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Studies On Transition-Metal-Catalyzed New Type C-H Bond Functionalization

Posted on:2017-04-20Degree:DoctorType:Dissertation
Country:ChinaCandidate:H ZhangFull Text:PDF
GTID:1221330503462839Subject:Chemistry
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The transition-metal-catalyzed C-H bond functionalization reaction have attracted a great deal of attention and demonstrated their powerful in introducing useful functionality, due to this strategy is a simple, convenient, atom economy and environment-firendly method. This thesis describes two new reactions of transition-metal-catalyzed C-H bond functionalization.According to the contents, this thesis includes the following three parts:1, The development of allylic C-H transformations were introduced systematically including C-O, C-C, C-Si, C-F, C-P bond formation. At the same time, the development and current methods of C-H bond acetoxylation were summarized. The reactions are classified by different reaction typs.2, The phosphorated-group directed C-H bond activations are introduced in detail. Moreover, a novel and effcient R2(O)P directed Pd(II)-catalyzed C–H acetoxylation is described. This approach could synthesize various substituted 2’-phosphorylbiphenyl-2-OAc compounds. Furthermore, chiral ligand of(R)-MeO-MOP is obtained throughout some conversion process. Notably, the reaction is easy to handle, shows good functional group tolerance, and generates high yields with high selectivity.3. The development of dearomative of indoles to construct fused indulines have been summarized in detail. We developed a novel dearomatization of substituted indoles triggered by C-H bond activation. The reaction employs Pd as catalyst and the presence of a catalytic amount of 2,5-DMBQ is proven to be a key factor for the high yield. Various C3-phenylpropenyl indolenine products get with this simple transformation. Preliminary mechanistic studies reveal that the π- allylpalladium complex is important intermediates in this reaction.
Keywords/Search Tags:acetoxylation, allylic C-H transformations, C-H bond functionalization, dearomation of indoles.R2(O)P directing group, transition-metal
PDF Full Text Request
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