We herein reported the N-heterocyclic carbene-palladium(ii)-1-methylimidazole complex catalyzed direct C-H bond arylation of imidazo[1,2-a]pyridines with aryl chlorides. Under suitable conditions, all reactions between various imidazo[1,2-a]pyridines and aryl chlorides worked well to give the desired C3-H arylated products in acceptable to high yields, giving a convenient and alternative method for the direct C-H bond arylation of imidazo[1,2-a]pyridines, using economic and easily available aryl chlorides as the arylating reagents.

A Rh-catalyzed decarbonylative C–H coupling of in-situ-generated acid fluorides with amide substrates bearing ortho-Csp2–H bonds has been developed. This method enables alkyl, aryl, and alkenyl carboxylic acids to undergo decarbonylative coupling with C–H bonds of (hetero)­aromatic or alkenyl amides in generally good yields via the in situ conversion of carboxylic acids into acid fluorides and also allows for the functionalization of a series of structurally complex carboxyl-containing natural products and pharmaceuticals as well as pharmaceutical amide derivatives.

A transition-metal-free, C-N bond-formation reaction between tertiary amines and aryl halides is reported. Under the optimal conditions, various aromatic and aliphatic tertiary amines react with aryl halides, including iodides, bromides, and chlorides, to give monoaminated products, N,N-dialkylanilines and N-alkyl-N-arylanilines, in good to high yields. Based on the experimental results, the reaction is believed to occur via an aryne intermediate derived from the aryl halide.

The Rh-catalyzed ortho-C(sp 2 )À H functionalization of 8-aminoquinoline-derived benzamides with aliphatic acyl fluorides generated in situ from the corresponding acids has been developed. This reaction initiated with 8-aminoquinoline-directed ortho-C(sp 2 )À H acylation, which was accompanied by subsequent intramolecular nucleophilic acyl substitution of amide group to produce alkylidene phthalides This approach exhibits high stereo-selectivity for Z-isomer products, and tolerates a variety of functional groups as well as aliphatic carboxylic acids with diverse structural scaffolds.The directing-group-assisted transition metal-catalyzed CÀ H bond functionalization reactions have been explored extensively over the last decades and therefore evolved into a powerful synthetic tool to rapidly forge new carbon-carbon and carbon-heteroatom bonds. [1] In this context, 8-aminoqunoline has been identified as a versatile bidentate auxiliary directing group to streamline syntheses of bioactive compounds via CÀ H bonds functionalization (Scheme 1a). [2] Among these approaches, the downstream conversion or removal of 8-aminoquinoline normally requires extra synthetic steps and harsh conditions, which are incompatible with certain subtle functionalities thus posing an obstacle to their synthetic applications. [3] To circumvent the manipulation of undesired directing groups, an ideal process is that directing-group-assisted CÀ H functionalization perform in tandem with subsequent transformations of directing groups, as demonstrated by Scheme 1b. [4] The methods established in this domain generally require the utilization of specific amides as directing groups, such as activated tertiary amides [4e-i] and secondary amides, [4j-t] which probably because their weakened amide CÀ N bonds due to steric distortion. [5] In spite of these significant progresses, the protocols that involve 8-aminoquinoline-based amide-directed CÀ H bond functionalization and subsequent conversion of 8aminoquinoline in a tandem manner remain rare. In this regard, only a handful of pioneering researches have been recently reported by Hirano and Miura, [6] Chatani, [7] Cheng [8] and Zhang, [9] which employed 8-aminoquinoline-based amide directing groups to promote CÀ H bond functionalization while forming additional CÀ O or CÀ C bonds in a one-pot cascade fashion (Scheme 1c). In these transformations, the 8-aminoquinoline released through carbon-nitrogen bond cleavage could be [a]