Formation of C-C and C-Heteroatom Bonds by C-H Activation by Metal Organic Frameworks as Catalysts or Supports

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acscatal.8b04506"[EN] Cross-coupling reactions catalyzed by transition metals are currently among the most widely used transformations in organic synthesis. In most of these reactions, the coupling involves the reaction of two complementary functional groups, particularly boronates and halides. For the sake of atom economy and simplicity of the starting materials, it is more advantageous when the coupling involves C-H activation of one substrate lacking a reactive functional group. The present review focuses on the use of metal organic frameworks (MOFs) as solid reusable catalysts to promote cross-coupling reactions involving C-H activation. After general considerations, the review is organized according to the bond formed in the coupling, either C-C or C-heteroatom (N, O, B and X). The purpose of this mini review is to show the performance of MOFs as heterogeneous catalysts in these reactions, combining a high activity due to the large percentage of accessible metal sites and high stability allowing the reuse of the material in consecutive cycles. Comparison with homogeneous analogous catalysts indicates that this improved performance derives from the porosity, large surface area and site isolation and immobilization occurring in the MOFs. Considering the growing interests in these reactions the last section forecasts future developments in these areas in near future.A.D. thanks the University Grants Commission, New Delhi, for the award of an Assistant Professorship under its Faculty Recharge Programme. A.D. also thanks the Department of Science and Technology, India, for the financial support through Extra Mural Research Funding (EMR/2016/006500). Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2015-69153-CO2-1) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged.Dhakshinamoorthy, A.; Asiri, A.; García Gómez, H. (2019). Formation of C-C and C-Heteroatom Bonds by C-H Activation by Metal Organic Frameworks as Catalysts or Supports. ACS Catalysis. 9(2):1081-1102. https://doi.org/10.1021/acscatal.8b04506S108111029