Kumada-Corriu-Tamao couplings catalyzed by Ni and Pd as an important tool for the biaryl synthesis

Abstract

Abstract:Cross-coupling reactions catalyzed by transition metal complexes are important tools in the synthesis of biaryls, building blocks in a variety of compounds with interesting applications. The contributions of the palladium-catalyzed cross-coupling reactions to organic synthesis were recognized in 2010 when R. F. Heck, E. Negishi and A. Suzuki were awarded the Nobel Prize in Chemistry. Biarylic systems are usually obtained by a C(sp 2 )-C(sp 2 ) bond formation process catalyzed by Ni or Pd and several methodologies are currently available for their synthesis, for example, the Suzuki reaction, or Stille, Hiyama, Negishi, or Kumada-Corriu-Tamao crosscoupling. In this work, the Kumada-Corriu-Tamao methodology is investigated. The main characteristics of the reaction, like the catalytic systems employed, the different classes of substrates, and the optimization of the experimental protocol will be discussed as well. Application of this methodology in the synthesis of molecules of interest will also be addressed. The Kumada-Corriu-Tamao methodology is claimed to be the precursor of all other cross-coupling methodologies, pushing the frontiers of the organic synthesis.Keywords: biaryls; C-C coupling; Kumada-Corriu-Tamao; niquel; palladium; Nobel 2010. ResumoOs acoplamentos cruzados catalisados por metais de transição são ferramentas muito importantes na construção de sistemas biarílicos, os quais estão presentes na estrutura de diversas substâncias com aplicações importantes na terapêutica médica e na indústria química. A importância dos acoplamentos cruzados foi reconhecida pela concessão do prêmio Nobel de 2010 aos pesquisadores R. F. Heck, E. Negishi e A. Suzuki. Geralmente, os sistemas biarílicos são obtidos mediante a formação de ligações C(sp 2 )-C(sp 2 ) entre dois anéis aromáticos através de um processo catalisado por Ni ou Pd. Várias metodologias de acoplamento estão disponíveis para o preparo de biarilas como, por exemplo, as reações de Suzuki, Stille, Hiyama, Negishi ou Kumada-Corriu-Tamao. Neste trabalho, será abordado o acoplamento de Kumada-Corriu-Tamao: as características principais, os sistemas catalíticos empregados, os diferentes substratos e o processo de desenvolvimento da metodologia que alavancou os acoplamentos cruzados conhecidos e largamente empregados atualmente.

Suzuki–Miyaura Cross-Coupling for the Synthesis of Key Intermediates of Ketoprofen and Bifonazole Analogues

“…In our research group, we apply Suzuki couplings as the synthetic tools to obtain compounds of biological importance [2,3]. The Suzuki coupling enable the formation of a C-C bond with the reaction between a boron organometallic and an electrophile (halide or pseudohalide) under palladium catalysis and in the presence of a base [4][5][6][7]. Carboxylic acids and their derivatives can also be employed as electrophiles in palladium-catalyzed coupling reactions, and they can generate ketones as products if they are used in Suzuki reactions [8][9][10][11][12].…”