Synthesis and Characterization of Organic and Inorganic Compounds with Biological and Material Applications Open Access
Jiang, Victoria Shuangbai (2013)
Published
Abstract
The synthesis of an iodonium-bridge activated cyclization model system is reported. A six-membered heterocyclic ether was synthesized through a seven-step linear synthesis using iodine as the activator. The cyclic ether product serves as a model system for generation of the trans-syn-trans stereochemistry displayed within the brevetoxin family. The results suggest that the trans-alkene diol generates a cyclic ether with trans-anti-trans stereochemistry.
A three-step synthetic route to septanose glycal from D-(-)-ribose is also reported. These seven-membered sugar rings can be polymerized to generate biopolymers capable of novel and predictable biological activity. This synthesis includes a one-carbon homologation of acetonide-protected ribofuranose using the Bestmann-Ohira modification of the Seyferth-Gilbert homologation. The subsequent alkynyl diol will be converted to a septanose carbohydrate using a W(CO)6-catalyzed cyclization reaction.
Lastly, the progress towards the synthesis and characterization of monothiopyrophosphate is reported. This pyrophosphate derivative is a promising therapeutic candidate for inhibition of vascular calcification characteristic of patients with increasing age, renal disease and diabetes.
Table of Contents
Table of Contents
I. Stereoselectivity of hydroxyalkene cyclizations: Model systems for the synthesis of marine polycyclization products 1
1. Introduction 1
Figure 1. 2
Figure 2 2
Figure 3 2
Figure 4 3
Figure 5 3
Scheme 1 6
Scheme 2 7
Scheme 3 8
Figure 6. 9
2. Experimental 9
2.1 General Experimental Procedures 9
2.2.1 4-((tert-butyldimethylsilyl)oxy)butanal. 9
2.2.2 (R)-1-((tert-butyldimethylsilyl)oxy)dec-5-yn-4-ol 10
2.2.3 (R,E)-dec-5-ene-1,4-diol. 10
2.2.4 (2S,3R)-2-((R)-1-iodopentyl)tetrahydro-2H-pyran-3-ol 11
2.2.5 (2S,3R)-2-((S)-1-iodopentyl)tetrahydro-2H-pyran-3-yl acetate. 12
2.2.6 (2R,3R)-2-pentyltetrahydro-2H-pyran-3-yl acetate 12
3. Results and Discussion 13
Scheme 4 13
Figure 7. 14
Figure 8. 15
4. Conclusions and Future Studies 15
II. Endo-Selective Alkynol Cycloisomerization: Utilization of One-carbon Homologation to Synthesize Seven-membered Ring Glycals 17
1. Introduction 17
Scheme 5 18
Scheme 6 18
Scheme 7 19
Scheme 8 19
Figure 9 20
2. Experimental 21
2.1 General Experimental Procedures 21
2.2.1 (3aR,6R,6aR)-6-(hydroxymethyl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-ol. 21
2.2.2 Dimethyl (2-oxopropyl)phosphonate 21
2.2.3 Dimethyl (1-diazo-2-oxopropyl)phosphonate. 22
2.2.4 (R)-1-((4R,5S)-5-ethynyl-2,2-dimethyl-1,3-dioxolan-4-yl)ethane-1,2-diol 23
3. Results and Discussion 24
Scheme 9 24
Scheme 10 24
Figure 10 25
Figure 11 26
Figure 12 27
4. Conclusions and Future Studies 28
III. Synthesis and Characterization of Monothiopyrophosphate: A Therapeutic Candidate for Inhibition of Vascular Calcification 29
1. Introduction 29
Figure 13 30
Figure 14 31
Scheme 11 33
2. Experimental 33
2.1 Monothiopyrophosphate 33
3. Results and Discussion 33
Figure 15 34
Figure 16 34
Figure 17 38
Figure 18 38
Figure 19 41
4. Conclusions and Future Studies 41
IV. Literature Cited 43
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