An efficient RuII‐catalyzed C−H bond redox‐neutral annulation of N‐nitrosoanilines with alkynes by employing water as the solvent has been developed. This transformation provides an easy and robust protocol for the synthesis of indoles with a broad range of functional group tolerance and excellent regioselectivity.

x-membered lactams were synthesized via either an amidation of sp3 C–H bonds or an electrophilic substitution of arenes via Ir-nitrene intermediates. With the employment of a readily available iridium catalyst in dichloromethane or hexafluoro-2-propanol, a wide range of lactams were synthesized in good to excellent yields with high selectivity.

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A catalytic method is developed for the diastereoselective acylation of the anomeric hydroxyl group in diverse carbohydrates to form either α- or β-anomeric esters. While exclusive formation of the β-isomer was observed in most sugar substrates with one enantiomer of the chiral catalyst, moderate to high α-selectivity was obtained by using the other enantiomer of the chiral catalyst. The resulting α- and β-anomeric esters have very different reactivity toward a reduction reaction.