Murahashi Coupling Polymerization: Nickel(II)–N-Heterocyclic Carbene Complex-Catalyzed Polycondensation of Organolithium Species of (Hetero)arenes

Abstract

Revisiting Murahashi coupling, we found that it effectively allows polymerization of lithiated (hetero)arenes by nickel(II)-catalyzed polycondensation. Deprotonative polymerization of 2-chloro-3-substituted thiophene with n-butyllithium gave head-to-tail-type poly(3-substituted thiophene). Poly(1,4-arylene)s were obtained by the reaction of the corresponding dibromides through lithium-bromine exchange. A lithiated thiophene derivative obtained via deprotonative halogen dance also underwent polymerization to afford a bromo-substituted polythiophene.

Nickel N-heterocyclic carbene complexes and their utility in homogeneous catalysis

“…The complex (278) [314] was reported for the Murahashi type coupling polymerization of thiophene derivatives.…”

Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage

“…[6] Ar emarkable improvement in the applicability of organolithium for cross-coupling reactions was achieved in 2013, when Feringae ta l. re-examined the Murahashi coupling and optimized both the selectivity (versus the lithium-halogen exchange) and efficiency. [8,9] Herein, we describe our recent studies on the TM-catalyzed cross-couplingo fo rganolithium with ethersa nd ammonium salts by aC ÀOo rC ÀNb ond cleavage with simultaneous CÀCb ond formation, and without lithium-halogen-exchange side reactions. [8,9] Herein, we describe our recent studies on the TM-catalyzed cross-couplingo fo rganolithium with ethersa nd ammonium salts by aC ÀOo rC ÀNb ond cleavage with simultaneous CÀCb ond formation, and without lithium-halogen-exchange side reactions.…”

Sequential Synthesis and Characterization of Novel Pyrazine Linked 1,2,4-Triazole Derivatives

“…Holla et al 15 reported the synthesis of a series of 7-arylidene-6-(2,4-dichloro-phenyl)-3-aryloxymethyl/anilinomethyl-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazines by the condensation of 3-aryl-1-(2,4-dichloro-5-fluorophenyl)-2-bromopropen-1-one.4-amino-5-mercapto-3-aryl-oxy. methyl/anilinomethyl-1,2,4-triazoles.The heterocyclic chemistry brings reagents and synthetic methods of its own usual activity in synthesis of drugs 16 , pesticides 17 and detergents 18 , as well as into the correlated fields such as biochemistry 19 , polymers 20,21 , Dyes 22,23 and material sciences 24 .…”