Ye PhD Candidate PTN Program NIBSChemistry Center 12272019 Introduction Isodon species Orindon 冬凌草甲素 Introduction Introduction Introduction Category Introduction Category ID: 1047140
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1. Molecule of The Year !Zhang Ye Ph.D. CandidatePTN Program, NIBS-Chemistry Center12-27-2019
2. IntroductionIsodon speciesOrindon, 冬凌草甲素
3. Introduction
4. Introduction
5. Introduction: Category
6. Introduction: Category
7. Introduction: Category
8. Introduction: Category
9. Introduction: Biogenesis
10. Introduction: Biogenesis
11. Scientific QuestionHow to achieve the enantioselective total synthesis of (−)-Oridonin ?
12. Previous Studies toward the Total Synthesis of ent-kauranoids(±)-Kaurene (Ireland, 1962)(±)-Kaurenoic (Mori, 1966)(±)-Steviol (Mori, 1970)(±)-Steviol methyl ester (Ziegler, 1977)(±)-Cafestol and atractyligenin (Corey, 1987)(±)-Isosteviol (Snider, 1998)(±)-Steviol (Baran, 2013)(±)-Cafestol (Hong, 2014)(-)-Oridonin A (Zhou, 1992)Lungshengenin D (Ma, 2017)(-)-Oridonin A (Luo, 2019)
13. Previous Studies toward the Total Synthesis of ent-kauranoids(±)-Kaurene (Ireland, 1962)(±)-Kaurenoic (Mori, 1966)(±)-Steviol (Mori, 1970)(±)-Steviol methyl ester (Ziegler, 1977)(±)-Cafestol and atractyligenin (Corey, 1987)(±)-Isosteviol (Snider, 1998)(±)-Steviol (Baran, 2013)(±)-Cafestol (Hong, 2014)(-)-Oridonin A (Zhou, 1992)Lungshengenin D (Ma, 2017)(-)-Oridonin A (Luo, 2019)
14. (±)-Kaurenoic (Mori, 1966)
15. Previous Studies toward the Total Synthesis of ent-kauranoids(±)-Kaurene (Ireland, 1962)(±)-Kaurenoic (Mori, 1966)(±)-Steviol (Mori, 1970)(±)-Steviol methyl ester (Ziegler, 1977)(±)-Cafestol and atractyligenin (Corey, 1987)(±)-Isosteviol (Snider, 1998)(±)-Steviol (Baran, 2013)(±)-Cafestol (Hong, 2014)Lungshengenin D (Ma, 2017)(-)-Oridonin A (Zhou, 1992)(-)-Oridonin A (Luo, 2019)
16. (±)-Steviol methyl ester (Ziegler, 1977)
17. Previous Studies toward the Total Synthesis of ent-kauranoids(±)-Kaurene (Ireland, 1962)(±)-Kaurenoic (Mori, 1966)(±)-Steviol (Mori, 1970)(±)-Steviol methyl ester (Ziegler, 1977)(±)-Cafestol and atractyligenin (Corey, 1987)(±)-Isosteviol (Snider, 1998)(±)-Steviol (Baran, 2013)(±)-Cafestol (Hong, 2014)Lungshengenin D (Ma, 2017)(-)-Oridonin A (Zhou, 1992)(-)-Oridonin A (Luo, 2019)
18. (±)-Steviol (Baran, 2013)
19. Previous Studies toward the Total Synthesis of ent-kauranoids(±)-Kaurene (Ireland, 1962)(±)-Kaurenoic (Mori, 1966)(±)-Steviol (Mori, 1970)(±)-Steviol methyl ester (Ziegler, 1977)(±)-Cafestol and atractyligenin (Corey, 1987)(±)-Isosteviol (Snider, 1998)(±)-Steviol (Baran, 2013)(±)-Cafestol (Hong, 2014)(-)-Oridonin A (Zhou, 1992)Lungshengenin D (Ma, 2017)(-)-Oridonin A (Luo, 2019)
20. (±)-Cafestol (Hong, 2014)
21. Previous Studies toward the Total Synthesis of ent-kauranoids(±)-Kaurene (Ireland, 1962)(±)-Kaurenoic (Mori, 1966)(±)-Steviol (Mori, 1970)(±)-Steviol methyl ester (Ziegler, 1977)(±)-Cafestol and atractyligenin (Corey, 1987)(±)-Isosteviol (Snider, 1998)(±)-Steviol (Baran, 2013)(±)-Cafestol (Hong, 2014)(-)-Oridonin A (Zhou, 1992)Lungshengenin D (Ma, 2017)(-)-Oridonin A (Luo, 2019)
22. Lungshengenin D (Ma, 2017)
23. Previous Studies toward the Total Synthesis of ent-kauranoids(±)-Kaurene (Ireland, 1962)(±)-Kaurenoic (Mori, 1966)(±)-Steviol (Mori, 1970)(±)-Steviol methyl ester (Ziegler, 1977)(±)-Cafestol and atractyligenin (Corey, 1987)(±)-Isosteviol (Snider, 1998)(±)-Steviol (Baran, 2013)(±)-Cafestol (Hong, 2014)(-)-Oridonin A (Zhou, 1992)Lungshengenin D (Ma, 2017)(-)-Oridonin A (Luo, 2019)
24. (-)-Oridonin A (Luo, 2019)Retrosynthetic AnalysisSakurai reaction.Alkene as the nucleophile to trap the intermediate(Carbocation)L.A-catalyzed. Carbocation as thedriving force for the rearrangement.1,2-migration(acyloin rearrangement)
25. (-)-Oridonin A (Luo, 2019)The stereochemistry (C1 and C16) has paramount importance on the proposed Nazarov/Hosomi−Sakurai cascade
26. (-)-Oridonin A (Luo, 2019)
27. Summary1,2-migration(acyloin rearrangement)1,2-migration (alkyl-shift and H-shift)Summary, and something you can take home
28. SummaryA cascade sequence of Prins cyclization and Wagner−Meerwein rearrangement to construct the core of arcutinidine. (Ang Li, 2019, )Carbocation as thedriving force for the rearrangement.(−)-Maoecrystal V (P. S. Baran, 2016)
29. Summary(±)-Steviol (Baran, 2013)Talatisamine (Inoue, 2019)
30. SummaryAgain, the carbocation
31. Key References1. Constructive innovation of approaching bicyclo[3.2.1]octane in ent-kauranoids2. Total Synthesis of (−)-Oridonin: An Interrupted Nazarov Approach3. Asymmetric Total Synthesis of Arcutinidine, Arcutinine, and Arcutine4. Discovery and development of natural product oridonin-inspired anticancer agents5. 11-Step Total Synthesis of (−)-Maoecrystal V6. Total Synthesis of Talatisamine
32. Thank you for your attention !
33. Thank you for your attention !— naughty cation