Synthesis of functionalized and unfunctionalized olefins via cross and ring-closing metathesis

A method for preparing di- or tri-substituted olefins comprising contacting a first substituted or unsubstituted electron deficient olefin with a second substituted or unsubstituted electron deficient olefin in the presence of a metal carbene metathesis catalyst of the formula XX1LL1M═CRR1, wherein the first and second olefins are the same or different, to generate a di- or tri-substituted olefin in an intramolecular olefin cross-metathesis reaction;

• wherein
• M is ruthenium or osmium;
• L and L1 are each, independently, any neutral electron donor;
• X and X1 are each, independently, any anionic ligand;
• and
• R and R1 are each independently selected from hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkenyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20, alkenyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.

A method for preparing di- or tri-substituted olefins comprising contacting a substituted or unsubstituted aliphatic olefin with a substituted or unsubstituted electron-deficient olefin in the presence of a metal carbene metathesis catalyst of the formula XX1LL1M═CRR1 to generate a di- or tri-substituted olefin in an intermolecular olefin cross-metathesis reaction;

• wherein
• M is ruthenium or osmium;
• L and L1 are each, independently, any neutral electron donor;
• X and X1 are each, independently, any anionic ligand;
• and
• R and R1 are each independently selected from hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkenyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20, alkenyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.

A method for preparing trisubstituted olefins comprising contacting a first substituted or unsubstituted styrene with a second substituted or unsubstituted α-functionalized olefin in the presence of a metathesis catalyst to form a cross-product and stilbene, and contacting the stilbene with unsubstituted α-functionalized olefin in the presence of a metathesis catalyst, wherein the catalyst is of the formula:

• wherein:
• M is ruthenium;
• X and X1 are each independently selected from the group consisting of halide, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate;
• L is a phosphine of the formula PR3R4R5, where R3, R4, and R5 are each independently aryl, C1-C10 alkyl, or cycloalkyl;
• R is hydrogen;
• and,
• R1R6, R7, R8, and R9 are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.