Ruthenium complexes, methods of their preparation and application thereof in olefin cross metathesis

A method for preparing the compound of general formula 4,

• wherein
• R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17 independently of each other denote an entity selected from the group comprising hydrogen atom, alkyl group C1-C6, cycloalkyl group C3-C7, alkoxy group C1-C6, aryl group C6-C20, heteroaryl group C4-C20, and halogen atom;
• wherein the entity is optionally substituted with one or more moieties selected from the group comprising alkyl group C1-C6, cycloalkyl group C3-C7, aryl group C6-C20, heteroaryl group C4-C20, alkoxy group C1-C6, aryloxy group C6-C24, heteroaryloxy group C4-C24, and halogen atom,
• R18 denotes hydrogen atom,
• R19 denotes an entity selected from the group comprising aryl group C6-C20, heteroaryl group C4-C20, aralkyl group C7-C24, and alkenyl group C2-C6, wherein the entity is optionally substituted with one or more moieties selected from the group comprising alkyl group C1-C6, aryl group C6-C20, heteroaryl group C4-C20, aryloxy group C6-C24, heteroaryloxy group C4-C24, halogen atom, —OR′, —CH2R′, —CH2NR′R″, —SR′, —S(O)R′, —SO2R′, —SO2NH2, —SO2NHR′, —SO2NR′R″, —NR′R″, —NO2, —CN, —COOH, —COOR′, —CONR′R″, —NR′C(O)R″, —NHC(O)R′, —NR′C(O)OR″, —NHC(O)OR″, —CHO, and —COR′, in which R′ and R″ independently are selected from the group comprising alkyl C1-C6, cycloalkyl C3-C7, aryl C6-C24, heteroaryl C4-C20, and aralkyl C7-C24, in which R′ and R″ are optionally substituted with one or more moieties selected from the group comprising alkyl C1-C12, alkoxy C1-C12, aryloxy C6-C24, heteroaryloxy C4-C24, ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently are selected from the group comprising alkyl C1-C12, cycloalkyl C3-C12, aryl C6-C20, and heteroaryl C4-C20, wherein R′ and R″ or R′″ and R″″ are optionally linked to each other,
• or R18 and R19 are optionally linked to each other thereby forming an aromatic polycyclic system, which may be substituted with one or more substituents selected from group comprising alkyl group C1-C25, cycloalkyl group C3-C7, aryl group C6-C24, heteroaryl group C4-C20, alkenyl group C2-C25, cycloalkenyl group C3-C25, alkoxy group C1-C25, aryloxy group C6-C24, and heteroaryloxy group C4-C24,
• L denotes a neutral ligand, connected with the ruthenium atom via a coordination bond from the heteroatom that forms a part of a compound selected from the group comprising —NR′3, —PR′3, —OR′2, —SR′2, —S(O)R′2, halogen atom, and optionally substituted pyridine (C5H4NR′), in which R′ independently is selected from the group comprising hydrogen atom, alkyl C1-C12, cycloalkyl C3-C12, aryl C6-C20, heteroaryl C4-C20, alkoxy C1-C12, aryloxy C6-C24, heteroaryloxy C4-C24, and halogen atom, wherein R′ can be optionally substituted with one or more moieties selected from the group comprising alkyl group C1-C6, cycloalkyl group C3-C12, aryl group C6-C20, heteroaryl group C4-C20, alkoxy group C1-C6, aryloxy group C6-C24, heteroaryloxy group C4-C24, aralkyl group C7-C24, halogen atom, ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), in which R′″ and R″″ independently denote alkyl C1-C12, cycloalkyl C3-C12, aryl C6-C20, heteroaryl C4-C20, wherein R′ and R″ or R′″ and R″″ are optionally linked to each other,
• X denotes halogen atom, and
• n is 1 or 2,
• wherein L and R19 are optionally linked to each other,
• comprising:
• (1) reacting a salt of general formula 9
• wherein
• R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17 independently of each other are an entity selected from the group comprising hydrogen atom, alkyl group C1-C6, cycloalkyl C3-C7, alkoxy group C1-C6, aryl group C6-C20, heteroaryl C4-C20, and halogen atom;
• wherein the entity is optionally substituted with at one or more moieties selected from the group comprising alkyl group C1-C6, cycloalkyl group C3-C7, aryl group C6-C20, heteroaryl group C4-C20, alkoxy group C1-C6, aryloxy group C6-C24, heteroaryloxy group C4-C24, and halogen atom,
• A-denotes an anion selected from the group comprising halogen anion, BF4−, PF6−, ClO4−, CF3SO2O−, and HCl2−
• with a base selected from group comprising potassium bis(trimethylsilyl)amide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and lithium diisopropylamide;
• (2) subsequently contacting the reaction product of (1) with a complex of general formula 1
• wherein
• R18 denotes hydrogen atom,
• R19 denotes a compound selected from the group comprising aryl group C6-C20, heteroaryl group C4-C20, aralkyl group C7-C24, and alkenyl group C2-C6 wherein R19 optionally is substituted with one or more moieties selected from the group comprising alkyl group C1-C6, aryl group C6-C20, heteroaryl group C4-C20, aryloxy group C6-C24, heteroaryloxy group C4-C24, halogen atom, —OR′, —CH2R′, —CH2NR′R″, —SR′, —S(O)R′, —SO2R′, —SO2NH2, —SO2NHR′, —SO2NR′R″, —NR′R″, —NO2, —CN, —COOH, —COOR′, —CONR′R″, —NR′C(O)R″, —NHC(O)R′, —NR′C(O)OR″, —NHC(O)OR″, —CHO, and —COR′, wherein R′ and R″ independently are selected from the group comprising alkyl C1-C6, cycloalkyl C3-C7, aryl C6-C24, heteroaryl C4-C20, and aralkyl C7-C24, wherein R′ and R″ are optionally substituted with one or more moieties selected from the group comprising alkyl C1-C12, alkoxy C1-C12, aryloxy C6-C24, heteroaryloxy C4-C24, ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently denote alkyl C1-C12, cycloalkyl C3-C12, aryl C6-C20, heteroaryl C4-C20, wherein R′ and R″ or R′″ and R″″ are optionally linked to each other,
• or R18 and R19 are optionally linked to each other, forming an aromatic polycyclic system, which may be substituted with one or more substituents selected from group comprising alkyl group C1-C25, cycloalkyl group C3-C7, aryl group C6-C24, heteroaryl group C4-C20, alkenyl group C2-C25, cycloalkenyl group C3-C25, alkoxy group C1-C25, aryloxy group C6-C24 and heteroaryloxy group C4-C24,
• L denotes a neutral ligand, connected with the ruthenium atom via coordination bond from the heteroatom that forms a part of a compound selected from the group comprising —NR′3, —PR′3, —OR′2, —SR′2, —S(O)R′2, halogen atom, and optionally substituted pyridine (C5H4NR′), wherein R′ independently is selected from the group comprising hydrogen atom, alkyl C1-C12, cycloalkyl C3-C12, aryl C6-C20, heteroaryl C4-C20, alkoxy C1-C12, aryloxy C6-C24, heteroaryloxy C4-C24, and halogen atom, wherein R′ can be optionally substituted with one or more moieties selected from the group comprising alkyl group C1-C6, cycloalkyl group C3-C12, aryl group C6-C20, heteroaryl group C4-C20, alkoxy group C1-C6, aryloxy group C6-C24, heteroaryloxy group C4-C24, aralkyl group C7-C24, halogen atom, ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), and hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently denote alkyl C1-C12, cycloalkyl C3-C12, aryl C6-C20, heteroaryl C4-C20, wherein R′ and R″ or R′″ and R″″ are optionally linked to each other,
• L′ denotes the neutral ligand P(R′)3, wherein each substituent R′ independently is selected from the group comprising alkyl group C1-C12, cycloalkyl group C3-C12, aryl group C6-C20, heteroaryl group C4-C20, alkoxy group C1-C25, aryloxy group C6-C24, and heteroaryloxy group C4-C24, wherein two substituents R′ may be linked to each other thereby forming a heterocycloalkyl ring comprising a phosphorous atom as a ring atom,
• X denotes halogen atom,
• wherein L and R19 are optionally linked to each other;
• (3) optionally adding a compound of general formula 10
• wherein
• R20, R21, R22, R23, R24 independently are selected from the group comprising hydrogen atom, alkyl group C1-C6, aryl group C6-C20, heteroaryl group C4-C20, alkoxy group C1-C6, aryloxy group C6-C24, heteroaryloxy group C4-C24, halogen atom, —CH2R′, —SR′, —S(O)R′, —SO2R′, —SO2NH2, —SO2NHR′, —SO2NR′R″, —NR′R″, —NO2, —CN, —COOH, —COOR′, —CONR′R″, —NR′C(O)R″, —NHC(O)R′, —NR′C(O)OR″, —NHC(O)OR″, —CHO, and —COR′, wherein R′ and R″ independently denote alkyl C1-C5, aryl C6-C24, wherein R′ and R″ are optionally linked to each other,
• R24 denotes hydrogen atom or alkyl group C1-C6,
• G denotes halogen atom or substituent selected from group —OR′, —SR′, —NR′R″, —CH2NR′R″ wherein R′ and R″ independently denote alkyl group C1-C25, cycloalkyl group C3-C12, alkoxy group C1-C25, aralkyl group C7-C24, aryl group C6-C20, heteroaryl group C4-C20, aryloxy group C6-C24, heteroaryloxy group C4-C24, which are optionally substituted with at least one alkyl C1-C12, alkoxy C1-C12, aryloxy C6-C24, heteroaryloxy C4-C24, halogen atom, ester group (—COOR′″), amide group (—CONR′″R″″), formyl group (—CHO), ketone group (—COR′″), hydroxamic group (—CON(OR′″)(R″″)), wherein R′″ and R″″ independently denote alkyl C1-C12, cycloalkyl C3-C12, aryl C6-C20, heteroaryl C4-C20, wherein R′ and R″ or R′″ and R″″ are optionally linked to each other;
• and
• (4) optionally adding a copper (1) chloride or ArSO2Cl, wherein Ar denotes aryl group C6-C20.