Cross-metathesis of olefins directly substituted with an electron-withdrawing group using transition metal carbene catalysts

A method for synthesizing a substituted acrylonitrile, comprising contacting acrylonitrile with a substituted olefinic reactant in the presence of a catalyst composed of a Group 8 transition metal alkylidene complex under conditions and for a time period effective to allow cross-metathesis to occur, wherein the Group 8 transition metal is ruthenium and the catalyst has the structure of formula (VIII)

• in which:
• X1 and X2 are halo;
• Q is —CR11R12—CR13R14— wherein R11, R12, R13, and R14 are independently selected from hydrogen, C1-C12 alkyl, substituted C1-C12 alkyl, C1-C12 heteroalkyl, substituted C1-C12 heteroalkyl, phenyl, and substituted phenyl;
• and
• one of R1 and R2 is hydrogen, and the other is selected from C2-C6 alkenyl and phenyl;
• R3 and R4 are unsubstituted phenyl or phenyl substituted with up to three substituents selected from C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, C6-C24 aralkyl, C6-C24 alkaryl, or halide;
• n is zero or 1;
• and
• L2 and L3 are selected from pyridine, 3-substituted pyridine, and 4-substituted pyridine, wherein the substituents are halo, lower alkyl, or phenyl.

A method for synthesizing an olefin directly substituted with an electron-withdrawing group and substituted with at least one additional substituent, comprising contacting (a) a first olefinic reactant directly substituted with an electron-withdrawing group with (b) a second olefinic reactant substituted with a different substituent in the presence of (c) a catalyst composed of a Group 8 transition metal alkylidene complex under conditions and for a time period effective to allow cross-metathesis to occur, wherein the catalyst contains two anionic ligands, a carbene ligand, and two electron-donating heterocyclic ligands or one bidentate electron-donating heterocyclic ligand, and wherein the transition metal alkylidene complex has the structure of formula (VI)

• wherein:
• M is the Group 8 transition metal;
• n is zero or 1;
• X1 and X2 are the anionic ligands;
• L2 and L3 are the electron-donating heterocyclic ligands, or may be taken together to form a single bidentate electron-donating heterocyclic ligand provided that L 2 and L3 are selected from nitrogen-contaning heterocycles, sulfur-contaning heterocycles, and oxygen-contaning heterocycles;
• R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, or may be taken together to form a vinylidene moiety;
• X and Y are heteroatoms selected from N, O, S, and P;
• p is zero when X is O or S, and p is 1 when X is N or P;
• q is zero when Y is O or S, and q is 1 when Y is N or P;
• Q1, Q2, Q3, and Q4 are independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, and —(CO)—, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group;
• w, x, y, and z are independently zero or 1;
• and
• R3, R3A, R4, and R4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl,
• wherein any two or more of X1, X2, L2, L3, R1, and R2 can be taken together to form a cyclic group, and further wherein any one or more of X1, X2, L2, L3, R1, and R2 may be attached to a support.

A method for synthesizing an olefin directly substituted with an electron-withdrawing group and substituted with at least one additional substituent, comprising contacting (a) a first olefinic reactant directly substituted with an electron-withdrawing group with (b) a second olefinic reactant substituted with a different substituent in the presence of (c) a catalyst composed of a Group 8 transition metal alkylidene complex under conditions and for a time period effective to allow cross-metathesis to occur, wherein the catalyst contains two anionic ligands, a carbene ligand, and one or two electron-donating heterocyclic ligands, and wherein the carbene ligand is different from the one or two electron-donating heterocyclic ligands, and wherein the transition metal alkylidene complex has the structure of formula (VI)

• wherein:
• M is the Group 8 transition metal;
• n is zero or 1;
• X1 and X2 are the anionic ligands;
• L2 and L3 are the electron-donating heterocyclic ligands, or may be taken together to form a single bidentate electron-donating heterocyclic ligand, provided that L2 and L3 are selected from nitrogen-containing heterocycles;
• R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, or may be taken together to form a vinylidene moiety;
• X and Y are heteroatoms selected from N, O, S, and P;
• p is zero when X is O or S, and p is 1 when X is N or P;
• q is zero when Y is O or S, and q is 1 when Y is N or P;
• Q1, Q2, Q3, and Q4 are independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, and —(CO)—, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group;
• w, x, y, and z are independently zero or 1;
• and
• R3, R3A, R4, and R4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl,
• wherein any two or more of X1, X2, L2, L3, R1, and R2 can be taken together to form a cyclic group, and further wherein any one or more of X1, X2, L2, L3, R1, and R2 may be attached to a support.