Method for decarboxylating C—C cross-linking of carboxylic acids with carbon electrophiles
The invention relates to a method for decarboxylating C—C bond formation by reacting carboxylic salts with carbon electrophiles in the presence of transition metal compounds as catalysts. The method represents a decarboxylating C—C bond formation of carboxylic acid salts with carbon electrophiles, wherein the catalyst contains two transition metals and/or transition metal compounds, from which one is present, preferably, in the oxidation step, which are different from each other by one unit, and catalyzes a radical decarboxylation which is absorbed during the second oxidation steps, which are different from each other by two units and catalyzes the two electron processes of a C—C bond formation reaction.
1. 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 C 2 -C 20 -alkenyl, and also C 6 -C 20 -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 C 1 -C 10 -alkyl, linear, branched and cyclic C 2 -C 20 -alkenyl, and also C 6 -C 10 -aryl and heteroaryl, linear, branched and cyclic C 1 -C 10 -alkyloxy or C 1 -C 10 -aryloxy, linear, branched and cyclic C 1 -C 10 -alkyl- or C 1 -C 10 -arylaminocarbonyl, linear, branched and cyclic C 1 -C 10 -acyl, linear, branched and cyclic C 1 -C 10 -dialkylamino, C 1 -C 10 -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 R 1 —X where R 1 is selected from the group consisting of linear, branched and cyclic C 2 -C 20 -alkenyl, and also C 6 -C 20 -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 C 1 -C 10 -alkyl, linear, branched and cyclic C 2 -C 20 -alkenyl, and also C 6 -C 10 -aryl and heteroaryl, linear, branched and cyclic C 1 -C 10 -alkyloxy or C 1 -C 10 -aryloxy, linear, branched and cyclic C 1 -C 10 -alkyl- or C 1 -C 10 -arylaminocarbonyl, linear, branched and cyclic C 1 -C 10 -acyl, linear, branched and cyclic C 1 -C 10 -dialkylamino, C 1 -C 10 -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 [N 2 ] + ;
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 R 1 is not vinyl.
2. The process as claimed in claim 1 , wherein the second transition metal compound is palladium(II) acetylacetonate.
3. The process as claimed in claim 1 , wherein a cyclic amine is used as the ligand.
4. The process as claimed in claim 1 , wherein the ligand is an optionally substituted chelating cyclic amine selected from the group consisting of phenanthroline, bipyridine and terpyridine.
5. The process as claimed in claim 1 , which further comprises employing mutually independent amounts of the two catalysts of from 0.001 mol % to 100 mol % based on the carbon electrophile.
6. The process as claimed in claim 1 , which further comprises employing mutually independent amounts of the two catalysts of from 0.01 mol % to 5 mol % based on the carbon electrophile.
7. The process as claimed in claim 1 , wherein the substituent R is selected from the group consisting of linear, branched and cyclic C 2 -C 20 -alkenyl, and also C 6 -C 20 -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 C 1 -C 10 -alkyl, linear, branched and cyclic C 2 -C 20 -alkenyl, and also C 6 -C 10 -aryl and heteroaryl, linear, branched and cyclic C 1 -C 10 -alkyloxy or C 1 -C 10 -aryloxy, linear, branched and cyclic C 1 -C 10 -alkyl- or C 1 -C 10 -arylaminocarbonyl, linear, branched and cyclic C 1 -C 10 -acyl, linear, branched and cyclic C 1 -C 10 -dialkylamino, arylamino, formyl, thio, hydroxyl, carboxyl, nitro, cyano, nitroso, and halogens.
8. The process as claimed in claim 1 , wherein the substituent R 1 of the carbon electrophile is selected from the group consisting of linear, branched and cyclic C 2 -C 20 -alkenyl, and also C 6 -C 20 -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 C 1 -C 10 -alkyl, linear, branched and cyclic C 2 -C 20 -alkenyl, and also C 6 -C 10 -aryl and heteroaryl, linear, branched and cyclic C 1 -C 10 -alkyloxy or C 1 -C 10 -aryloxy, linear, branched and cyclic C 1 -C 10 -alkyl- or C 1 -C 10 -arylaminocarbonyl, linear, branched and cyclic C 1 -C 10 -acyl, linear, branched and cyclic C 1 -C 10 -dialkylamino, C 1 -C 10 -arylamino, formyl, oxo, thio, hydroxyl, carboxyl, nitro, cyano, nitroso, and halogens.
9. The process as claimed in claim 1 , which is carried out at a reaction temperature of from 80° C. to 200° C.
10. The process as claimed in claim 1 , which is carried out at a reaction temperature of from 120° C. to 160° C.
11. The process as claimed in claim 1 , wherein traces of water are removed during the reaction.
12. The process as claimed in claim 1 , wherein the carbon electrophile is a carbonyl derivative selected from the group consisting of carbonyl chloride, carboxylic anhydride, aldehyde, ketone, ester, α,β-unsaturated aldehyde, α,β-unsaturated ketone, and α,β-unsaturated ester.