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Attempted Azidation of Carbohydrate Secondary Alcohols Using Arylsulfonyl Azides

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Attempted Azidation of Carbohydrate Secondary Alcohols Using Arylsulfonyl Azides Attempted Azidation of Carbohydrate Secondary Alcohols Using Arylsulfonyl Azides by Morgan Mayieka Submitted in Partial Fulfilment of the Requirements for the Degree of Master of Science in the Chemistry Program YOUNGSTOWN STATE UNIVERSITY August 2020 Attempted Azidation Of Carbohydrate Secondary Alcohols Using Arylsulfonyl Azides Morgan Ongaga Mayieka I hereby release this thesis to the public. I understand this thesis will be made available from the OhioLINK ETD Center and the Maag Library Circulation Desk for public access. I also authorize the University or other individuals to make copies of this dissertation as needed for scholarly research. Signature: ____________________________________________________________ Morgan Ongaga Mayieka, Student Date Approvals: ____________________________________________________________ Dr. Peter Norris, Thesis Advisor Date ____________________________________________________________ Dr. John A. Jackson, Committee Member Date ____________________________________________________________ Dr. Nina Stourman, Committee Member Date ____________________________________________________________ Dr. Salvatore A. Sanders, Dean of Graduate Studies Date Thesis Abstract This thesis deals with an attempted “one-pot”azidation of carbohydrate secondary alcohols using arylsulfonyl azides. It also deals with the investigation of the reaction mechanism through which the attempted azidation process takes place. The results showed that the attempted azidation did not occur. Instead, the reactions led to the isolation of different sulfonate ester intermediates. A combination of steric (and stereoelectronic) problems were suspected to be the probable cause shutting down the substitution pathway. iii Acknowledgements I would like to, most sincerely, thank Dr. Peter Norris for not only being my research advisor but also my mentor. Thank you for being so patient with me and making me realize my potential both in research and course work. I would also like to thank Dr. John Jackson for making me a better person in synthesis of organic compounds and for being in my thesis committee. I also thank Dr. Sherri Lovelace for the advice and encouragement. I am also indebted to thank Dr. Chris Arnsten for the wonderful insight on Spartan Molecular Modeling, Dr. Matthias Zeller for the X-ray crystal data, Dr. Caleb Tatebe for helping me draw crystal structures and Ray Hoff for teaching me how to use the NMR instrumentation. I am grateful to the YSU chemistry department and the YSU graduate school for giving me a wonderful opportunity and financial support in my studies. I thank the entire YSU chemistry faculty especially Dr. Nina Stourman for being in my thesis committee and Dr. Douglas Genna for the knowledge he imparted in me. I am grateful to my colleagues in the Norris research group; Moffat, Angela, Haron and Salam, for making my graduate experience enjoyable. I would also like to thank my family and friends for being so supportive throughout this course. Lastly, I would like to thank God for the gift of life and for seeing me through this entire process. iv Table of Contents Title Page...........…………………………………………………………………………. i Signature Page…………………………………………………………………………… ii Abstract.………………….…..…………………………………………………………. iii Acknowledgements……………………………………………………………………... iv Table of Contents…..……………………………………………………………………. v List of Figures………………………………………………………………………....... vii List of Tables……………………………………………………………………………. ix List of Schemes……………………………………………………………………..……. x List of Equations…………………………………………………………………………. x Introduction Azides…………………………………………………………………………………….. 1 Synthesis of Organic Azides…….……………………………………………………….. 3 Statement of Problem……...………………………………………………………...…… 8 Results and Discussion……………………………………………………………..…….. 9 Conclusion………………………………………………………………………………. 27 Experimental Synthesis of p-nitrobenzenesulfonyl azide (2)…………………………………………. 27 Synthesis of o-nitrobenzenesulfonyl azide (4)…………………………………………. 28 Reaction of diacetone glucose with o-nitrobenzenesulfonyl azide (4)…………..……. 29 3-O-Sulfonate ester intermediate (6) from o-nitrobenzenesulfonyl chloride (3)………. 30 3-O-Sulfonate ester intermediate (6) from o-nitrobenzenesulfonyl chloride (3)………. 32 v Side reaction product (8) from o-nitrobenzenesulfonyl chloride and nimethylamino- pyridine………………………………………………………………………………..... 33 3-O-Sulfonate Ester Intermediate (9) from p-nitrobenzenesulfonyl chloride…………... 34 1,2:5,6-di-o-isopropylidene-3-o-toluenesulfonyl-α-D-glucofuranose (11).…………….. 35 1,2:5,6-Di-O-isopropylidene-3-O-trifluoromethanesulfonyl-α-D-glucofuranose (12)..... 36 Attempted Synthesis of 1,2:5,6-Di-O-isopropylidene-3-azido-3-deoxy-α-D-allofuranose (7)……………………………………………………………………………………...... 37 3-Deoxy-1,2:5,6-di-o-isopropylidene-α-D-erythrohex-3-enofuranose (13) from the Tosylate (11)……………………………………………………………………………. 38 o-Nitrobenzenesulfonate ester (17)……………………………………………………... 39 Preparation of the azide anion…………………………………………………………... 40 References………………………………………………………………………………. 41 Appendix A NMR and IR spectra data.………………………………………………………….….... 43 vi List of Figures Figure 1 A general form of an organic azide……………………………………… 1 Figure 2 A β-glucosyl azide structure……………………… …………………….. 2 Figure 3 Zidovudine structure…….……………………………………………….. 2 Figure 4 Structures of DPPA, bis(p-nitrophenyl) phosphorazidate and bis(2,4- dichlorophenyl) phosphate……………………………………………….. 5 Figure 5 Triphenylphosphine structure………….………………………………… 6 Figure 6 The structures of p-nitrobenzenesulfonyl azide and o-nitrobenzenesulfonyl azide………………………………...……………………………………. 7 Figure 7 Diacetone D-glucose structure……………..…………………………….. 8 Figure 8 X-Ray crystal structure of 3-O-(2-nitrobenzenesulfonate) ester 6……... 13 Figure 9 Structure of the suspected side product due to the side reaction between DMAP and o-NBSCl…………………………………………………… 15 Figure 10 1H NMR spectrum of the attempted synthesis of 1,2:5,6-di- -3-azido-3-deoxy- α-D-allofuranose 7………….………………………. 19 Figure 11 1H NMR spectrum of 1,2:5,6-di-O-isopropylidene-3- O- trifluoromethanesulfonyl-α-D-glucofuranose 12……………………….. 19 Figure 12 1H NMR spectrum of 3-deoxy-1,2:5,6-di-o-isopropylidene-α-D- erythrohex-3-enofuranose 13…………………………………………… 19 Figure 13 Minimized structure of 3-O-(2-nitrobenzenesulfonate) ester 6………… 23 Figure 14 1H NMR spectrum of p-nitrobenzenesulfonyl azide 2………………….. 44 vii Figure 15 13C NMR spectrum of p-nitrobenzenesulfonyl azide 2……...………….. 45 Figure 16 1H NMR spectrum of o-nitrobenzenesulfonyl azide 4………………….. 46 Figure 17 13C NMR spectrum of o-nitrobenzenesulfonyl azide 4……...………….. 47 Figure 18 1H NMR spectrum of 3-O-Sulfonate ester intermediate 6……………… 48 Figure 19 13C NMR spectrum of 3-O-Sulfonate ester intermediate 6……….….… 49 Figure 20 1H NMR spectrum of attempted synthesis of 1,2:5,6-di-O-isopropylidene-3-azido-3-deoxy-α-D-allofuranose 7…….. 50 Figure 21 13C NMR spectrum of attempted synthesis of 1,2:5,6-di-O-isopropylidene-3-azido-3-deoxy-α-D-allofuranose 7…….. 51 Figure 22 1H NMR spectrum of side reaction product 8 …………………………. 52 Figure 23 13C NMR spectrum of side reaction product 8 …………………………. 53 Figure 24 1H NMR spectrum of 3-O-Sulfonate Ester Intermediate 9……………... 54 Figure 25 13C NMR spectrum of 3-O-Sulfonate Ester Intermediate 9……………... 55 Figure 26 1H NMR spectrum of 1,2:5,6-di-o- isopropylidene-3-o-toluenesulfonyl-α-D-glucofuranose 11……………. 56 Figure 27 13C NMR spectrum of 1,2:5,6-di-o- isopropylidene-3-o-toluenesulfonyl-α-D-glucofuranose 11……………. 57 Figure 28 1H NMR spectrum of 1,2:5,6-di-O- isopropylidene-3-O-trifluoromethanesulfonyl-α-D-glucofuranose 12….. 58 Figure 29 13C NMR spectrum of 1,2:5,6-di-O- viii isopropylidene-3-O-trifluoromethanesulfonyl-α-D-glucofuranose 12….. 59 Figure 30 1H NMR spectrum of 3-deoxy-1,2:5,6-di-o-isopropylidene-α- D-erythrohex-3-enofuranose 13………………………………………… 60 Figure 31 13C NMR spectrum of 3-deoxy-1,2:5,6-di-o-isopropylidene-α- D-erythrohex-3-enofuranose 13………………………………………… 61 Figure 32 1H NMR spectrum of o-nitrobenzenesulfonate ester 17………………… 62 Figure 33 13C NMR spectrum of o-nitrobenzenesulfonate ester 17………………… 63 Figure 34 IR spectrum of ionic azide Scheme 7……………………………………. 64 Figure 35 IR spectrum showing the formation of an ionic azide…………………… 65 List of Tables Table 1 List of conditions varied for the synthesis of 3-O-(2- nitrobenzenesulfonate) ester from o-nitrobenzenesulfonyl chloride….... 14 Table 2 Duration of Spartan model energy minimization……………………….. 20 Table 3 Various angles within different sulfonate esters as calculated by the Spartan molecular modeling software………………………...………… 21 Table 4 Spartan models of o-nitrosulfonate ester 6 intermediate synthesized…… 22 Table 5 Spartan models of p-nitrosulfonate ester 9 intermediate synthesized…… 24 Table 6 Spartan models of O-(trifluoromethyl)sulfonate ester 12 intermediate synthesized…………………………………………...…… 25 ix List of Schemes Scheme 1 A classic nucleophilic substitution method of azidation…………...…...... 4 Scheme 2 The Mitsunobu method of azidation…………...…………………..…….. 5 Scheme 3 Attempted azide synthesis using p-ABSA………………..…...……….… 7 Scheme 4 Attempted azide synthesis using p-NBSA and o-NBSA………...…..…… 7 Scheme 5 Proposed azidation pathway……………………………………………… 8 Scheme 6 Attempted azidation using o-NBSA……………………………......…… 11 Scheme 7 A suggested reaction mechanism in the generation of the intermediate… 12 List of Equations Equation 1 The 1,3-dipolar cycloaddition reaction………………...…………...…..... 2 Equation 2 An alternative to DEAD in azide synthesis…………....…………..…….. 6 Equation 3 Synthesis of p-nitrobenzenesulfonyl
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