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Formation of C-C bond bonds is one of the most remarkable transformations in organic chemistry, and it has received special attention since the second half of the 20th century. By the late 1970s, Pd-catalyzed cross-coupling reactions emerged as a powerful tool for the construction of C-C bonds, providing new ways to build molecules. Indeed, in 2010, Heck, Suzuki and Negishi received the Nobel Prize in Chemistry for their contribution to enhancing the efficiency of organic synthesis. Although, these methodologies supposed a significant breakthrough in organic chemistry, they have some limitations such as the instability of some organometallic nucleophiles, the formation of undesired waste due to the use of stoichiometric amounts of organometallic nucleophiles, or the requirement of pre-functionalizated starting materials. During the last decade, transition metal-catalyzed CH functionalization protocols and bimetallic catalytic systems have emerged as an attractive alternative to overcome some of this problems.
Selective transition metal-catalyzed functionalization of inert bonds is one of the most useful methods in synthetic chemistry. In the past decades, noble transition metals have played a crucial role, especially in CH bond activation. In contrast, the development of catalytic processes based on more cost-effective first-row metals, is scarce. Over the past few years, cobalt-catalyzed CH functionalization reactions have shown their potential to promote CC bond-forming reactions. Despite this significant progress, these Co systems are still at their infancy compared with the analogous rhodium and palladium ones. Another alternative approach that has shown its capability to promote CC bond forming reactions is bimetallic catalysis. Compared to more traditional Pd-catalyzed cross-coupling methodologies, this bimetallic approach offers the benefit of using more ready available and cheaper starting materials. Another advantage is the minimization of by-products formation. The cooperation of two metal centers is well known in biological systems. Enzymes involving multiple metal centers represent an exceptional example of how the cooperativity of different metals can perform challenging transformations. However, it was not until the last
decade when bimetallic catalysis emerged as an attractive tool for the synthesis of CC bonds. The mechanism proposed for these bimetallic systems involves two different catalytic cycles (each with one transition-metal (TM) catalyst) connected by a transmetalation step. Despite the inherit utility and benefits exhibited by these protocols, there is a limited understanding of the mechanism of these transformations.
In this regard, this proposal will have two Work Packages (WP):
(i) WP1: investigate the mechanism of some key steps involved in different Co-catalyzed C-H functionalization reactions.
(ii) WP2: gain mechanistic insights into bimetallic systems, relevant to catalysis.
COBIST
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Ministerio de Ciencia e Innovación