Transition metal-catalyzed direct functionalization of C–H bonds is one of the key emerging strategies that is currently attracting tremendous attention with the aim to provide alternative environmentally friendly and efficient ways for the construction of C–C and C–hetero bonds. In particular, the strategy involving regioselective C–H activation assisted by various functional groups shows high potential, and significant achievements have been made in both the development of novel reactions and the mechanistic study. In this review, we attempt to give an overview of the development of utilizing the functionalities as directing groups. The discussion is directed towards the use of different functional groups as directing groups for the construction of C–C and C–hetero bonds via C–H activation using various transition metal catalysts. The synthetic applications and mechanistic features of these transformations will be discussed, and the review is organized on the basis of the type of directing groups and the type of bond being formed or the catalyst.

Transition metal-catalyzed C–H bond functionalizations by the use of diverse directing groups

Transition-Metal-Catalyzed Direct Addition of Unactivated C–H Bonds to Polar Unsaturated Bonds

Esters are valuable commodity chemicals widely found in agrochemicals, pharmaceuticals, and advanced materials. They are also important synthetic building blocks for chemical transformation. Recent advances of ester synthesis via transition-metal-catalyzed C–H activation have provided highly efficient and atom-economical alternatives to the traditional methods. Herein, we summarize recent advances on ester synthesis via transition-metal-catalyzed C–H activation. On the basis of the modes of reactivity and the types of C–H bonds, transition-metal-catalyzed alkoxycarbonylation of C–H bonds with various esterification reagents will be discussed in sections 2 and 3. Finally, hydroesterification/hydroacylation of C–C or C–O double bonds via formate C–H activation will be discussed in sections 4 and 5.

Recent Advances on Ester Synthesis via Transition-Metal Catalyzed C–H Functionalization

Olefinic C-H functionalization represents an atom- and step economic approach to valuable olefin derivatives from simpler ones, but controlling the selectivity remains a challenge. Remarkable progress has been made in the site-selective C-H functionalization of arenes and alkanes, but there are still limited examples of selective C-H functionalization of olefins presumably due to the lability and easy decomposition of the alkenyl moiety. Chelation-assisted C-H activation represents an efficient protocol for site- and stereo-selective construction of carbon-carbon and carbon-heteroatom bonds. This review highlights recent advances in vicinal- and geminal-group-directed olefinic C-H functionalization, including alkenylation, arylation, alkynylation, alkylation, halogenation, silylation, cyanation and annulation by the formation of exo-/endo-metallocycles. In particular, geminal-group-directed C-H functionalization is covered for the first time, as well as distal-selective alkenyl C-H functionalization under palladium/norbornene cooperative catalysis, which provides novel disconnections in retrosynthetic analysis and represents the future trend in green chemistry.

Recent advances in chelation-assisted site- and stereoselective alkenyl C-H functionalization.

Pd-Catalyzed Oxidative Coupling of Enamides and Alkynes for Synthesis of Substituted Pyrroles

Palladium‐Catalyzed Oxidative Carbonylation of the Alkenyl CH Bonds of Enamides: Synthesis of 1,3‐Oxazin‐6‐ones

Reported herein is the development of the first enantioselective monodentate ligand assisted Pd-catalyzed domino Heck carbonylation reaction with CO. The highly enantioselective domino Heck carbonylation of N-aryl acrylamides and various nucleophiles, including arylboronic acids, anilines, and alcohols, in the presence of CO was achieved. A novel monodentate phosphoramidite ligand, Xida-Phos, has been developed for this reaction and it displays excellent reactivity and enantioselectivity. The reaction employs readily available starting materials, tolerates a wide range of functional groups, and provides straightforward access to a diverse array of enantioenriched oxindoles having β-carbonyl-substituted all-carbon quaternary stereocenters, thus providing a facile and complementary method for the asymmetric synthesis of bioactive hexahydropyrroloindole and its dimeric alkaloids.

Palladium-Catalyzed Enantioselective Heck Carbonylation with a Monodentate Phosphoramidite Ligand: Asymmetric Synthesis of (+)-Physostigmine, (+)-Physovenine, and (+)-Folicanthine.

A novel palladium-catalyzed carbonylation of indoles with CO and aromatic boronic acids for the synthesis of indol-3-yl aryl ketones was developed. The reaction tolerates a wide range of functional groups and gives a variety of valuable indol-3-yl aryl ketones in high yields under mild conditions.

Palladium-Catalyzed Carbonylation of Indoles for Synthesis of Indol-3-yl Aryl Ketones

Hydroaminocarbonylation of alkenes is one of the most promising yet challenging methods for the synthesis of amides. Herein, we reported the development of a novel and effective Pd-catalyzed Markovnikov hydroaminocarbonylation of 1,1-disubstituted or 1,1,2-trisubstituted alkenes with aniline hydrochloride salts to afford amides bearing an α quaternary carbon. The reaction makes use of readily available starting materials, tolerates a wide range of functional groups, and provides a facile and straightforward approach to a diverse array of amides bearing an α quaternary carbon. Mechanistic investigations suggested that the reaction proceeded through a palladium hydride pathway. The hydropalladation and CO insertion are reversible, and the aminolysis is probably the rate-limiting step.

Palladium-Catalyzed Markovnikov Hydroaminocarbonylation of 1,1-Disubstituted and 1,1,2-Trisubstituted Alkenes for Formation of Amides with Quaternary Carbon.

A one-pot three-component reaction of aldehydes, nitroalkanes and NaN3 for the synthesis of NH-1,2,3-triazoles has been developed. The reaction provides a safe, efficient and step-economic approach for the synthesis of various NH-1,2,3-triazoles in good to excellent yields.

One‐Pot Synthesis of 4‐Aryl‐NH‐1,2,3‐Triazoles through Three‐Component Reaction of Aldehydes, Nitroalkanes and NaN3

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