Alkanes are considered as plausible raw materials in chemistry on the basis of their availability. However, their chemical inertness has yet circumvented such use, that is yet restricted to a few examples. Moreover, this family of compounds displays quite different behavior on the basis of the chain length: the lighter members (C1-C4) are gaseous at atmospheric pressure, then the alkanes becoming liquids and solids when increasing the number of carbon in the chain. Because of this, the direct comparison of their relative reactivity has been difficult to achieve, avoiding the accessibility to a scale of reactivity for the overall group of CnH2n+2 hydrocarbons. We have recently discovered the catalytic capabilities of silver-containing catalysts for the functionalization of alkanes upon transfer of the carbene unit CHCO2Et from ethyl diazoacetate, including the C1-C4 members, on the basis of the employment of supercritical carbon dioxide as the reaction medium.1 We have now taken advantage of such catalytic behavior to carry out a series of competition experiments from which an overall relative reactivity scale from methane to adamantane has been built. 1. (a) Caballero, A.; Despagnet-Ayoub, E.; Díaz, A.; Díaz-Requejo, M. M.; González-Núñez, M. E.; Mello, R.; Muñoz, B.K.; Ojo, W.-S.; Asensio, G.; Etienne, M.; Pérez, P. J. Science 2011, 332, 835. (b) Fuentes, M.A.; Olmos, A.; Muñoz, B. K.; Jacob, K.; González-Núñez, M. E.; Mello, R.; Asensio, G.; Caballero, A.; Etienne, M.; Pérez, P. J. Chem. Eur. J. 2014., 20, 11013.

Relative reactivity scale of alkanes from C-H bond functionalization reactions

249th National Meeting (2015)

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