本論文為開發以一價銅以及二價銠金屬之催化合成策略，過程中經由N-磺醯化-1,2,3-三唑 (N-sulfonyl-1,2,3-triazoles) 化合物脫氮合成各種不同含氮之雜環化合物。利用一價銅催化反應，會經由N-磺醯化乙烯亞胺 (ketenimine)中間體，而以二價銠金屬催化，則會經由氮代乙烯銠化類碳烯 (aza vinyl rhodium carbenoid) 中間體，相對應兩種不同的反應過程。其中，成功地發展了以一價銅進行催化反應，從相對應的炔丙醯胺 (N-propargylamides) 化合物經由乙烯亞胺中間體，可以簡易地製備二氫嘧啶 (dihydropyrimidinone) 類似物的方法。這個合成策略同時也應用在從α-胺基酸合成β-胺基酸類似物。然後透過有效的銅/銠金屬催化反應，從N-炔丙基苯胺 (N-propargylanilines) 經由二價銠金屬催化脫氮環化 (N-sulfonyl-1,2,3-triazoles) 合成3-吲哚亞胺 (3-indolylimines)。最後，我們也展示了，利用一價銅催化經由乙烯亞胺中間體之合成策略，可以應用在合成所感興趣的醣類目標分子。這些過程顯示透過溫和且有效的反應條件，發展於合成各種廣泛的基材，特別是可以應用在多樣化小分子資料庫的合成。

In this research, we have developed new methodologies to synthesize various N-heterocyclic compounds using copper (I) and rhodium (II) catalyzed denitrogenative reactions of N-sulfonyl-1,2,3-triazoles. While the usage of copper catalysts involves N-sulfonyl ketenimine intermediate, the rhodium (II) catalyst generates aza vinyl rhodium carbenoid intermediates. By utilizing copper (I) catalyzed N-sulfonyl ketenimine chemistry, a simple and convenient method to prepare dihydropyrimidinone analogues from the corresponding N-propargylamides was developed. This strategy was also applied in the synthesis of β-amino acids analogues from the equivalent α-amino acids. Later, an efficient Cu/Rh-catalyzed method was developed for the synthesis of 3-indolylimines from N-propargylanilines through Rh(II)-catalyzed denitrogenative annulation of N-sulfonyl-1,2,3-triazoles. Then, copper (I) catalyzed synthesis of 2,3-dihydroquinolinimines has been achieved by applying the N-sulfonyl ketenimine intermediate chemistry to the corresponding N-substituted propargyl anilines. Finally, we have also demonstrated that this copper (I) catalyst N-sulfonyl ketenimine chemistry can be applied in the synthesis of interesting sugar targets. The methods we have developed are consists of mild and effective reaction conditions promise a broad substrate scope particularly can be used in small molecular library and diversity oriented synthesis.

Table of Contents

Thesis Validation Certificate……………………………………………………….……………………i
Thesis Submission Certificate…………………………………………………………………………...ii
Acknowledgements...…………………………………………………………………………...……….iii
Keywords………...……………………………………………………………………………………….v
Abstract in Chinese……………………………………………………………………………………...vi
Abstract in English…………………………………………………………………………………..…vii
Preface………………………………………………………………………………….………………viii
List of Figures………………………………………………………………………….…….…….…...xiv
List of Schemes………………………………………………………………..……………………...…xv
List of Tables…………………………………………………………………………………………...xix
List of 1H, 13C NMR and HRMS spectra………………………………………...………..………..…xx
List of Abbreviations………………………………………………………………………….….....xxxix

Chapter 1:.………………………………………………………………………………..……….…...001
1.1Introduction………………………………………………………………………….……….......…001
1.2 Chemistry of α –diazocarbonyl compounds…………………………………………..……………002
1.2.1 Synthesis of α-diazocarbonyl compounds…………………………………………..…….……...003
1.2.2 Reactivity of α-diazocarbonyl compounds………………………………….………..……….….005
1.2.2.1 Insertion reactions……………………………………………….…….……………..…………007
1.2.2.2 Cyclopropanations…………………………………………………………….….…….………009
1.2.2.3 Reactions with aromatics……………………………………………………….….….………..010
1.3 Chemistry of α- imino diazo intermediate…………………………………………..….….……….012
1.3.1 Copper catalyst denitrogenative reactions via ketenimine intermediate………………….……...013
1.3.2 Modified CuAAC multicomponent reactions (MCR):………………………….………..………016
1.3.2.1 Detailed mechanistic studies………………………………………….…………..…………….019
1.3.2.2 Validity of ketenimine as a key intermediate………………………………….….……………020
1.3.2.3 Copper catalyzed ketenimine chemistry: Intermolecular multicomponent reactions……...……023
1.3.2.4 Intramolecular reactions of N-sulfonyl ketenimine intermediates…………………….………..028
1.4 Rhodium catalyst denitrogenative reactions of N-sulfonyl-1,2,3-triazoles…………….….………..032
1.4.1 Synthesis of N-sulfonyl triazoles…………………………………………………….….………..034
1.4.2 Reactions of N-sulfonyl-1,2,3-triazoles…………………………………………….…………….035
1.4.2.1 Insertion reactions………………………………………………………………….….………..037
1.4.2.2 Cyclopropanation reactions…………………………………………………………….………040
1.4.2.3 Transannulation/ Annulation/ Cyclization reactions…………………………………….……..042
1.5 Research motivation and objective…………………………………………….………………..…..046

Chapter 2: Cu(I)-catalyzed synthesis of dihydropyrimidin-4-ones toward the preparation of β- and β3- amino acid analogs …….………………………………………………………………….……………050
2.1 Introduction…………………………………………………………….…………….……….…….050
2.2 Results and discussion……………………………………………………………….……..……….053
2.3 Synthesis of β-Amino acids analogues……………………………………………….…………….061
2.4 Conclusion………………………………………………………………………………………….063
2.5 Experimental section and spectral data……………………………....………………….……..……063
2.5.1 General considerations…………….………………………………………….….………..……...063
2.5.2 General experimental procedures………………..…………………………..……….….……..064
2.5.3 Representative procedure for the preparation of Dihydropyrimid-4-ones……………………...064
2.5.4 Representative procedure for the preparation of β and β3 amino acid analogs (221-225)…...…071
2.5.5 Representative procedure for the hydrolysis of the dihydropyrimid-4-ones (226 & 227)………....073
2.5.6 Representative procedure for the preparation of chiral propargyl amides
from N-Boc-α-amino acids………………………………………..…………..….……………………075
.
Chapter 3: Synthesis of Substituted 3-Indolylimines and Indole-3-carboxaldehydes by Rhodium(II)-Catalyzed Annulation…………………………………………..………………………….……..….…087
3.1 Introduction……………………………………………………………………………….………..087
3.2 Results and discussion……………………………………………………………………..……….089
3.3 Conclusion.........................................................................................................................................096
3.4. Experimental Procedures and spectral data……………………………….……..………………...096
3.4.1. General considerations.………………………………..…………….…………………………..096
3.4.2 Representative procedure for the preparation of 3-Indolylimines:Synthesis
of (E)-4-methyl-N-((1-methyl-1H-indol-3-yl)methylene)benzenesulfonamide (228)…..……..…..097
3.4.3 Representative procedure for the preparation of Indole-3-carboxyaldehydes: Synthesis of 1-methyl-1H-indole-3-carbaldehyde (251)…….…………………………………………………099
3.4.4 3.4.4 Synthesis of 4-methyl-N-((1-methyl-1H-indol-3-yl)methyl)benzenesulfonamide…..…..100
3.4.5 Representative procedure for the preparation of N-sulfonyltriazoles: Synthesis of N-methyl-N-((1-tosyl-1H-1,2,3-triazol-4-yl)methyl)aniline (a-228)……………………...…………….…...102
3.4.6 Synthesis of N-methyl-N-(prop-2-ynyl)aniline (b-228)……....……………….………..……...104

Chapter 4: Synthesis of 2,3-Dihydroquinolin-4-imines by Cu(I)-Catalyzed Annulation via ketenimine intermediate….………………………………………………..……………………………..……..…..117
4.1 Introduction………………………………………………………………….…………………...…117
4.2 Results and Discussion…………………………………..………..……..………………………....120
4.2.1 Optimization of conditions for Cu (I)-catalyzed annulation……...……………………...………..120
4.2.2 Expansion of substrate scope……………………………………………...……………………..123
4.2.3 Synthetic applications of 2,3-dihydroquinolin-4-imines………………….………….…………..126
4.2.4 Photophysical properties of 2,3-dihydroquinolin-4-imines……………………….……….……..127
4.3 Conclusion……………………………………………………………………..…………….….….130
4.4 Experimental Procedures and spectral data………………………….…………...……..….……….131
4.4.1 General considerations……………………………………………………………..…..…………131
4.4.2 Representative procedure for the synthesis of compound 258………………………….….....….132
4.4.3 Synthesis of N-(1-benzyl-7-methoxy-1,2,3,4-tetrahydroquinolin-4-yl)-4-methylbenzenesulfonamide (284)……………………………..…………….……..…………..136
4.4.4 Representative procedures for the synthesis of 3-methoxy-N-(4-methoxyphenyl)aniline (b-260)……………………………………………………………………………..………….…...137
4.4.5 Representative procedures for the synthesis of 3-methoxy-N-(4-methoxyphenyl)aniline (a-260)………………………………………………………….………….………………………………138
4.4.6 Reaction procedure for the synthesis of compound 290………………………………..………....140
4.4.7 Reaction Procedure for the synthesis of compound 291…………..…………………………....…141

Chapter 5: Copper (I) catalyzed synthesis of 2-deoxy imino sugar analogues and 2-deoxy aldonolactones via ketenimine intermediate ..……………………….……………………..…………………………..161
5.1 Introduction………………………………………………………..…………….………….….…..161
5.2 Results and discussion………………………………………………..…………..…..…….………166
5.3 2D NMR experiment explanation for the compound 328……………..….…….……….…………172
5.4 Conclusion……………………………………………………….……………………….……..….176
5.4 Experimental Procedures…………………………………….…….……..….…………….……….176
5.4.1 General Considerations……………….…………………….…………………….…….…..…….176
5.4.2 Reaction procedure for the synthesis of compound 328………………………………..…....……177
5.4.3 Reaction procedure for the synthesis of compound 340……………………………..……………178
5.4.4 Reaction procedure for the synthesis of compound 322 & 323………………………...….………175
5.4.5 Reaction procedure for the synthesis of compound 324.…………………….………………..…..182
5.4.6 Reaction procedure for the synthesis of compound 325…………………...……………….……..183
5.4.7 Reaction procedure for the synthesis of compound 326…………………….…..……….…..……185
5.4.8 Reaction procedure for the synthesis of compound 327……………………………..……………186
5.4.9 Spectral Data………………………………………………………………….…………………..187


Chapter 6: Conclusions and perspectives………………………..…….………………….…………..198
6.1 Conclusions………………………………………………………………………………….……..199
6.2 Perspectives……………………………………………………………….…………..……………200
References………………………………………………………………………………………….…..202

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