Anaerobic functionalization of remote unactivated carbon-hydrogen bond by polyoxometalates

The excited states of a representative heteropolytungstate. -PW₁₂O₄₀^3-, and a representative Isopotytungstate, W₁₀O₃₂^4-, accessible with near UV or blue light, oxidize alkanes and conventionally far more reactive organic molecules including alcohols, alkenes, N-alkylacetamides, and Ketones. at comparable rates. One or more of the latter three types of compounds are produced upon irradiation of acetonitrile solutions containing the polyoxotungstate and alkane substrate under anaerobic conditions. Comparison of alcohol versus alkane reactivities under absolute and competitive kinetic conditions indicates that alcohol- polyoxotungstate preassociation can be important in these processes. Reaction of cis- and trans-2-decalones in these systems indicates that functionalization of unactivated positions (primarily incorporation of the olefiaic unit) remote from the usually activating ketone group can be accomplished.