The functionalization of alkanes and, particularly, methane, yet constitutes an area of interest given the relatively low number of catalytic systems reported to date toward that end . The large availability of methane in natural or shale gas deposits makes it an excellent C1-source for synthetic purposes, albeit the catalytic systems described to date do not meet the required activity (TON (minimum) = 1 s-1) for industrial uses.
Our group has been involved in the area of hydrocarbon C-H functionalization using the strategy of carbene transfer from diazo compounds, which along the years has been developed until methane could be reached. In this contribution an account of such development, including the importance of the reaction medium and the nature of the carbon-hydrogen bond in the reaction outcome will be presented. An extensive study of relative reactivity of a number of alkanes, from C1 to C8 has led to a model that allows the estimation of the reactivity based on a few simple rules.
 P. J. Pérez,Alkane C-H Activation by Single-Site Metal Catalysis, Springer, Dordrecht, 2012.
 A. Caballero, P. J. Pérez, Chem. Soc. Rev. 2013, 42, 8809-8820.
A. Caballero, M. M. Díaz-Requejo, M. R. Fructos, A. Olmos, J. Urbano, P. J. Pérez, Dalton Trans. 2015, 44, 20295-20307.
 A. Caballero, E. Despagnet-Ayoub, M. M. Díaz-Requejo, A. Díaz-Rodríguez, M. E. González-Núñez, R. Mello, B. K. Muñoz, W. Solo Ojo, G. Asensio, M. Etienne and P. J. Pérez, Science, 2011, 332, 835–838.