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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
Title | Synthesis of axially chiral vinylallenes, and their subsequent reactions : silver(I) catalyzed enantioselective diels-alder reaction and aerobic oxidation |
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Authors | |
Issue Date | 2015 |
Publisher | The 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. |
Abstract | The 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). |
Degree | Master of Philosophy |
Subject | Allene Chirality |
Dept/Program | Chemistry |
Persistent Identifier | http://hdl.handle.net/10722/246862 |
HKU Library Item ID | b5610943 |
DC Field | Value | Language |
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dc.contributor.author | Chan, Yu-man | - |
dc.contributor.author | 陳宇文 | - |
dc.date.accessioned | 2017-10-06T01:37:50Z | - |
dc.date.available | 2017-10-06T01:37:50Z | - |
dc.date.issued | 2015 | - |
dc.identifier.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. | - |
dc.identifier.uri | http://hdl.handle.net/10722/246862 | - |
dc.description.abstract | The 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.language | eng | - |
dc.publisher | The University of Hong Kong (Pokfulam, Hong Kong) | - |
dc.relation.ispartof | HKU Theses Online (HKUTO) | - |
dc.rights | This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. | - |
dc.rights | The author retains all proprietary rights, (such as patent rights) and the right to use in future works. | - |
dc.subject.lcsh | Allene | - |
dc.subject.lcsh | Chirality | - |
dc.title | Synthesis of axially chiral vinylallenes, and their subsequent reactions : silver(I) catalyzed enantioselective diels-alder reaction and aerobic oxidation | - |
dc.type | PG_Thesis | - |
dc.identifier.hkul | b5610943 | - |
dc.description.thesisname | Master of Philosophy | - |
dc.description.thesislevel | Master | - |
dc.description.thesisdiscipline | Chemistry | - |
dc.description.nature | published_or_final_version | - |
dc.identifier.doi | 10.5353/th_b5610943 | - |
dc.identifier.mmsid | 991043962599803414 | - |