Transition metal-catalyzed radical functionalization of alkenes with alcohols and formamide derivatives
This thesis describes the transition metal-catalyzed radical functionalization of alkene with alcohols and formamides. A copper- or cobalt-catalyzed reaction protocol wherein the 1,3-enynes and arylalkenes underwent three-component oxyalkylation reaction with alcohols and hydroperoxides has been est...
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sg-ntu-dr.10356-692092023-02-28T23:49:15Z Transition metal-catalyzed radical functionalization of alkenes with alcohols and formamide derivatives Cheng, Jun Kee Loh Teck Peng School of Physical and Mathematical Sciences DRNTU::Science::Chemistry This thesis describes the transition metal-catalyzed radical functionalization of alkene with alcohols and formamides. A copper- or cobalt-catalyzed reaction protocol wherein the 1,3-enynes and arylalkenes underwent three-component oxyalkylation reaction with alcohols and hydroperoxides has been established. Direct α-C(sp3)-H activation of alcohol was achieved to assemble 1,3-dioxygenated molecular framework. Downstream chemical transformation allowed the β-peroxy alcohol product to give facile entry towards β-hydroxyynone and propargylic 1,3-diol. Building on this work, the reaction has been extended to employing formamide derivatives as the sources of aminocarbonyl moieties for oxycarbonylation reaction of alkenes via direct formyl C-H functionalization of formamides. The β-peroxy amide product could be subjected to chemical manipulation to afford the respective β-hydroxy amide, β-keto amide and β–lactam in follow-up reactions. In addition to the difunctionalization reaction, oxidative coupling of formamides and enamides was also successfully realized for the assembly of N-acyl enamine amides. The densely-functionalized amide products allowed efficient syntheses of pyrimidin-4-ones and 4-hydroxy-2-pyridinones. DOCTOR OF PHILOSOPHY (SPMS) 2016-11-28T04:31:49Z 2016-11-28T04:31:49Z 2016 Thesis Cheng, J. K. (2016). Transition metal-catalyzed radical functionalization of alkenes with alcohols and formamide derivatives. Doctoral thesis, Nanyang Technological University, Singapore. https://hdl.handle.net/10356/69209 10.32657/10356/69209 en 167 p. application/pdf |
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DRNTU::Science::Chemistry Cheng, Jun Kee Transition metal-catalyzed radical functionalization of alkenes with alcohols and formamide derivatives |
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This thesis describes the transition metal-catalyzed radical functionalization of alkene with alcohols and formamides. A copper- or cobalt-catalyzed reaction protocol wherein the 1,3-enynes and arylalkenes underwent three-component oxyalkylation reaction with alcohols and hydroperoxides has been established. Direct α-C(sp3)-H activation of alcohol was achieved to assemble 1,3-dioxygenated molecular framework. Downstream chemical transformation allowed the β-peroxy alcohol product to give facile entry towards β-hydroxyynone and propargylic 1,3-diol. Building on this work, the reaction has been extended to employing formamide derivatives as the sources of aminocarbonyl moieties for oxycarbonylation reaction of alkenes via direct formyl C-H functionalization of formamides. The β-peroxy amide product could be subjected to chemical manipulation to afford the respective β-hydroxy amide, β-keto amide and β–lactam in follow-up reactions. In addition to the difunctionalization reaction, oxidative coupling of formamides and enamides was also successfully realized for the assembly of N-acyl enamine amides. The densely-functionalized amide products allowed efficient syntheses of pyrimidin-4-ones and 4-hydroxy-2-pyridinones. |
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Loh Teck Peng |
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Loh Teck Peng Cheng, Jun Kee |
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Theses and Dissertations |
author |
Cheng, Jun Kee |
author_sort |
Cheng, Jun Kee |
title |
Transition metal-catalyzed radical functionalization of alkenes with alcohols and formamide derivatives |
title_short |
Transition metal-catalyzed radical functionalization of alkenes with alcohols and formamide derivatives |
title_full |
Transition metal-catalyzed radical functionalization of alkenes with alcohols and formamide derivatives |
title_fullStr |
Transition metal-catalyzed radical functionalization of alkenes with alcohols and formamide derivatives |
title_full_unstemmed |
Transition metal-catalyzed radical functionalization of alkenes with alcohols and formamide derivatives |
title_sort |
transition metal-catalyzed radical functionalization of alkenes with alcohols and formamide derivatives |
publishDate |
2016 |
url |
https://hdl.handle.net/10356/69209 |
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1759856252447358976 |