-C12 alkyl, C3-C12 cycloalkyl, C5-C20 aryl, C7-C24 aralkyl, C5-C24 perfluoroaryl, 5-12-membered heteroaryl;
• or wherein two R′ can be combined together to form a cycloalkyl ring containing phosphorus atom in the ring;
• X1 and X2 are each independently an anionic ligand selected from halogen, —CN, —SCN, —OR′, —SR′, —O(C═O)R′, —O(SO2)R′, and —OSi(R′)3 group, wherein R′ is C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, each of which is optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or halogen;
• R11 and R12 are each independently hydrogen, halogen, optionally substituted C1-C25 alkyl, optionally substituted C1-C25 perfluoroalkyl, optionally substituted C2-C25 alkene, optionally substituted C3-C7 cycloalkyl, optionally substituted C2-C25 alkenyl, optionally substituted C3-C25 cycloalkenyl, optionally substituted C2-C25 alkynyl, optionally substituted C3-C25 cycloalkynyl, optionally substituted C1-C25 alkoxy, optionally substituted C5-C24 aryloxy, optionally substituted C5-C20 heteroaryloxy, optionally substituted C5-C24 aryl, optionally substituted C5-C20 heteroaryl, optionally substituted C7-C24 aralkyl, optionally substituted C5-C24 perfluoroaryl, or optionally substituted 3-12-membered heterocycle;
• or
• wherein R11 and R12 substituents are combined together to form a ring selected from the group consisting of C3-C7 cycloalkyl, C3-C25 cycloalkenyl, C3-C25 cycloalkynyl, C5-C24 aryl, C5-C20 heteroaryl, C5-C24 perfluoroaryl, 3-12-membered heterocycle, each of which is optionally substituted independently with one or more substituents selected from the group consisting of hydrogen, halogen, C1-C25 alkyl, C1-C25 perfluoroalkyl, C2-C25 alkene, C3-C7 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C1-C25 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, C5-C24 aryl, C5-C20 heteroaryl, C7-C24 aralkyl, C5-C24 perfluoroaryl, or 3-12-membered heterocycle;
• is reacted with a carbene represented by the Formula 3
• wherein:
• Ar is an aryl group substituted with hydrogen atoms or optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, and C5-C20 heteroaryloxy group, or halogen;
• R7, R8, R9, and R10 are each independently hydrogen atom, or C1-C25 alkyl group;
• or R7 and R8, R7 and R9, R8 and R10, or R9 and R10 are combined to form a cyclic system;
• or independently C1-C12 alkyl group, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, C5-C24 perfluoroaryl, each of which is optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or halogen;
• thus formed reaction mixture is then contacted with a compound represented by the Formula 4
• wherein:
• Z is selected from the group consisting of O, S, NR′, wherein 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, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or halogen;
• R1 and R2 are each independently hydrogen, C1-C25 alkyl group, C1-C25 alkoxy group, C2-C25 alkenyl group, C1-C12 perfluoroalkyl, C5-C20 aryl, C5-C24 aryloxy, C5-C20 heteroaryloxy;
• or R1 and R2 are combined together to form substituted or unsubstituted C4-C10 cyclic or C4-C12 polycyclic system;
• or an ester (—COOR′), amide (—CONR′2), formyl (—CHO), ketone (—COR′), and hydroxamic (—CON(OR′)(R′)) group, in which R′ is C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, each of which is optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or halogen;
• R3, R4, R5, R6 are each independently hydrogen, C1-C25 alkyl group, C1-C25 alkoxy group, or C2-C25 alkenyl group;
• or R3, R4, R5, R6 substituents can be combined together to form a substituted or unsubstituted C4-C10 cyclic or C4-C12 polycyclic system;
• or an alkoxy (—OR′), sulfide (—SR′), sulfoxide (—S(O)R′), sulfonium (—S+R′2), sulfone (—SO2R′), sulfonamide (—SO2NR′2), amine (—NR′2), ammonium (—N+R′3), nitro (—NO2), cyano (—CN), phosphonate (—P(O)(OR′)2), phosphinate (—P(O)R′(OR′)), phosphoninum (—P(OR′)2), phosphine (—PR′2), phosphine oxide (—P(O)R′2), phosphonium (—P+R′3), carboxy (—COOH), ester (—COOR′), amide (—CONR′2, or —NR′C(O)R′), formyl (—CHO), or ketone (—COR′) group, wherein R′ is C1-C5 alkyl, C1-C5 perfluoroalkyl, C5-C24 aryl, C7-C24 aralkyl, or C5-C24 perfluoroaryl;
• and
• R13 is hydrogen, halogen, C1-C25 alkyl group, C1-C25 alkoxy group, C2-C25 alkenyl group, C1-C12 perfluoroalkyl, C5-C20 aryl, C5-C24 aryloxy, C5-C20 heteroaryloxy;
• or are combined together to form a substituted or unsubstituted C4-C10 cyclic or C4-C12 polycyclic system;
• to form the compound represented by the Formula 1.