Regioselective C-H Alkenylation and Unsymmetrical Bis-olefination of Heteroarene Carboxylic Acids with Ruthenium Catalysis in Water.

An efficient weak carboxylate-assisted oxidative cross-dehydrogenative C-H/C-H coupling (CDC) of heteroarenes with readily available olefins has been devised employing water as green solvent under ruthenium(II) catalysis. The reaction is operationally simple, accommodates a large variety of heteroaromatic carboxylic acids as well as olefins, and facilitates a diverse array of high-value olefin-tethered heteroarenes in high yields (up to 87%). The potential of this ortho-C-H bond activation strategy has also been exploited toward tunable synthesis of densely functionalized heteroarenes through challenging unsymmetrical bis-olefination process in a one-pot sequential fashion. Mechanistic investigation demonstrates a reversible ruthenation process and C-H metalation step might not be involved in the rate-determining step.