Substituted benzimidazole phosphine compounds and a method for decarboxylating carbon-carbon bond

摘要

Preparing hydrocarbon compounds (III), comprises reacting carboxylic acid derivatives (I) with sulfonic acid ester compounds (II) in presence of a catalyst comprising (a) at least one copper complex comprising an amine, or at least one silver complex comprising an amine, and (b) at least one palladium complex present in oxidation state (II) or (0), having benzimidazolyl phosphine ligands (IV). Preparing hydrocarbon compounds of formula (R1-R41) (III), comprises reacting carboxylic acid derivatives of formula (R1-COOM) (I) with sulfonic acid ester compounds of formula (R11-O-SO 2-R21) (II) in presence of a catalyst comprising (a) at least one copper complex comprising an amine, or at least one silver complex comprising an amine, and (b) at least one palladium complex present in oxidation state (II) or (0), having benzimidazolyl phosphine ligands of formula (IV). R1 : H, optionally substituted group bonded through sp2-hybridized carbon atom, preferably 6-20C aryl, 3-20C heteroaryl or 2-20C alkenyl; R41 : cyclic compounds of formula (IIIa); R3 : 6-20C aryl or heteroaryl (both optionally substituted), preferably pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazinyl, tetrazinyl, pyrrolyl, pyrazolyl, isoxazolyl, imidazolyl, oxazolyl, thiazolyl, thiophenyl or furyl, or organic group, preferably 1-10C alkyl or 2-20C alkenyl; either X : N or C-R4; and R2, R4 : H or R3; or R2+X-R3 : optionally substituted (hetero)cyclic ring, preferably benzyl, naphthalenyl, dihydro-naphthalenyl, cyclopent-1-enyl, phenanthrenyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, tetrazinyl, pyrrolyl, pyrazolyl, isoxazolyl, imidazolyl, oxazolyl, thiazolyl, thiophenyl or furyl; M : positively charged ion, preferably Li-, Na-, K-, Rb-, Cs- or ammonium cation; R21 : 1-20C alkyl, preferably CH 3; either R5, R6 : 1-20C alkyl, 2-20C vinyl, 6-20C aryl, 3-20C heteroaryl, 1-20C alkoxy, 6-20C aryloxy, 1-20C alkylamino, 6-20C arylamino or di-6-20C arylamino; or R5+R6 : 2-18C alkanediyl; R7-R10 : H, formyl, OH, NH 2, CN, NO 2, F, Cl, Br, I, 1-20C alkyl, 2-20C vinyl, 6-20C aryl or 3-20C heteroaryl; either R12, R13 : H, carboxy, CN, NO 2, F, Cl, Br, I, 1-20C alkyl, 2-20C vinyl, 6-20C aryl or 3-20C heteroaryl; or R12+R13 : non-aromatic or (hetero)aromatic ring; and R11 : H, 1-20C alkyl, 2-20C vinyl, 6-20C aryl or 3-20C heteroaryl. Independent claims are also included for: (1) palladium complex present in oxidation state (II) or (0), having benzimidazolyl phosphine ligands of formula (IVa); (2) the palladium complex comprising palladium in the oxidation state (0) or (II) and (IV); and (3) the catalyst. Either R25, R26 : R5 or R6; or R25+R26 : 2-18C alkanediyl; R27-R30 : R7-R10; either R32, R33 : H, carboxy, CN, NO 2, F, Cl, Br, I, 1-20C alkyl, 1-20C alkoxy, 2-20C vinyl, 6-20C aryl or 3-20C heteroaryl; or R32+R33 : non-aromatic or (hetero)aromatic ring; and R31 : H, 1-20C alkyl, 1-20C alkoxy, 2-20C vinyl, 6-20C aryl or 3-20C heteroaryl. [Image] [Image].