Water as reaction medium for intermolecular C-H alkane functionalization in micellar catalysis

Abstract

A series of alkanes CnH2n+2 have been functionalized in water as the reaction medium, using a silver-based catalyst, upon insertion of carbene (CHCO2Et from N2CHCO2Et) groups into their carbon-hydrogen bonds of hexane, cyclohexane or 2-methylbutane, among others. The regioselectivity toward the distinct reaction sites is identical to that found in neat alkane, the water-based system allowing the use of a much shorter excess of the hydrocarbon. This is the first example of the intermolecular functionalization of alkanes with this strategy in water. The functionalized alkanes partially undergoes a incorporation of a second carbene unit to provide a-(acyloxy)acetates, in an unprecedented tandem reaction of this nature.