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Study On C-H Bond Functionalization Of Triarylphosphonate Oxides Catalyzed By Iridium(Ⅲ)

Posted on:2022-06-05Degree:DoctorType:Dissertation
Country:ChinaCandidate:Q X LouFull Text:PDF
GTID:1481306491975289Subject:Chemistry
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Organophosphorus compounds have been recognized as a kind of important functional molecules with a wide range of applications in the areas of life sciences,medicinal chemistry,synthetic chemistry,and functional materials.In particular,they are widely used as catalytic ligands,synthetic intermediates,coupling partners and organocatalysts in many organic synthesis reactions.Herein,the development of highly efficient and environmentally benign approaches to the construction of organophosphorus compounds has attracted a great deal of attention.We have designed and synthesized varieties of novel phosphorus-containing compounds by combining the straightforward and powerful strategy of transition metal catalyzed C-H bond activation with the guidance of phosphine oxygen(P=O)group.In this paper,we focus on the C-H bond activation/carbene insertion reaction catalyzed by iridium with the direction of phosphine oxygen.First,in recent ten years,the progress of phosphorus-containing compounds as directing groups in transition metal catalyzed C-H bond activation are outlined.The catalytic models and development process of transition metal catalyzed C-H bond functionalization assisted by phosphine oxide,phosphine sulfide,phosphonic acid,phosphonamide and trivalent phosphine as directing groups,are introduced.Second,with triphenylphosphine oxide serving as both the directing group and the reagent,we have developed a Cp*Ir(III)-catalyzed direct C-H functionalization of triphenylphosphine oxide with 3-diazooxindoles to afford a range of3-(2-(diphenylphosphoryl)phenyl)indolin-2-one derivatives in moderate to excellent yields.The title products are potentially important building blocks for organic synthesis through various chemical transformations.This protocol is simple and efficient and offers high atom economy with only N2 as the byproduct.Third,a new reaction of Cp*Ir(III)-catalyzed direct C-H functionalization of triarylphosphine oxides with dicarbonyldiazepines via carbene insertion has been perfomed.This strategy provides a simple and efficient route to the construction ofα-arylated 1,3-dicarbonyls,which are important building blocks in pharmaceutical chemistry.
Keywords/Search Tags:Organophosphorus compounds, transition metal catalyzed, direct group, iridium(Ⅲ)-catalyzed, C-H bond functionalization, diazo compounds
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