Abstract
Oxidative C-H functionalization with O(2) is a sustainable strategy to convert feedstock-like chemicals into valuable products. Nevertheless, eco-friendly O(2)-utilizing chemical processes, which are scalable yet operationally simple, are challenging to develop. Here, we report our efforts, via organo-photocatalysis, in devising such protocols for catalytic C-H bond oxidation of alcohols and alkylbenzenes to ketones using ambient air as the oxidant. The protocols employed tetrabutylammonium anthraquinone-2-sulfonate as the organic photocatalyst which is readily available from a scalable ion exchange of inexpensive salts and is easy to separate from neutral organic products. Cobalt(ii) acetylacetonate was found to be greatly instrumental to oxidation of alcohols and therefore was included as an additive in evaluating the alcohol scope. The protocols employed a nontoxic solvent, could accommodate a variety of functional groups, and were readily scaled to 500 mmol scale in a simple batch setting using round-bottom flasks and ambient air. A preliminary mechanistic study of C-H bond oxidation of alcohols supported the validity of one possible mechanistic pathway, nested in a more complex network of potential pathways, in which the anthraquinone form - the oxidized form - of the photocatalyst activates alcohols and the anthrahydroquinone form - the relevant reduced form of the photocatalyst - activates O(2). A detailed mechanism, which reflected such a pathway and was consistent with previously accepted mechanisms, was proposed to account for formation of ketones from aerobic C-H bond oxidation of both alcohols and alkylbenzenes.