meta-C−H Functionalization and Sustainable Electro- /Photoelectrocatalytic C−H/Si−H/Ge−H Activation

by Wen Wei
Doctoral thesis
Date of Examination:2024-05-16
Date of issue:2024-06-18
Advisor:Prof. Dr. Lutz Ackermann
Referee:Prof. Dr. Manuel Alcarazo
Referee:Prof. Dr. Konrad Koszinowski
Referee:Prof. Dr. Dr. Lutz Tietze
Referee:Prof. Dr. Johannes C. L. Walker
Persistent Address: http://dx.doi.org/10.53846/goediss-10552

 

 

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Abstract

English

C−H activation provides a crucial new tool for the construction of C−C bonds in organic chemical synthesis, especially for agrochemistry, the pharmaceutical industry, and materials science, using a large number of existing metals on Earth. This dissertation overcomes the major challenge of selective functionalization of inert C-H bonds, which is related to the ubiquity of C-H bonds in organic compounds, and introduces several innovative synthesis methods. These methods use low-cost ruthenium and photocatalysis to achieve sustainable and selective C-H transformations. In the first project, we developed ruthenium-catalyzed meta-C-H secondary alkylation and benzylation using Katritzky pyridine salts that are easy to prepare. Ruthenium catalysis is characterized by good chemical selectivity and wide functional group tolerance. The second part describes the multicomponent transformation of glycosyl bromides catalyzed by ruthenium. General C-alkyl glycosides with high meta- and anomeric selectivity have been prepared. Our ruthenium-catalyzed multicomponent reaction has extremely mild reaction conditions and a broad substrate scope, which makes it possible to use in the synthesis of C-alkyl glycosides. In the third project, we developed the first palladium-catalyzed electro-C-H dearomatic spiro-annulation of 1-aryl-2-naphthalene enantioselective [3+2] cyclization catalyzed by chiral rhodium. Electrocatalysis provides a simple method for the formation of structurally distinct helical ring compounds. In the fourth project, we developed a highly efficient iron-catalyzed photoelectrochemical silane functionalization to selectively obtain silyl oxoindole with excellent chemo- and regio-selectivity. The photochemical reaction of iron (III) complexes was first used for hydro germane activation. In the fifth project, we report the photoelectrochemical borylation of C(sp3)-H bonds by combining LMCT and HAT processes, enabling the feedstock chemical transformation into value-added compounds.
Keywords: C-H Activation; meta-C-H Alkylation; Electrocatalysis; Photoelectrocatalysis; C-H Borylation
 
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