Part I : Palladium-catalyzed radical alkylation of arenes. Part II : Nickel-catalyzed asymmetric hydrogenation of quinoxalines using formic acid
We developed a general procedure for palladium-catalyzed radical alkylation of activated arenes. Electron-deficient benzenes and naphthalene derivatives reacted to give alkylated products in moderate to good yields. The alkyl radicals added to para position of strong electron-withdrawing groups on t...
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| Formato: | Thesis |
| Idioma: | English |
| Publicado em: |
2017
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| Acesso em linha: | http://hdl.handle.net/10356/69709 |
| _version_ | 1826114079566069760 |
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| author | Lim, Li Hui |
| author2 | Zhou Jianrong |
| author_facet | Zhou Jianrong Lim, Li Hui |
| author_sort | Lim, Li Hui |
| collection | NTU |
| description | We developed a general procedure for palladium-catalyzed radical alkylation of activated arenes. Electron-deficient benzenes and naphthalene derivatives reacted to give alkylated products in moderate to good yields. The alkyl radicals added to para position of strong electron-withdrawing groups on the arenes. This alkylation method complements with traditional Friedel-Crafts alkylation which reacted well with electron-rich and neutral arenes.
We reported asymmetric transfer hydrogenation of 2-substituted quinoxalines using Ni/TangPhos as the catalyst and formic acid as the source of hydrogen. Moderate to good enantioselectivities were obtained depending on the substituents. We also realized a one-pot reductive amination between 1,2-phenylenediamine and substituted glyoxal. The two spontaneously condensed to form quinoxalines. The later was not isolated and subjected to nickel catalyzed asymmetric transfer hydrogenation.
We realized a challenging Heck arylation of N-substituted maleimides, which are exceedingly prone to basic hydrolysis. We found a combination of weak base KOAc in ethylene carbonate solvent helped to slow down the ring-opening side reactions of sensitive maleimide to form the Heck product in good yield and with good generality. |
| first_indexed | 2024-10-01T03:33:20Z |
| format | Thesis |
| id | ntu-10356/69709 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T03:33:20Z |
| publishDate | 2017 |
| record_format | dspace |
| spelling | ntu-10356/697092023-02-28T23:36:54Z Part I : Palladium-catalyzed radical alkylation of arenes. Part II : Nickel-catalyzed asymmetric hydrogenation of quinoxalines using formic acid Lim, Li Hui Zhou Jianrong School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Physical chemistry::Catalysis We developed a general procedure for palladium-catalyzed radical alkylation of activated arenes. Electron-deficient benzenes and naphthalene derivatives reacted to give alkylated products in moderate to good yields. The alkyl radicals added to para position of strong electron-withdrawing groups on the arenes. This alkylation method complements with traditional Friedel-Crafts alkylation which reacted well with electron-rich and neutral arenes. We reported asymmetric transfer hydrogenation of 2-substituted quinoxalines using Ni/TangPhos as the catalyst and formic acid as the source of hydrogen. Moderate to good enantioselectivities were obtained depending on the substituents. We also realized a one-pot reductive amination between 1,2-phenylenediamine and substituted glyoxal. The two spontaneously condensed to form quinoxalines. The later was not isolated and subjected to nickel catalyzed asymmetric transfer hydrogenation. We realized a challenging Heck arylation of N-substituted maleimides, which are exceedingly prone to basic hydrolysis. We found a combination of weak base KOAc in ethylene carbonate solvent helped to slow down the ring-opening side reactions of sensitive maleimide to form the Heck product in good yield and with good generality. Doctor of Philosophy (SPMS) 2017-03-20T07:37:56Z 2017-03-20T07:37:56Z 2017 Thesis Lim, L. H. (2017). Part I : Palladium-catalyzed radical alkylation of arenes. Part II : Nickel-catalyzed asymmetric hydrogenation of quinoxalines using formic acid. Doctoral thesis, Nanyang Technological University, Singapore. http://hdl.handle.net/10356/69709 10.32657/10356/69709 en 140 p. application/pdf |
| spellingShingle | DRNTU::Science::Chemistry::Physical chemistry::Catalysis Lim, Li Hui Part I : Palladium-catalyzed radical alkylation of arenes. Part II : Nickel-catalyzed asymmetric hydrogenation of quinoxalines using formic acid |
| title | Part I : Palladium-catalyzed radical alkylation of arenes. Part II : Nickel-catalyzed asymmetric hydrogenation of quinoxalines using formic acid |
| title_full | Part I : Palladium-catalyzed radical alkylation of arenes. Part II : Nickel-catalyzed asymmetric hydrogenation of quinoxalines using formic acid |
| title_fullStr | Part I : Palladium-catalyzed radical alkylation of arenes. Part II : Nickel-catalyzed asymmetric hydrogenation of quinoxalines using formic acid |
| title_full_unstemmed | Part I : Palladium-catalyzed radical alkylation of arenes. Part II : Nickel-catalyzed asymmetric hydrogenation of quinoxalines using formic acid |
| title_short | Part I : Palladium-catalyzed radical alkylation of arenes. Part II : Nickel-catalyzed asymmetric hydrogenation of quinoxalines using formic acid |
| title_sort | part i palladium catalyzed radical alkylation of arenes part ii nickel catalyzed asymmetric hydrogenation of quinoxalines using formic acid |
| topic | DRNTU::Science::Chemistry::Physical chemistry::Catalysis |
| url | http://hdl.handle.net/10356/69709 |
| work_keys_str_mv | AT limlihui partipalladiumcatalyzedradicalalkylationofarenespartiinickelcatalyzedasymmetrichydrogenationofquinoxalinesusingformicacid |