Nickel-catalyzed asymmetric transfer hydrogenation

• Main Author: Guo, Siyu
• Other Authors: Zhou Jianrong
• Format: Theses and Dissertations
• Language: English
• Published: 2017
• Subjects: DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds
• Online Access: http://hdl.handle.net/10356/72886
• Institution: Nanyang Technological University

This thesis describes my work on nickel-catalyzed asymmetric transfer hydrogenation of unsaturated C=C and C=N bonds using various hydride sources. It contains three main parts. Chapter one reported a highly enantioselective asymmetric hydrogenation of a,b-unsaturated esters with a chiral phosphine ligand, (R)-Me-DuPhos. With formic acid and triethyl amine worked as hydrogen source, excellent conversion and enantioselectivity were obtained. Furthermore, deuterium labeling experiments revealed a possible mechanism. I also reported asymmetric transfer hydrogenation of a,b-unsatureated esters with DMF and water as hydride source. Chapter two described asymmetric transfer hydrogenation of cinnamates, beta- dehydroacetamidoesters and hydrazones with acetic acid and indium powder. With nickel/(S)-Binapine or (R)-Me-DuPhos catalytic system, a series of C=C and C=N gave high enantioselectivities. Chapter three reported asymmetric deuteration of a,b-unsaturated esters with deuterium water and indium powder as hydride source. For all the substrates which we tested, excellent conversion, enantioselectivity and deuterium incorporation were obtained. This work provided a novel methodology for fine chiral deuterated products without expensive and explosive deuterium gas. Remove