Selective C–H Activation by Ruthenium(II) Carboxylate and Nickelaelectro-Catalysis
von Shoukun Zhang
Datum der mündl. Prüfung:2021-01-11
Erschienen:2021-01-28
Betreuer:Prof. Dr. Lutz Ackermann
Gutachter:Prof. Dr. Shoubhik Das
Gutachter:Prof. Dr. Manuel Alcarazo
Gutachter:Prof. Dr. Dietmar Stalke
Gutachter:Dr. Johannes C. L. Jun.-prof. Walker
Gutachter:Dr. Michael John
Dateien
Name:PhD dissertation_Shoukun Zhang.pdf
Size:34.1Mb
Format:PDF
Description:meta- or ortho- C–H Activation by Ruthenium(II) Carboxylate; Nickelaelectro-Catalyzed C-H amination, secondary alkoxylation, phosphorylation
Zusammenfassung
Englisch
This doctoral thesis was divided into two main parts. In the first part, ruthenium(II)-catalyzed ortho-C–H alkynylations of diverse benzoic acids were achieved for the synthesis of aromatic alkynes. And meta-C–H activations, including mono- or difluoromethylation and alkylation through the σ-activation of the cyclometallated intermediate were also efficiently developed by ruthenium catalysis. In the second part, the first nickela-electrochemical C–H activation, including C–H amination, challenging secondary alkoxylation and phosphorylation in a dehydrogenative manner employing green and cheap electricity as the oxidant, providing an expedient approach to arylamines, aryl ethers and arylphosphonates. Detailed mechanistic studies including the isolation of catalytically relevant nickel(III) complex, cyclovoltammetry, and computation provided strong support for an oxidation-induced reductive elimination at nickel(III).
Keywords: meta-C–H difluomethylation or monofluomethylation; C–H Activation; C–H Amination; C–H Alkoxylation; C–H Phosphorylation; ortho-C–H alkynylation; Nickel; Ruthenium; Electrochemistry; Electrocatalysis