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研究生：	王釋央 Wang, Shi-Yang
論文名稱：	探討氮轉移試劑的化學選擇性及其官能基耐受性 The Investigation on the Chemoselectivity and Functional Group Tolerance of the N-Transfer Reagent
指導教授：	周鶴軒 Chou, Ho-Hsuan
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2020
畢業學年度：	108
語文別：	英文
論文頁數：	159
中文關鍵詞：	氮轉移試劑、重氮化合物、重氮鹽、三氮烯
外文關鍵詞：	N-tranfer reagent, diazo compound, diazonium salt, triazene
相關次數：	點閱：51 下載：0
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利用實驗室所發展之氮轉移試劑針對較敏感的官能基進行耐受度及化學選擇性之測試──重氮鹽與胺類反應形成中間體三氮烯，藉由三氮烯的裂解取得重氮化合物 (Scheme 2)。
重氮化合物具有廣泛的應用性，在先前的研究中，雖然重氮化合物的合成已發展出多種方法，但多數條件及反應所需起始物仍受到許多限制，例如它們反應的起始物需要經過多步的合成，或者高危險性的條件如強氧化劑、強酸、強鹼等等條件才能取得，這些方法相對耗時且不易操作，由於條件嚴苛的問題，導致重氮化合物合成之結構因此受到局限，難以合成出多樣的產物，為了解決以上問題，本實驗室致力於發展、設計出一種較溫和且可廣泛利用的方法，進而改善先前合成的問題。
本實驗室已發展了一種新穎的試劑，可將胺基逕轉為重氮化合物的氮轉移試劑，也已經對此試劑之性質及穩定性深入探討，然而在本篇論文中，為了更進一步的瞭解此試劑條件下胺類的官能基耐受度，我們利用新一代的氮轉移試劑進行反應之測試，將已確定穩定於此反應的N-Boc-glycine-N-benzylamide作為基本架構，藉此延伸出多種具有較敏感官能基的反應物，以此方法來了解各種官能基在反應條件中的穩定性及試劑對於不同官能基與胺類之間的化學選擇性。
從實驗結果來看，此試劑及反應條件都相當溫和，對帶有不同敏感之官能基均表現相當穩定的產率，每個例子都維持70%以上不錯的產率，也在實驗中發現了一些反應對於不同官能基可能產生的問題並且做了一些改善，以便於此試劑運用於多種化合物及更廣泛的領域中。

In this essay, we used the N-transfer reagent our laboratory developed to test the tolerance and chemoselectivity of functional groups that are more sensitive. The main idea is based on the decomposition of the intermediate, triazene, which is formed by diazonium salt reacting with amine, to obtain the diazo (Scheme 1).
Although there are many different pathways to synthesize the diazo compounds, most conditions and substrates are still limited. In these methods, some conditions are harsh, and some require specific structures. For example, their substrates require more steps for synthesis or dangerous conditions such as reactive oxidants, strong acid and strong base. The reasons above result to the limitation of diazo, making it difficult to synthesize various structures. Therefore, we dedicate to designing a milder method that can be widely applied to various fields.
Our laboratory developed a novel N-transfer reagent for directly converting amines into diazo compounds. We also explored the properties and stabilities of the reagent. Moreover, we want to further understand the tolerance of the functional groups under our reaction condition. We used the stable N-transfer reagent to demonstrate our reactions, and chose N-Boc-glycine-N-benzylamide, which is stable in our reactions, as the basic skeleton. Also, substrates with more sensitive functional groups derived from this skeleton. By this method, we can understand the stability of various functional groups in our reaction condition, and the chemoselectivity between amine and different functional groups of the reagent.
The reaction presented excellent results and gave good yields over 70%. We also made some improvements on the problems we encountered, so that this reagent can be applied to multiple structures and more extensive fields.

Abstract	I
摘要	II
致謝	III
Table of Contents	IV
List of Figure	VI
List of Tables	VII
List of Schemes	VIII
Abbreviation	X
1.	Introduction	1
1-1.	Diazo compound	1
1-2.	α-Diazocarbonyl compounds	2
1-3.	Triazenes	4
1-4.	Diazonium salt	5
1-5.	Motivation	6
2.	Results and Discussion	8
2-1.	N-transfer reagent	8
2-2.	Experimental designs	8
2-3.	Formation of substrates	10
2-4.	N-transfer reaction	25
3.	Conclusion	33
4.	Experimental Section	34
4-1. General information	34
4-2. General procedure for the synthesis of compound 1f-1h, 1u	35
4-3. General procedure for the synthesis of compound 5u, 1u	36
4-4. Synthesis of compound 1i	37
4-5. General procedure for the synthesis of compound 2a-2i	38
4-6. Synthesis of compound 2j	45
4-7. Synthesis of compound 2k	45
4-8. Synthesis of compound 2l	46
4-9. Synthesis of compound 2m	47
4-10. Synthesis of compound 2n	48
4-11. Synthesis of compound 2o	49
4-12. Synthesis of compound 2p	50
4-13. Synthesis of compound 2q	51
4-14. Synthesis of compound 2r-2t	52
4-15. Synthesis of compound 2u	54
4-16. General procedure for the synthesis of compound 3a-3u	55
4-17. General procedure for the synthesis of compound 4a-4u	68
4-18. General procedure for the synthesis of compound 5f-5h, 5u	79
4-19. Synthesis of compound 6-9 (N-transfer reagent)	81
4-20. Synthesis of compound 10.11	84
5.	Reference	86
6.	Appendix	91
                                    

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