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Contents
I. Introduction 11
1. The Classification, Natural Occurrence and Biological Activities of Sugar-mimic Glycosidase Inhibitors 13
1.1. Classification and Natural Occurrence 13
1.1.1. Polyhydroxylated Pyrrolidine Alkaloids 13
1.1.2. Polyhydroxylated Piperidine Alkaloids 14
1.1.3. Polyhydroxylated Pyrrolizidine Alkaloids 18
1.1.4. Polyhydroxylated Indolizidine Alkaloids 20
1.1.5. Polyhydroxylated Nortropane Alkaloids 21
1.2. Biological Activities 23
1.2.1. Glycosidase Inhibition 23
1.2.1.1. Digestive Glycosidases 23
1.2.1.2. Lysosomal Glycosidases 27
1.2.1.3. Processing Glycosidases 28
1.2.2. Cancer and Immune Response 30
1.2.3. Antiviral Activity 32
2. The Synthetic Approaches to Typical Polyhydroxylated Alkaloids as Glycosidase Inhibitors 33
2.1. 1,4-Dideoxy-1,4-Imino-D-Arabinitol(DAB1) 33
2.1.1. Fleet's Approach 33
2.1.2. Kitahara's Approach 35
2.1.3. Trombini's Approach 37
2.1.4. Genisson's Approach(이미지참조) 38
2.2. (-)-Lentiginosine 40
2.2.1. Gurjar's Approach 40
2.2.2. Greene's Approach 41
2.2.3. Brandi's Approach 43
2.2.4. Singh's Approach 45
2.3. D-1-Deoxynojirimycin and Its Analogues 47
2.3.1. Kibayashi's Approach 47
2.3.2. Comins's Approach 50
2.3.3. Hirai's Approach 52
2.3.4. Takahata's Approach 54
3. Chlorosulfonyl Isocyanate in Organic Synthesis 58
3.1. Nucleophilic Addition to the Isocyanate Carbon(Type I) 60
3.1.1. Reactions of HX(X = OR, SR, NR²) 60
3.1.2. Reactions with Carbonyl Compounds (Ketone and Aldehyde) 61
3.1.2.1. Aldehyde 61
3.1.2.2. Ketone 62
3.1.3. Reactions with Carboxylic Acid 63
3.1.4. Reactions with Oxirane and Acetal 64
3.1.4.1. Acetal 64
3.1.4.2. Oxirane 64
3.1.5. Reactions with Aromatic Compounds 65
3.1.6. Reactions with β-Diketones and β-Keto Esters 65
3.2. Cycloaddition to the Isocyanate C=N (Type II) 68
3.2.1. [2+2] Cycloaddition Reaction of Alkenes and CSI 68
3.2.2. [3+2] Annulation of Allylsilanes and CSI 70
3.3. Nucleophilic Addition to the Chlorosulfonyl Portion (Type III) 72
3.4. Reaction of Allyl Ethers with CSI 73
II. Results and Discussion 79
1. Total Synthesis of Polyhydroxylated Alkaloids from Sugar-derived Chiral Template 79
1.1. Regioselective and Diastereoselective Amination of Cinnamyl Polybenzyl Ethers 79
1.1.1. Synthesis of Cinnamyl Polybenzyl Ethers from D-Sugars 80
1.1.2. Reaction of Cinnamyl Polybenzyl Ethers with CSI 82
1.2. Total Syntheses of Polyhydroxylated Alkaloids 87
1.2.1. Total Synthesis of 1,4-Dideoxy-1,4-Imino-D-Arabinitol (DAB1) 88
1.2.2. Total Synthesis of (-)-Lentiginosine 89
1.2.3. Total Synthesis of (1R,2R,7aR)-1,2-Dihydroxypyrrolizidine 91
2. Asymmetric Total Synthesis of Polyhydroxylated Piperidine Alkaloids 93
2.1. An Efficient Stereoselective Synthesis of (2S,3S)-3-Hydroxy-pipecolic Acid and (+)-Febrifugine 93
2.1.1. Reaction of 1,2-Dibenzyl Ethers with CSI 95
2.1.2. Total Synthesis of(2S,3S)-3-Hydroxypipecolic Acid 100
2.1.3. Synthesis of (2R,3S)-2-Hydroxymethylpiperidin-3-ol and (+)-Febrifugine 102
2.2. Concise Enantioselective Syntheses of D-1-Deoxynojirimycin and Its Stereoisomers 103
2.2.1. Total Syntheses of D-1-Deoxymannojirimycin and D-1-Deoxyallonojirimycin 105
2.2.2. Total Syntheses of D-1-Deoxynojirimycin and D-1-Deoxyaltronojirimycin 112
III. Conclusion 116
IV. Experimental Sections 118
General Methods 118
1. Total Synthesis of Polyhydroxylated Alkaloids from Sugar-derived Chiral Template 119
2. Asymmetric Total Synthesis of Polyhydroxylated Piperidine Alkaloids 148
V/IV. References and Notes 186
VI/V. 국문초록 211
VII/VI. Appendix 215
Table 1. Diastereoselective CSI reaction of cinnamyl polybenzyl ether 221 in various solvents and at different temperatures. 83
Table 2. Diastereoselective CSI reaction of cinnamyl polybenzyl ethers 221-224. 84
Table 3. Diastereoselective CSI reaction of anti-1,2-dibenzyl ether 243 in various solvents and at different temperatures. 95
Table 4. Diastereoselective CSI reaction of syn-1,2-dibenzyl ether 244 in various solvents and at different temperatures. 97
Table 5. Diastereoselective dihydroxylation of the piperidine 247. 109
Figure 1. Structure of polyhydroxylated pyrrolidine alkaloids. 13
Figure 2. Structure of nojirimycin and its analogues. 15
Figure 3. Structure of 1-deoxynojirimycin and its analogues. 16
Figure 4. Structure of polyhydroxylated piperidine alkaloids. 17
Figure 5. Structure of polyhydroxylated pyrrolizidine alkaloids. 19
Figure 6. Structure of polyhydroxylated indolizidine alkaloids. 20
Figure 7. Structure of polyhydroxylated nortropane alkaloids. 22
Figure 8. Structure of miglitol and N-butyldeoxynojirimycin. 24
Figure 9. Structure of 1-deoxynojirimycin derivatives. 25
Figure 10. Structure of valienamine derivatives. 26
Figure 11. Structure of acarbose. 27
Figure 12. The processing of the oligosaccharide chains of the N-linked glycoproteins. 29
Figure 13. The classification of CSI reaction types. 59
Figure 14. The stability order of carbocations in solution phase. 75
Figure 15. Reaction mechanism of cinnamyl polybenzyl ethers 221 and 224 with CSI. 86
Figure 16. Structure of biologically active hydroxylated piperidines. 93
Figure 17. Cieplak electronic model of nucleophilic attack toward the p-methoxybenzylic carbocation. 98
Figure 18. Neighboring group effect of nucleophilic attack on the p-methoxybenzylic carbocation. 99
Figure 19. Structure of D-1-deoxynojirimycin and its steroisomers. 103
Figure 20. nOe experimental study of 252a and 252b. 106
Figure 21. Conformational structures of N-alkylated and N-acylated piperidines. 108
Figure 22. Diastereoselective dihydroxylation of unsaturated piperidine 247. 110
Figure 23. Substitution reaction of the tosylates 261a and 261b with CsOAc. 113
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