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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 邱靜雯 | zh_TW |
| dc.contributor.advisor | Ching-Wen Chiu | en |
| dc.contributor.author | 謝宗睿 | zh_TW |
| dc.contributor.author | Tsung-Jui Hsieh | en |
| dc.date.accessioned | 2026-02-26T16:35:25Z | - |
| dc.date.available | 2026-02-27 | - |
| dc.date.copyright | 2026-02-26 | - |
| dc.date.issued | 2026 | - |
| dc.date.submitted | 2026-02-05 | - |
| dc.identifier.citation | Mather, B. D.; Viswanathan, K.; Miller, K. M.; Long, T. E., Michael addition reactions in macromolecular design for emerging technologie. Prog Polym Sci. 2006, 31 (5), 487–531.
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/101672 | - |
| dc.description.abstract | 麥可加成因其高原子經濟性與在建立碳–碳與碳–雜原子鍵結方面的多樣性而廣受重視。然而，由於醯胺本質上具有低親電性，此類反應鮮少應用於醯胺反應物，尤其是成功應用在未活化醯胺的範例更是罕見。此研究發現，在高路易士酸性的鋁陽離子催化，芳香硫醇對未活化 α,β-不飽和醯胺進行的對映選擇性之硫-麥可加成反應。而且此鋁陽離子催化系統具有廣泛的官能基耐受性，在 0 ℃ 下最高可達 96% 分離產率與 90% 對映選擇性。值得注意的是，在加入催化量1,8-二氮雜二環[5.4.0]十一碳-7-烯後，酸性較低的脂肪硫醇也能順利反應。此外，即便是具挑戰性的反應物，如 2-巰基吡啶，在本催化系統中亦具良好相容性，突顯了鋁陽離子在不對稱催化中的潛力。 | zh_TW |
| dc.description.abstract | Michael additions are well-known for their high atom economy and efficiency in constructing carbon–carbon and carbon–heteroatom bonds. However, due to the inherently low electrophilicity of amides, such transformations are rarely applied to amide substrates, and successful examples involving unactivated amides remain scarce. Herein, we report the first enantioselective thia-Michael addition of aromatic thiols to unactivated α,β-unsaturated amides, enabled by a highly Lewis acidic aluminum cation catalyst. The substrate scope demonstrates the broad tolerance of the aluminum cation catalytic system, achieving up to 96% isolated yield and 90% stereoselectivity at 0 ℃. Notably, aliphatic thiols also undergo this transformation upon the addition of catalytic amount of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). Furthermore, even the challenging substrate 2-mercaptopyridine exhibits good compatibility under the present catalytic conditions, emphasizing the potential of aluminum cations in asymmetric catalysis. | en |
| dc.description.provenance | Submitted by admin ntu (admin@lib.ntu.edu.tw) on 2026-02-26T16:35:25Z No. of bitstreams: 0 | en |
| dc.description.provenance | Made available in DSpace on 2026-02-26T16:35:25Z (GMT). No. of bitstreams: 0 | en |
| dc.description.tableofcontents | 口試委員審定書 i
致謝 ii 摘要 iii Abstract iv Contents v List of Abbreviations vii List of Figures viii List of Schemes ix List of Tables x Chapter 1 Introduction 1 1.1 Michael addition and its limitation 1 1.2 Aluminum cationic complexes 5 Chapter 2 Results and Discussion 7 2.1 Preliminary Catalyst Screening 7 2.2 Reaction optimization 8 2.3 Substrate scope 16 2.4 Mechanism Study 19 2.4.1 Mechanism Experiments 19 2.4.2 Proposed Mechanism 22 Chapter 3 Conclusion 24 Chapter 4 Experimental Section 25 4.1 General information 25 4.2 Synthesis of α,β-unsaturated amides 26 4.3 General Procedures 27 4.4 Characterization Data 28 Chapter 5 Appendix 49 5.1 NMR spectra 49 5.2 HPLC Chromatogram 92 5.3 Crystal data 111 References 113 | - |
| dc.language.iso | en | - |
| dc.subject | 硫-麥可加成反應 | - |
| dc.subject | 未活化 α,β-不飽和醯胺 | - |
| dc.subject | 鋁陽離子催化劑 | - |
| dc.subject | thia-Michael addition | - |
| dc.subject | unactivated α,β-unsaturated amides | - |
| dc.subject | aluminum cation catalyst | - |
| dc.title | 鋁陽離子催化對映選擇性硫-麥可加成反應用於未活化α,β-不飽和醯胺 | zh_TW |
| dc.title | Aluminum Cation Catalyzed Enantioselective Thia-Michael Reaction to Unactivated α,β-Unsaturated Amides | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 114-1 | - |
| dc.description.degree | 碩士 | - |
| dc.contributor.oralexamcommittee | 陳榮傑;林文偉 | zh_TW |
| dc.contributor.oralexamcommittee | Rong-Jie Chein;Wen-Wei Lin | en |
| dc.subject.keyword | 硫-麥可加成反應,未活化 α,β-不飽和醯胺鋁陽離子催化劑 | zh_TW |
| dc.subject.keyword | thia-Michael addition,unactivated α,β-unsaturated amidesaluminum cation catalyst | en |
| dc.relation.page | 116 | - |
| dc.identifier.doi | 10.6342/NTU202600212 | - |
| dc.rights.note | 未授權 | - |
| dc.date.accepted | 2026-02-08 | - |
| dc.contributor.author-college | 理學院 | - |
| dc.contributor.author-dept | 化學系 | - |
| dc.date.embargo-lift | N/A | - |
| 顯示於系所單位： | 化學系 | |
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