Method for decarboxylating C—C cross-linking of carboxylic acids with carbon electrophiles

A process for decarboxylating and C—C bond formation comprising reacting carboxylic acid salts with carbon electrophiles in the presence of a catalyst system to achieve decarboxylating C—C bond forming cross-coupling, said catalyst system comprising first and second transition metal compounds and one or more ligands;

• wherein the carboxylic acid salts are selected from the group consisting of carboxylic acid salts of the Formula 1 where n, m, q, p are numbers from 1 to 6 and r is a number from 0 to 6;
• M(m+) is a cation of a metal selected from the group consisting of Li, Na, K, Mg, Ca, B, Al, Ag, Cu, Mn, Fe, Co, Ni, Mo, and Ru;
• R is selected from the group consisting of linear, branched and cyclic C2-C20-alkenyl, and also C6-C20-aryl and heteroaryl selected from the group consisting of pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, tetrazinyl, pyrrolyl, pyrazolyl, isoxazolyl, imidazolyl, oxazolyl, thiazolyl, thiophenyl and furanyl, and may in turn bear further substituents selected from the group consisting of linear, branched and cyclic C1-C10-alkyl, linear, branched and cyclic C2-C20-alkenyl, and also C6-C10-aryl and heteroaryl, linear, branched and cyclic C1-C10-alkyloxy or C1-C10-aryloxy, linear, branched and cyclic C1-C10-alkyl- or C1-C10-arylaminocarbonyl, linear, branched and cyclic C1-C10-acyl, linear, branched and cyclic C1-C10-dialkylamino, C1-C10-arylamino, formyl, thio, hydroxyl, carboxyl, nitro, cyano, nitroso, and halogens;
• and Y(p−) is an anion:
• wherein the carbon electrophiles are selected from the group consisting of carbon electrophiles of the formula formula R1—X where R1 is selected from the group consisting of linear, branched and cyclic C2-C20-alkenyl, and also C6-C20-aryl and heteroaryl selected from the group consisting of pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, tetrazinyl, pyrrolyl, pyrazolyl, isoxazolyl, imidazolyl, oxazolyl, thiazolyl, thiophenyl and furanyl, and may in turn bear further substituents from the group of linear, branched and cyclic C1-C10-alkyl, linear, branched and cyclic C2-C20-alkenyl, and also C6-C10-aryl and heteroaryl, linear, branched and cyclic C1-C10-alkyloxy or C1-C10-aryloxy, linear, branched and cyclic C1-C10-alkyl- or C1-C10-arylaminocarbonyl, linear, branched and cyclic C1-C10-acyl, linear, branched and cyclic C1-C10-dialkylamino, C1-C10-arylamino, formyl, oxo, thio, hydroxyl, carboxyl, nitro, cyano, nitroso, and halogens;
• and X is selected from the group consisting of halides selected from the group consisting of I, Br, and Cl, and pseudohalides selected from the group consisting of toluenesulfonate, methylsulfonate, trifluorosulfonate, trifluoroacetate, carboxylate and [N2]+;
• wherein the first transition metal compound is selected from the group consisting of copper compounds;
• wherein the second transition metal compound is selected from the group consisting of palladium compounds;
• wherein the one or more ligands are selected from the group consisting of amines, phosphines, N-heterocyclic carbenes, nitriles and olefins;
• provided that if R represents aryl or heteroaryl, then R1 is not vinyl.