Studies On Transition-Metal-Catalyzed C-O/S Bond Forming Via C-H Functionalization

The functionalization of transition-catalyzed arene C-H bond played an important role in natural pharmacologies, organic and biological synthesis. For a long time, it has been the focus in the field of synthesis since the large bond energy of C-H bond as well as the inertness in the reaction. Thus, it is also a goal for chemical scientists to struggle tirelessly. The text will narrate the studies of C-H functionalization in crabon-oxygen and sulfur formation. Firstly, an concised narration on the recent development of the transition-catalyzed C-H functionalization is addressed depending on the directing groups and without special chelation-assisted groups. Secondly, we described the transition-catalyzed acyloxylation of sp3 C-H bond on directing groups. Thirdly, the transition-catalyzed thiolation of sp C-H bond without chelation-assisted groups was demonsrated.The main contexts are as follows:In part one, the recent advances were reviewed about the C-H bond functionalization on the directing groups or without chelation-assisted groups. The advantages of constructing C-C/C-hetero bonds via C-H functionalization as well as the potential value of applying for organic and pharmacological fields, and chemical industries were mentioned.In part two, the chelation-assisted palladium-catalyzed acyoxylation of 8-methyl quinoline and aryl acids with the PhI(OR)2 as an oxidant which was produced by the exchange reaction of aryl acids and PhI(OAc)2 was reported. The reaction was operated simply an conveniently to afford C-O bond products from moderate to good yields, and various groups were also well-tolerated in the reaction. Particularly, the aryl halogen and hydroxy are also very reactive, which could be easily further modifiable.In the last part, the free chelation-assisted copper-catalyzed thiolation of thimethoxybenzene with disulfides employing oxygen as an oxidant was described. The reaction enjoys the advantages of mild rection conditions, facil operation, well selectivity, and commercially available materials. It is notable that the reaction represents an important significance which could be applied in the pharmacological and organic synthesis.