Remarkable recent progress has been accomplished in direct C-H functionalizations for the formation of C-N and C-O bonds through the use of readily accessible ruthenium catalysts. Particularly, ruthenium(II) complexes allowed for challenging direct C(sp(2))-H hydroxylation of arenes. These catalysts set the stage for step-economical C-H functionalization with electron-rich as well as electron-deficient (hetero)arenes and, therefore, provided versatile access to diversely decorated phenols. While a number of synthetically useful protocols for ruthenium-catalyzed C(sp(3))-H bond nitrogenation have been elaborated, the analogous transformations of more stable C(sp(2))-H bonds were very recently achieved.

Highway to Heck: An efficient new one‐pot palladium‐catalyzed synthesis is described which affords a wide range of 9‐fluorenone derivatives in good to excellent yields. A mechanism for the two distinct catalytic steps, CH bond activation followed by oxidative intramolecular Heck cyclization, is proposed and reaction intermediates supporting this mechanism have been isolated.

Hydroxyl-assisted oxidative annulations of alkynes were accomplished with an inexpensive ruthenium(II) complex, delivering fluorescent pyrans via highly site selective as well as chemo- and regioselective C-H/O-H bond functionalizations.

Ruthenium complexes enabled first C(sp(2))-H bond oxygenations of aromatic ketones with excellent functional group tolerance, and broad scope as well as high chemoselectivity and site selectivity.

Heteroaryl-substituted arenes and heteroarenes were efficiently amidated through ruthenium-catalyzed C-H bond functionalizations with a variety of sulfonyl azides. Particularly, cationic ruthenium(II) complexes proved to be most effective and allowed nitrogenations of electron-rich and electron-deficient arenes with ample substrate scope.