Please use this identifier to cite or link to this item: https://scholarbank.nus.edu.sg/handle/10635/150363
Title: RHODIUM-CATALYZED ENANTIOSELECTIVE ISOMERIZATION OF HOMOALLYLIC AND BISHOMOALLYLIC SECONDARY ALCOHOLS AND COBALT-CATALYZED ENANTIOSELECTIVE VINYLATION AND ALKYNYLATION OF ACTIVATED KETONES
Authors: HUANG RUIZHI
Keywords: rhodium, enantioselective, isomerization, cobalt, vinylation, alkynylation
Issue Date: 3-Aug-2018
Citation: HUANG RUIZHI (2018-08-03). RHODIUM-CATALYZED ENANTIOSELECTIVE ISOMERIZATION OF HOMOALLYLIC AND BISHOMOALLYLIC SECONDARY ALCOHOLS AND COBALT-CATALYZED ENANTIOSELECTIVE VINYLATION AND ALKYNYLATION OF ACTIVATED KETONES. ScholarBank@NUS Repository.
Abstract: The catalytic isomerization of readily accessible alkenyl alcohols to the corresponding synthetically valuable carbonyl compounds is a fundamental reaction in organic synthesis. In this thesis, an unprecedented enantioselective redox isomerization of homoallylic and bishomoallylic secondary alcohols is presented, which is catalyzed by commercially available rhodium-complex and base. For the reaction of homoallylic alcohols, both efficient stereoconvergent isomerization to chiral ketones and kinetic resolution of the racemic alcohol substrates have been achieved. In the case of bishomoallylic alcohol isomerization, an intriguing ligand effect was observed. By choosing different bisphosphine ligands, a selective terminal-to-internal alkene isomerization and the desired redox isomerization to produce chiral ketones were both developed. A cobalt-catalyzed enantioselective vinylation of activated ketones such as α-ketoesters and isatins has been developed, which delivers a range of synthetically useful allylic alcohols in high enantiopurity. A cobalt/zinc-catalyzed enantioselective alkynylation of the same substrates has also been realized.
URI: http://scholarbank.nus.edu.sg/handle/10635/150363
Appears in Collections:Ph.D Theses (Open)

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