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Graduate School of Ajou University Department of Pharmacy 4. Theses(Ph.D)

Stereoselective Total Syntheses of both (+)-2,5-cis- and (+)-2,5-trans- Tetrahydrofuranoid Oxylipids

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dc.contributor.advisor김형수-
dc.contributor.author장홍준-
dc.date.accessioned2022-11-29T03:01:25Z-
dc.date.available2022-11-29T03:01:25Z-
dc.date.issued2020-02-
dc.identifier.other29841-
dc.identifier.urihttps://dspace.ajou.ac.kr/handle/2018.oak/21148-
dc.description학위논문(박사)--아주대학교 일반대학원 :약학과,2020. 2-
dc.description.tableofcontentsI. Introductions .......................................................................................................... 1 I.1. 3-Oxygenated Tetrahydrofuranoids Natural Products ................................. 2 I.1.1. Mono-THFs ........................................................................................ 2 I.1.2. Fused Bis-THFs .................................................................................. 7 I.1.3. Adjacent Bis-THFs ............................................................................. 9 I.1.4. THF-Containing Macrolides ............................................................ 12 I.1.5. Mono-THF fused with Medium-Sized Ether Ring ........................... 14 I.2. C19 Nematocidal Tetrahydrofuranoids Marine Oxylipids .......................... 17 I.2.1. Introduction: Determination of C19 Nematocidal Tetrahydrofuranoids Oxylipids.................................................................................................... 17 I.2.2. Biosynthetic Pathway of C19 Nematocidal Tetrahydrofuranoids Oxylipids.................................................................................................... 19 I.3. Previous Synthesis of C19 Nematocidal Tetrahydrofuranoids Marine Oxylipids .......................................................................................................... 23 I.3.1. Williams Synthesis of (±)-1a (1984) ................................................ 27 I.3.2. Takano Synthesis of (+)-1a (1985) ................................................... 29 I.3.3. Gurjar Synthesis of (+)-1a (1990) .................................................... 30 I.3.4. Chikashita Synthesis of (+)-1a (1993) ............................................. 31 I.3.5. Wang Synthesis of (+)-1a (1998) ..................................................... 32 I.3.6. Mori Synthesis of (+)-1a (1999) ...................................................... 34 I.3.7. Martin Synthesis of (+)-1a and (+)-1b (2000,2001) ........................ 35 I.3.8. Lowary Synthesis of (+)-1b (2001) .................................................. 37 I.3.9. Yoda Synthesis of (+)-1b (2001) ...................................................... 39 I.3.10. Pradilla Synthesis of (+)-1a (2007, 2009) ...................................... 40 I.3.11. Britton Synthesis of (+)-1a and (+)-1b (2009) ............................... 42 I.3.12. McErlean Synthesis of (−)-1a and (−)-1b (2011) ........................... 44 I.3.13. Spilling Synthesis of (+)-1a and (+)-1b (2012) ............................. 45 I.3.14. Song Synthesis of (+)-1b (2013) .................................................... 47 II. Result and Discussions ....................................................................................... 49 II.1. Previous Studies on Amide Enolate Alkylation ........................................ 49 II.1.1. Kim’s Divergent Construction of 2,5-cis- and 2,5-trans-Disubstituted THFs by Intramolecular Amide Enolate or Nitrile Anion Alkylation ....... 49 II.1.2. Kim’s Protecting Group-Dependent Intermolecular Amide Enolate Alkylation .................................................................................................. 51 II.2. Intramolecular Protecting Group-Dependent Amide Enolate Alkylation . 53 II.2.1. Substrate Scope for IAEA Reaction ................................................ 54 II-3. Total Synthesis of C19 Nematocidal Tetrahydrofuranoids Oxylipids 1a and 1b ................................................................................................................ 59 II-3-1. Retrosynthetic Plan ......................................................................... 59 II-3-2. Construction of key 2,5-trans- and 2,5-cis-THF intermediates 3a and 3b ............................................................................................................... 61 II-3-3. Determination the Relative Stereochemistries of IAEA Adducts in Scheme 25 and 26 by Chemical Correlations ............................................ 69 II-3-4. Construction of 2,3-trans-2,5-trans- and 2,3-trans-2,5-cis-THFs 3c and 3d ........................................................................................................ 71 II-3-5. Determination the Relative Stereochemistries of IAEA Adducts in Scheme 31 and 32 by Chemical Correlations ............................................ 75 II-3.6. Completion of the Total Synthesis of 1a and 1b ............................ 77 III. Conclusions ....................................................................................................... 80 IV. Exprimentals ...................................................................................................... 81 V. References ........................................................................................................ 195-
dc.language.isoeng-
dc.publisherThe Graduate School, Ajou University-
dc.rights아주대학교 논문은 저작권에 의해 보호받습니다.-
dc.titleStereoselective Total Syntheses of both (+)-2,5-cis- and (+)-2,5-trans- Tetrahydrofuranoid Oxylipids-
dc.title.alternativeHongJun Jang-
dc.typeThesis-
dc.contributor.affiliation아주대학교 일반대학원-
dc.contributor.alternativeNameHongJun Jang-
dc.contributor.department일반대학원 약학과-
dc.date.awarded2020. 2-
dc.description.degreeDoctoral-
dc.identifier.localId1133985-
dc.identifier.uciI804:41038-000000029841-
dc.identifier.urlhttp://dcoll.ajou.ac.kr:9080/dcollection/common/orgView/000000029841-
dc.description.alternativeAbstractThe concise, highly stereoselective, substrate-controlled asymmetric total syntheses of both 2,5-trans- and 2,5-cis-tetrahydrofuranoid nematocidal oxylipids from the Australian brown algae Notheia anomala have been accomplished in a stereodivergent fashion. The highly stereoselective intramolecular amide enolate alkylation strategy provides access to both stereoisomers of the 3-hydroxy-2,5- disubstituted tetrahydrofuran core of these marine natural products through chelate and nonchelate control, which is driven by the C(3)-hydroxy protecting group. This approach offers an optional and highly stereoelective access to any of the eight possible stereoisomers of the 2,5-disubstituted-3-oxygenated tetrahydrofuran skeleton, an important structural feature which is present in many biologically active natural products.-
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