Novel ruthenium complexes, method of their synthesis, intermediate compounds used in this method, method of their synthesis and use of novel ruthenium complexes in olefin metathesis reactions

A ruthenium complex of formula 1-Ru

• wherein:
• X1 and X2 independently of each other denote an anionic ligand selected from the group comprising a halogen anion, a —CN, —SCN, —ORa, —SRa, —O(C═O)Ra, —O(SO2)Ra and —OSi(Ra)3 group, wherein Ra denotes C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl or C5-C20 aryl, which is optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxyl, C5-C24 aryloxyl, C5-C20 heteroaryloxyl or a halogen atom;
• R1, R2, R3, R4 and R5 denote independently a hydrogen atom, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C5-C20 aryl group or a C5-C20 heteroaryl group, a C5-C25 aralkyl group, which may be independently substituted with one and/or more substituents selected from the group comprising a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 perfluoroalkyl group, a C5-C20 aryl group, a C5-C20 perfluoroaryl group, a C5-C20 heteroaryl group, a C1-C12 alkoxyl group, a C5-C24 aryloxyl group, a C5-C20 heteroaryloxyl group, a sulfide group (—SR″), an amino group (—NR″2), in which the R″ group independently denotes a hydrogen atom, C1-C5 alkyl, C6-C24 aryl, C7-C24 aralkyl,
• alternatively R1, R2, R3, R4 and R5 are bonded with each other to form a C5-C25 ring;
• each substituent R6, R7, and R8 denotes a hydrogen atom, a halogen atom, a C1-C12 alkyl group, or a C5-C20 aryl group, which may be substituted independently with one and/or more substitutes selected from the group comprising a hydrogen atom, a C1-C12 alkyl group, a C1-C12 perfluoroalkyl group, a C5-C20 aryl group, a C5-C20 perfluoroaryl group, a C5-C20 heteroaryl group, C1-C12 alkoxyl group, a C5-C24 aryloxyl group, a C5-C20 heteroaryloxyl group or halogen atom, a sulfide group (—SR″), an amino group (—NR″2), in which the group R″ independently denotes a hydrogen atom, C1-C5 alkyl, C6-C24 aryl, C7-C24 aralkyl;
• R9 substituent denotes a substituted or unsubstituted heterocyclic group and/or organometallic complex group selected from thiophene, benzothiophene, furan, benzofuran or ferrocene, which may be substituted independently with one and/or more substituents selected from the group comprising a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 perfluoroalkyl group, a C5-C20 aryl group, a C5-C20 perfluoroaryl group, a C5-C20 heteroaryl group, a C1-C12 alkoxyl group, a C5-C24 aryloxyl group, a C5-C20 heteroaryloxyl group, a sulfide group (—SR″), an amino group (—NR″2), in which the R″ group denotes independently a hydrogen atom, C1-C5 alkyl, C6-C24 aryl, C7-C24 aralkyl,
• R16 and R17 denote independently a hydrogen atom, a halogen atom, C1-C25 alkyl, C3-C25 cycloalkyl, C1-C12 perfluoroalkyl, C2-C25 alkene, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C1-C25 alkoxyl, C5-C25 aryl, C5-C25 aryloxyl, C6-C25 arylalkyl, C5-C25 heteroaryl, C5-C25 heteroaryloxyl, C5-C25 perfluoroaryl, a 3-12-membered heterocycle comprising a sulfur, oxygen, nitrogen, selenium or a phosphorus atom;
• whereby the substituents R16 and R17 may be linked together to form a ring selected from the group comprising C3-C25 cycloalkyl, C3-C25 cycloalkenyl, C3-C25 cycloalkynyl, C5-C25 aryl, C5-C25 heteroaryl, C5-C25 perfluoroaryl, a 3-12-membered heterocycle comprising a sulfur, oxygen, nitrogen, selenium or a phosphorus atom, which may be substituted independently by one or more substituents selected from the group comprising a hydrogen atom, a halogen atom, C1-C25 alkyl, C3-C25 cycloalkyl, C7-C12 perfluoroalkyl, C2-C25 alkene, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C1-C25 alkoxyl, C5-C25 aryl, C5-C25 aryloxyl, C6-C25 arylalkyl, C5-C25 heteroaryl, C5-C25 heteroaryloxyl, C5-C25 perfluoroaryl, a 3-12-membered heterocycle;
• G is selected from such as
• ligand with the formula CAAC-1
• in which X and the substituents R1 to R9 have the above defined meanings
• either
• heteroatom 1
• selected from the group comprising an oxygen atom, a sulfur atom, a selenium atom, substituted by a group selected from such as a hydrogen atom, a fluorine atom, an oxygen atom, C1-C25 alkyl, C1-C25 perfluoroalkyl, C3-C25 cycloalkyl, C5-C20 alkoxyl, C5-C20 aryl, C5-C20 perfluoroaryl, C7-C20 aralkyl, C5-C24 aryloxyl, C2-C12 alkenyl, C6-C20 heteroaryl or C5-C24 heteroaryloxyl, a 3-12-membered heterocycle, optionally substituted with an acyl group (—COR′), a cyano group (—CN), a carboxyl group (—COOH), an ester group (—COOR′), an ester group (—CH2COOR′), an ester group (—CHR′COOR′), an ester group (—C(R′)2COOR′), an amide group (—CONR′2), a Weinreb-type amide (—CON(R′)(OR′)), a sulfone group (—SO2R′), a formyl group (—CHO), a sulfonamide group (—SO2NR′2), a ketone group (—COR′), a thioamide group (—CSNR′2), a thioketone (—CSR′), a thionoester group (—CSOR′), a thioester group (—COSR′), a dithioester group (—CS2R′), in which the group R′ denotes independently C1-C25 alkyl, C1-C25 perfluoroalkyl, C3-C25 cycloalkyl, C5-C20 alkoxyl, C5-C20 aryl, C5-C20 perfluoroaryl, C7-C20 aralkyl, C5-C24 aryloxyl, C2-C12 alkenyl, C6-C20 heteroaryl, C5-C24 heteroaryloxyl and then the dashed line denotes a direct bond between a heteroatom and the substituent R17 or denotes a bond between the substituent R17 and a heteroatom via a methylene bridge —CH2—, —CHR′—, or —CR′2— wherein the substituent R14 is C5-C15 aryl, optionally substituted with 1-4 substituents, independently selected from a group comprising a hydrogen atom, a halogen atom, C1-C25 alkyl, C3-C25 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C1-C25 perfluoroalkyl, C5-C20 alkoxyl, C5-C20 aryl, C5-C20 perfluoroaryl, C7-C20 aralkyl, C5-C24 aryloxyl, C6-C20 heteroaryl or C5-C24 heteroaryloxyl, a 3-12-membered heterocycle, an alkoxyl group (—OR″), a sulfide group (—SR″), a sulfoxide group (—S(O)R″), a sulfonium group (—S+R″2), a sulfone group (—SO2R″), a sulfonamide group (—SO2NR″2), an amino group (—NR″2), an ammonium group (—N+R″3), a nitro group (—NO2), a cyano group (—CN), a phosphinous group (—P(O)(OR″)2), a phosphinic group (—P(O)R″(OR″)), a phosphonine group (—P(OR″)2), a phosphine group (—PR″2), a phosphine oxide group (—P(O)R″2), a phosphonium group (—P+R″3), a carboxyl group (—COOH), an ester group (—COOR″), an amide group (—CONR″2), an amide group (—NR″C(O)R″), a formyl group (—CHO), a ketone group (—COR″), a thioamide group (—CSNR″2), a thioketone group (—CSR″), a thionoester group (—CSOR″), a thioester group (—COSR″), a dithioester group (—CS2R″), in which the R″ group denotes C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C24 aryl, C7-C24 aralkyl, C5-C24 perfluoroaryl, or
• heteroatom 2
• selected from a group comprising a nitrogen atom or a phosphorus atom, substituted with the group selected from such as a hydrogen atom, methylidene, optionally substituted with the substituent R′, C1-C25 alkyl, C1-C25 perfluoroalkyl, C3-C25 cycloalkyl, C5-C20 alkoxyl, C5-C20 aryl, C5-C20 perfluoroaryl, C7-C20 aralkyl, C5-C24 aryloxyl, C2-C12 alkenyl, C6-C20 heteroaryl or C5-C24 heteroaryloxyl, a 3-12-membered heterocycle, an acyl group (—COR′), an ester group (—COOR′), a tert-butyl butyloxycarbonyl group (t-Boc) or a 9-fluorenylmethoxycarbonyla group (Fmoc), a carbamine group (—CONR′2), a sulfone group (—SO2R′), a formyl group (—CHO), in which the R′ group denotes C1-C25 alkyl, C1-C25 perfluoroalkyl, C3-C25 cycloalkyl, C5-C20 alkoxyl, C5-C20 aryl, C5-C20 perfluoroaryl, C7-C20 aralkyl, C5-C24 aryloxyl, C2-C12 alkenyl, C6-C20 heteroaryl or C5-C24 heteroaryloxyl, optionally substituted with an acyl group (—COR′), a cyano group (—CN), a carboxyl group (—COOH), an ester group (—COOR′), an ester group (—CH2COOR′), an ester group (—CHR′COOR′), an ester group (—C(R′)2COOR′), an amide group (—CONR′2), a sulfone group (—SO2R′), a formyl group (—CHO), a sulfonamide group (—SO2NR′2), a ketone group (—COR′), a thioamide group (—CSNR′2), a thioketone group (—CSR′), a thionoester group (—CSOR′), a thioester group (—COSR′), a dithioester group (—CS2R′), in which the R′ group denotes C1-C25 alkyl, C1-C25 perfluoroalkyl, C3-C25 cycloalkyl, C5-C20 alkoxyl, C5-C20 aryl, C5-C20 perfluoroaryl, C7-C20 aralkyl, C5-C24 aryloxyl, C2-C12 alkenyl, C6-C20 heteroaryl or C5-C24 heteroaryloxyl, and then the dashed line denotes a direct bond between the heteroatom and the substituent R14 or it denotes a bond between the substituent R17 with a heteroatom via methylene bridge (CH2)—, —(CHR′)—, or —(CR′2)—;
• wherein the substituent R17 is C5-C15 aryl, optionally substituted with 1-4 substituents independently selected from the group comprising a hydrogen atom, a halogen atom, C1-C25 alkyl, C3-C25 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C1-C25 perfluoroalkyl, C5-C20 alkoxyl, C5-C20 aryl, C5-C20 perfluoroaryl, C7-C20 aralkyl, C5-C24 aryloxyl, C6-C20 heteroaryl or C5-C24 heteroaryloxyl, a 3-12-membered heterocycle, an alkoxyl group (—OR″), a sulfide group (—SR″), a sulfoxide group (—S(O)R″), a sulfonium group (—S+R″2), a sulfone group (—SO2R″), a sulfonamide group (—SO2NR″2), an amino group (—NR″2), an ammonium group (—N+R″3), a nitro group (—NO2), a cyano group (—CN), a phosphinous group (—P(O)(OR″)2), a phosphinic group (—P(O)R″(OR″)), a phosphonine group (—P(OR″)2), a phosphine group (—PR″2), a phosphine oxide group (—P(O)R″2), a phosphonium group (—P+R″3), a carboxyl group (—COOH), an ester group (—COOR″), an amide group (—CONR″2), an amide group (—NR″C(O)R″), a formyl group (—CHO), a ketone group (—COR″), a thioamide group (—CSNR″2), a thioketone group (—CSR″), a thionoester group (—CSOR″), a thioester group (—COSR″), a dithioester group (—CS2R″), in which the group R″ denotes C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C24 aryl, C7-C24 aralkyl, C5-C24 perfluoroaryl, or
• heteroatom 3
• selected from a group comprising a halogen atom and then the dashed line denotes a direct bond between the heteroatom and the R17 substituent, wherein the R17 substituent is C5-C15 aryl, or C5-C25 polyaryl, optionally substituted with 1-4 substituents selected independently from a group comprising a hydrogen atom, a halogen atom, C1-C25 alkyl, C3-C25 cycloalkyl, C2-C25 alkenyl, C3-C25 cycloalkenyl, C2-C25 alkynyl, C3-C25 cycloalkynyl, C1-C25 perfluoroalkyl, C5-C20 alkoxyl, C5-C20 aryl, C5-C20 perfluoroaryl, C7-C20 aralkyl, C5-C24 aryloxyl, C6-C20 heteroaryl or C5-C24 heteroaryloxyl, a 3-12-membered heterocycle, an alkoxy group (—OR″), a sulfide group (—SR″), a sulfoxide group (—S(O)R″), a sulfonium group (—S+R″2), a sulfone group (—SO2R″), a sulfonamide group (—SO2NR″2), an amino group (—NR″2), an ammonium group (—N+R″3), a nitro group (—NO2), a cyano group (—CN), a phosphonous group (—P(O)(OR″)2), a phosphinous group (—P(O)R″(OR″)), a phosphonine group (—P(OR″)2), a phosphine group (—PR″2), a phosphine oxide group (—P(O)R″2), a phosphonium group (—P+R″3), a carboxyl group (—COOH), an ester group (—COOR″), an amide group (—CONR″2), an amide group (—NR″C(O)R″), a formyl group (—CHO), a ketone group (—COR″), a thioamide group (—CSNR″2), a thioketone group (—CSR″), a thionoester group (—CSOR″), a thioester group (—COSR″), a dithioester group (—CS2R″), in which the R″ group denotes C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C24 aryl, C7-C24 aralkyl, C5-C24 perfluoroaryl.