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postgraduate thesis: Synthesis of axially chiral vinylallenes, and their subsequent reactions : silver(I) catalyzed enantioselective diels-alder reaction and aerobic oxidation

TitleSynthesis of axially chiral vinylallenes, and their subsequent reactions : silver(I) catalyzed enantioselective diels-alder reaction and aerobic oxidation
Authors
Issue Date2015
PublisherThe University of Hong Kong (Pokfulam, Hong Kong)
Citation
Chan, Y. [陳宇文]. (2015). Synthesis of axially chiral vinylallenes, and their subsequent reactions : silver(I) catalyzed enantioselective diels-alder reaction and aerobic oxidation. (Thesis). University of Hong Kong, Pokfulam, Hong Kong SAR. Retrieved from http://dx.doi.org/10.5353/th_b5610943.
AbstractThe pursuit of highly enantioselective reactions for the generation of complex organic molecules with point/axial chirality is everlasting for synthetic organic chemists. Axially chiral vinylallenes are important structural motifs present in natural products and are versatile chiral synthons attributed to axial-to-point chirality transfer. In this work, a series of axially chiral vinylallenes were successfully synthesized and two subsequent reactions: enantioselective silver(I) catalyzed Diels-Alder reaction and aerobic oxidation of vinylallenes, are described. A series of axially chiral vinylallenes (up to 98% ee) were generated in good yields (up to 81%) by reacting chiral propargylamines in acetonitrile at 40°C. The optically active vinylallenes underwent silver-catalyzed cycloaddition with maleimines and azodicarboxylates in water at 40°C to form different cycloadducts as single diastereomers in excellent yields (up to 82%) with excellent enantioselectivity (up to 97% ee). The chiral vinylallenes also underwent silver-catalyzed aerobic oxidation in acetonitrile at 40°C and light-induced oxidative cyclization via singlet oxygen in toluene at room temperature upon irradiation by a 300 W xenon lamp. For aerobic oxidation, a series of achiral cyclopentenones were synthesized in good yields (up to 79%). For light-induced oxidative cyclization via singlet oxygen, a new series of chiral 2H-pyranones were synthesized in excellent yields (up to 98%) with good enantioselectivity (up to 83% ee).
DegreeMaster of Philosophy
SubjectAllene
Chirality
Dept/ProgramChemistry
Persistent Identifierhttp://hdl.handle.net/10722/246862
HKU Library Item IDb5610943

 

DC FieldValueLanguage
dc.contributor.authorChan, Yu-man-
dc.contributor.author陳宇文-
dc.date.accessioned2017-10-06T01:37:50Z-
dc.date.available2017-10-06T01:37:50Z-
dc.date.issued2015-
dc.identifier.citationChan, Y. [陳宇文]. (2015). Synthesis of axially chiral vinylallenes, and their subsequent reactions : silver(I) catalyzed enantioselective diels-alder reaction and aerobic oxidation. (Thesis). University of Hong Kong, Pokfulam, Hong Kong SAR. Retrieved from http://dx.doi.org/10.5353/th_b5610943.-
dc.identifier.urihttp://hdl.handle.net/10722/246862-
dc.description.abstractThe pursuit of highly enantioselective reactions for the generation of complex organic molecules with point/axial chirality is everlasting for synthetic organic chemists. Axially chiral vinylallenes are important structural motifs present in natural products and are versatile chiral synthons attributed to axial-to-point chirality transfer. In this work, a series of axially chiral vinylallenes were successfully synthesized and two subsequent reactions: enantioselective silver(I) catalyzed Diels-Alder reaction and aerobic oxidation of vinylallenes, are described. A series of axially chiral vinylallenes (up to 98% ee) were generated in good yields (up to 81%) by reacting chiral propargylamines in acetonitrile at 40°C. The optically active vinylallenes underwent silver-catalyzed cycloaddition with maleimines and azodicarboxylates in water at 40°C to form different cycloadducts as single diastereomers in excellent yields (up to 82%) with excellent enantioselectivity (up to 97% ee). The chiral vinylallenes also underwent silver-catalyzed aerobic oxidation in acetonitrile at 40°C and light-induced oxidative cyclization via singlet oxygen in toluene at room temperature upon irradiation by a 300 W xenon lamp. For aerobic oxidation, a series of achiral cyclopentenones were synthesized in good yields (up to 79%). For light-induced oxidative cyclization via singlet oxygen, a new series of chiral 2H-pyranones were synthesized in excellent yields (up to 98%) with good enantioselectivity (up to 83% ee).-
dc.languageeng-
dc.publisherThe University of Hong Kong (Pokfulam, Hong Kong)-
dc.relation.ispartofHKU Theses Online (HKUTO)-
dc.rightsThis work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.-
dc.rightsThe author retains all proprietary rights, (such as patent rights) and the right to use in future works.-
dc.subject.lcshAllene-
dc.subject.lcshChirality-
dc.titleSynthesis of axially chiral vinylallenes, and their subsequent reactions : silver(I) catalyzed enantioselective diels-alder reaction and aerobic oxidation-
dc.typePG_Thesis-
dc.identifier.hkulb5610943-
dc.description.thesisnameMaster of Philosophy-
dc.description.thesislevelMaster-
dc.description.thesisdisciplineChemistry-
dc.description.naturepublished_or_final_version-
dc.identifier.doi10.5353/th_b5610943-

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