Studies On C-P Bond Construction With R₂P（O）H And R₂P（O）-Directed Hydroxylation

The organophosphorus compounds play important roles in organic synthesis and the life science, so many endeavors have been focused on the development of efficient approaches to the synthesis of organophosphorus compounds. In this thesis, we describe the methods of C-P bond construction with R2P(O)H via cross-coupling of aryl chlorides and amino-phosphorus difunctionalization of the alkenes. Moreover, this is the first example of the R2P(O)-directed C-H hydroxylation. This thesis primarily includes three parts:1. The development and current methods of the C-P bond construction were summarized in detail and these methods are classified by the types of reaction modes. We describe a versatile method of constructing a C-P bond by Ni-catalyzed cross-coupling of aryl chlorides with R2P(O)H compounds in detail. Importantly, this process is generally cheaper because the accessible and inexpensive aryl chloride is used. Moreover, the process is simple, avoids the use of Ar2P(O)M and operates under mild reaction conditions.2. We presented a novel and convenient approach to the synthesis of various phosphorated indolines via a copper-catalyzed radical cascade cyclization reaction in detail. The reaction employs cheap copper as the catalyst and K2S2O8 as the oxidant under mild conditions. Various alkenes and P-radical precursors are compatible with this transformation. Preliminary mechanistic studies reveal that the addition of the P-radical may initiate the reaction, and then oxidative cyclization achieves.3. The phosphorated-group directed C-H activations are introduced systematically including phosphoric acids, phosphoric amidates, phosphoric esters and phosphine oxide. Moreover, a novel R2(O)P-directed Pd(Ⅱ)-catalyzed C-H hydroxylation to synthesize various substituted 2’-phosphorylbiphenyl-2-ol compounds is described in detail. Notably, this reaction is easy to handle under mild conditions and displays good functional group tolerance.