Palladium-Catalyzed C-H Functionalization Promoted By Organophosphorus/Sulphonate Hypervalent-Iodine

This paper mainly studies the application of palladium-catalyzed hypervalent iodine promoted C-H functionalization in organic synthesis,includes phosphate hypervalent iodine as a source of oxidants and functional groups,direct palladium-catalyzed chelating directed oxidative functionalization of unactivated C-H bonds to achieve phosphation of benzyl C(sp~3)-H bonds and hydroxylation of C(sp~2)-H bonds of aryl groups,and sulfonic acid hypervalent iodine as a source of oxidant and functional groups,direct palladium-catalyzed chelating directed oxidative functionalization of unactivated C-H bonds to achieve sulfonate and hydroxylation of benzyl C(sp~3)-H bonds,and aryl arylation of C(sp~2)-H.This paper mainly consists of three parts,the main contents are as follows:1?The research progress of transition metal catalyzed C-H bond activation of C-O bond formation in organic synthesis is described.The main description of C-H bond activation to form strong nucleophilic functionalization including hydroxylation,acyloxylation and alkoxylation,and the research progress of weak nucleophilic functionalized OTs.The application of palladium catalyzed hypervalent iodine promoted C-H bond functionalization and the reaction mechanism are briefly described,which opens up new possibilities for C-H functionalization.2?The important role of phosphate esters in natural and biologically active compounds and the synthesis of traditional phosphate esters are briefly described.We synthesize the existing phosphate hypervalent iodine as a source of oxidants and phosphates,using palladium acetate as a catalyst,achieve benzyl phosphate esterification of 8-methylquinoline compounds,hydroxylization of diphenylpyridines and achieve the phosphorylation of the C-5 position of the 8-aminoquinoline starting material without the need for a catalyst.Finally,the range of substrate suitability was tested and the mechanism of the reaction was explored.3?The important biological activities of sulfonate and its application in organic chemistry as well as the synthesis of traditional sulfonate are briefly introduced.We synthesize the existing hypervalent iodine of sulfonic acid as a source of oxidant and sulfonate,using palladium acetate as a catalyst,achieve sulfonation and hydroxylation of 8-methylquinoline compounds and arylation of diphenylpyridines.Finally,the range of substrate suitability was tested and the derivatization reaction was studied.In this paper,a new method for the formation of C-O bonds by palladium-catalyzed C-H functionalization using hypervalent iodine is proposed,which provides a new and effective synthesis strategy for the synthesis and application of phosphorylation,sulfonation and hydroxylation.