Herein we report the first versatile and expeditious method for the site-selective C−H fluoromethylation of aryl iodides via Pd/norbornene cooperative catalysis, which could work as a robust toolbox for the diversity-oriented synthesis (DOS) of fluoromethylated arenes. This methodology features the use of the low-cost industrial raw material CH 2 IF as the fluoromethyl source, an excellent functional group tolerance, and a broad ipso termination scope and can be expanded to the late-stage modification of biorelevant molecules.

An efficient, PhI(OAc)2-mediated, radical azidoheteroarylation of alkenes under transition-metal-free conditions is reported by employing TMSN3 and quinoxalin-2(1H)-ones as coupling partners. This domino reaction allows an efficient synthesis of valuable orangoazides containing quinoxalin-2(1H)-one derivatives and could be extended to phosphinyl-alkylated quinoxalin-2(1H)-one in a single step in moderate to excellent yields under mild conditions, as demonstrated by the preliminary antibacterial evaluation against Magnaporthe grisea for the first time. Mechanistic studies revealed that this transformation undergoes a cascade addition pathway controlled by a polar radical.

We herein report the nickel-catalyzed enantioselective hydrofluoromethylation of enamides and enol esters with CH 2 FI as the fluoromethyl source to enable the diversity-oriented synthesis (DOS) of chiral α-fluoromethylated amides as well as esters with features of wide functional group compatibility as well as excellent enantioselectivity. The synthetic value of this protocol was demonstrated by transformations of the resulted α-fluoromethylated amides to different scaffolds including amine, oxazoline, thiazoline, and α-fluoromethylated tetrahydroquinoline.