Total asymmetric syntheses of iminosugars
<p>This thesis is concerned with the development of ring-closing iodoamination and ringexpansion methodology and its subsequent application to the asymmetric syntheses of pyrrolidine and piperidine iminosugars.</p> <p><strong>Chapter 1</strong> highlights the remarkable...
| मुख्य लेखकों: | , |
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| अन्य लेखक: | |
| स्वरूप: | थीसिस |
| भाषा: | English |
| प्रकाशित: |
2015
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| विषय: |
| _version_ | 1826278484935180288 |
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| author | Figuccia, A Aude Figuccia |
| author2 | Davies, S |
| author_facet | Davies, S Figuccia, A Aude Figuccia |
| author_sort | Figuccia, A |
| collection | OXFORD |
| description | <p>This thesis is concerned with the development of ring-closing iodoamination and ringexpansion methodology and its subsequent application to the asymmetric syntheses of pyrrolidine and piperidine iminosugars.</p> <p><strong>Chapter 1</strong> highlights the remarkable biological properties displayed by iminosugars and introduces methods for the formation of the pyrrolidine and piperidine sub-classes.</p> <p><strong>Chapter 2</strong> describes investigations into the ring-closing iodoamination of bishomoallylic amines which occurs with concomitant <i>N</i>-debenzylation to give an iodomethyl pyrrolidine scaffold. Conversion to the corresponding aziridinium species followed by its regioselective intermolecular ring-opening by H<sub>2</sub>O enabled the synthesis of (+)-2,5-dideoxy-2,5-imino-Dglucitol (DGDP). A protocol for the preparation of its 1-deoxy-1-amino analogue (+)-ADGDP was also developed.</p> <p><strong>Chapter 3</strong> details studies into the ring-expansion of iodomethyl pyrrolidine scaffolds via the trapping of CO<sub>2</sub> (from NaHCO<sub>3</sub>) to produce cyclic carbonates as single diastereoisomers. Subsequent deprotection of these piperidines allowed the syntheses of (−)-1-deoxymannojirimycin (DMJ) and (+)-1-deoxyallonojirimycin (DANJ) to be completed.</p> <p><strong>Chapter 4</strong> delineates investigations into the trapping of alternative “X=C=Y” electrophiles, via the ring-expansion methodology developed in Chapter 3, initially utilising a model system. These studies culminated in the development of the trapping of <i>p</i>-TsNCO and the application of this methodology in the total asymmetric syntheses of (−)-ADMJ and (+)-ADANJ, the 2-deoxy-2-amino analogues of (−)-DMJ and (+)-DANJ, respectively.</p> <p><strong>Chapter 5</strong> contains full experimental procedures and characterisation data for all compounds synthesised in Chapters 2, 3 and 4.</p> |
| first_indexed | 2024-03-06T23:44:37Z |
| format | Thesis |
| id | oxford-uuid:7075b45f-e3e1-4ae6-a544-4d6e54d4714e |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T23:44:37Z |
| publishDate | 2015 |
| record_format | dspace |
| spelling | oxford-uuid:7075b45f-e3e1-4ae6-a544-4d6e54d4714e2022-03-26T19:37:19ZTotal asymmetric syntheses of iminosugarsThesishttp://purl.org/coar/resource_type/c_db06uuid:7075b45f-e3e1-4ae6-a544-4d6e54d4714eNatural productsOrganic chemistryOrganic synthesisEnglishOxford University Research Archive - Valet2015Figuccia, AAude FigucciaDavies, S<p>This thesis is concerned with the development of ring-closing iodoamination and ringexpansion methodology and its subsequent application to the asymmetric syntheses of pyrrolidine and piperidine iminosugars.</p> <p><strong>Chapter 1</strong> highlights the remarkable biological properties displayed by iminosugars and introduces methods for the formation of the pyrrolidine and piperidine sub-classes.</p> <p><strong>Chapter 2</strong> describes investigations into the ring-closing iodoamination of bishomoallylic amines which occurs with concomitant <i>N</i>-debenzylation to give an iodomethyl pyrrolidine scaffold. Conversion to the corresponding aziridinium species followed by its regioselective intermolecular ring-opening by H<sub>2</sub>O enabled the synthesis of (+)-2,5-dideoxy-2,5-imino-Dglucitol (DGDP). A protocol for the preparation of its 1-deoxy-1-amino analogue (+)-ADGDP was also developed.</p> <p><strong>Chapter 3</strong> details studies into the ring-expansion of iodomethyl pyrrolidine scaffolds via the trapping of CO<sub>2</sub> (from NaHCO<sub>3</sub>) to produce cyclic carbonates as single diastereoisomers. Subsequent deprotection of these piperidines allowed the syntheses of (−)-1-deoxymannojirimycin (DMJ) and (+)-1-deoxyallonojirimycin (DANJ) to be completed.</p> <p><strong>Chapter 4</strong> delineates investigations into the trapping of alternative “X=C=Y” electrophiles, via the ring-expansion methodology developed in Chapter 3, initially utilising a model system. These studies culminated in the development of the trapping of <i>p</i>-TsNCO and the application of this methodology in the total asymmetric syntheses of (−)-ADMJ and (+)-ADANJ, the 2-deoxy-2-amino analogues of (−)-DMJ and (+)-DANJ, respectively.</p> <p><strong>Chapter 5</strong> contains full experimental procedures and characterisation data for all compounds synthesised in Chapters 2, 3 and 4.</p> |
| spellingShingle | Natural products Organic chemistry Organic synthesis Figuccia, A Aude Figuccia Total asymmetric syntheses of iminosugars |
| title | Total asymmetric syntheses of iminosugars |
| title_full | Total asymmetric syntheses of iminosugars |
| title_fullStr | Total asymmetric syntheses of iminosugars |
| title_full_unstemmed | Total asymmetric syntheses of iminosugars |
| title_short | Total asymmetric syntheses of iminosugars |
| title_sort | total asymmetric syntheses of iminosugars |
| topic | Natural products Organic chemistry Organic synthesis |
| work_keys_str_mv | AT figucciaa totalasymmetricsynthesesofiminosugars AT audefiguccia totalasymmetricsynthesesofiminosugars |