In this review, a summary of transition metal-catalyzed C–H activation by utilizing the functionalities as directing groups is presented.

A new method of cobalt-catalyzed synthesis of pyrrolidinones from aliphatic amides and terminal alkynes was discovered through a C-H bond functionalization process on unactivated sp(3) carbons with the silver cocatalyst using a bidentate auxiliary. For the first time, a broad range of easily accessible alkynes are exploited as the reaction partner in C(sp(3))-H bond activation to give the important 5-ethylidene-pyrrolidin-2-ones in a site-selective fashion. The reaction tolerates a wide variety of functional groups including -F, -Cl, -Br, -CF3, ether, cyclopropane, and thiophene. Both pyridine ligand and aromatic solvent play the important role for the promotion of reactivity. This cobalt-catalyzed cyclization reaction can be successfully extended to a variety of aromatic amides to afford a variety of isoindolinones. Attractive features of this catalytic system include its low cost, easy operation, and convenient access to a wide range of pyrrolidinones and isoindolinones.

The first enantioselective Satoh-Miura-type reaction is reported. Av ariety of CÀNa xially chiral N-aryloxindoles have been enantioselectively synthesized by an asymmetric rhodium-catalyzed dual C À Hactivation reaction of N-aryloxindoles and alkynes.H igh yields and enantioselectivities were obtained (up to 99 %yield and up to 99 %ee). To date,itisalso the first example of the asymmetric synthesis of CÀNa xially chiral compounds by such aC ÀHactivation strategy.

Direct construction of N−C axial chirality via Pd-catalyzed atroposelective C−H olefination of N-arylindoles is reported. The crucial role of chiral amino acid as a cocatalyst in the regio-and stereocontrol has been disclosed. In this reaction, a wide range of arylindoles and functional alkenes could be well tolerated. Moreover, the practicality and synthetic value of this process were demonstrated by the divers and simple transformations of the products.

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An ickel-catalyzed facile synthesiso fs tructurallyd iverse five-membered lactams from aliphatic amides and terminal acetylenes with the assistance of an 8-aminoquinolyl auxiliary hasb een achieved. Ab road range of terminala cetylenes anda liphatic amides proved to be the efficient coupling partners, furnishing the corresponding lactams in moderate to good yields. Thet ransformation is proven to undergo an oxidative alkynylation followed by the intramoleculara nnulation process.T he methodology can be extended to aromatic amides and acrylamides,w hich providesa ne fficient and straightforward protocol for the construction of av arietyo fi soindolinone and pyrrolidinone derivatives.

A novel copper-mediated method for the aryloxylation and vinyloxylation of β-C(sp(3))-H bonds of propioamides with organosilanes is described. The reaction proceeds with the assistance of an 8-aminoquinolyl auxiliary in a tandem way by the first oxidation of β-C(sp(3))-H bonds and subsequent arylation/vinylation to give the aryloxylation/vinyloxylation products. This unusual aryloxy/vinyloxy forming reaction offers a new avenue for the functionalization of unactivated sp(3) C-H bonds in organic synthesis.

The first enantioselective Satoh-Miura-type reaction is reported. Av ariety of CÀNa xially chiral N-aryloxindoles have been enantioselectively synthesized by an asymmetric rhodium-catalyzed dual C À Hactivation reaction of N-aryloxindoles and alkynes.H igh yields and enantioselectivities were obtained (up to 99 %yield and up to 99 %ee). To date,itisalso the first example of the asymmetric synthesis of CÀNa xially chiral compounds by such aC ÀHactivation strategy.