PDF herunterladen
Synlett 2023; 34(04): 327-331
DOI: 10.1055/a-1984-0686
account

Total Synthesis of the Caged Diterpenoid Atropurpuran

Jing Xu  ∗
a   Department of Chemistry and Shenzhen Grubbs Institute and Guangdong Provincial Key Laboratory of Catalysis and Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Southern University of Science and Technology, Shenzhen 518055, P. R. of China
b   Shenzhen Bay Laboratory, Shenzhen 518132, P. R. of China
› InstitutsangabenThis research was funded by NSFC (21971104 and 22271136), ­Education Department of Guangdong Province, Key research projects in colleges and universities in Guangdong Province (2021ZDZX2035), Shenzhen Bay Laboratory (SZBL2019062801006), Guangdong Provincial Key Laboratory of Catalysis (2020B121201002), Shenzhen Nobel Prize Scientists Laboratory Project (C17783101), Guangdong Innovative Program (2019BT02Y335), Innovative Team of Universities in Guangdong Province (2020KCXTD016) and Shenzhen Science and Technology Innovation Committee (ZDSYS20190902093215877, JCYJ20190809140611364).
› Weitere Informationen
    Lizenzen und Reprints Alle Artikel dieser Rubrik


Abstract

In this account, we wish to share some stories behind our 13-step synthesis of the caged complex diterpenoid atropurpuran. Although our approach might appear to have proceeded smoothly, the unraveling of the core-construction puzzle and late-stage decorations was full of drama.

1 Introduction

2 Total Synthesis of Atropurpuran

3 Conclusion

Key words

atropurpuran - diterpenoids - total synthesis - caged natural products - ring-closing metathesis - Diels–Alder reaction


Publikationsverlauf

Eingereicht: 02. November 2022

Angenommen nach Revision: 22. November 2022

Accepted Manuscript online:
22. November 2022

Artikel online veröffentlicht:
19. Dezember 2022

© 2022. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

  • References and Notes

  • 1 Tang P, Chen Q.-H, Wang F.-P. Tetrahedron Lett. 2009; 50: 460
    Crossref
    • 2a Wang F.-P, Liang X.-T. Alkaloids (San Diego, CA U. S.) 2002; 59: 1
    • 2b Wang F.-P, Chen Q.-H, Liu X.-Y. Nat. Prod. Rep. 2010; 27: 529
      CrossrefPubMed
    • 2c Cherney EC, Baran PS. Isr. J. Chem. 2011; 51: 391
      CrossrefPubMed
    • 2d Hamlin AM, Kisunzu JK, Sarpong R. Org. Biomol. Chem. 2014; 12: 1846
      CrossrefPubMed
    • 2e Liu X.-Y, Qin Y. Asian J. Org. Chem. 2015; 4: 1010
      Crossref
    • 2f Zhu G, Liu R, Liu B. Synthesis 2015; 47: 2691
      Artikel in Thieme Connect
    • 2g Liu X.-Y, Qin Y. Nat. Prod. Rep. 2017; 34: 1044
      CrossrefPubMed
    • 2h Liu X.-Y, Ke B.-W, Qin Y, Wang F.-P. Alkaloids (San Diego, CA U. S.) 2022; 87: 1
    • 2i Liu X.-Y, Wang F.-P, Qin Y. Acc. Chem. Res. 2021; 54: 22
      CrossrefPubMed
    • 2j McCowen SV, Doering NA, Sarpong R. Chem. Sci. 2020; 11: 7538
      CrossrefPubMed
  • 3 Gong J, Chen H, Liu X.-Y, Wang Z.-X, Nie W, Qin Y. Nat. Commun. 2016; 7: 12183
    CrossrefPubMed
  • 4 Xie S, Chen G, Yan H, Hou J, He Y, Zhao T, Xu J. J. Am. Chem. Soc. 2019; 141: 3435
    CrossrefPubMed
  • 5 Suzuki T, Koyama T, Nakanishi K, Kobayashi S, Tanino K. J. Org. Chem. 2020; 85: 10125
    CrossrefPubMed
  • 6 Nie W, Gong J, Chen Z, Liu J, Tian D, Song H, Liu X.-Y, Qin Y. J. Am. Chem. Soc. 2019; 141: 9712
    CrossrefPubMed
  • 7 Zhou S, Xia K, Leng X, Li A. J. Am. Chem. Soc. 2019; 141: 13718
    CrossrefPubMed
  • 8 Owens KR, McCowen SV, Blackford KA, Ueno S, Hirooka Y, Weber M, Sarpong R. J. Am. Chem. Soc. 2019; 141: 13713
    CrossrefPubMed
  • 9 Huck CJ, Boyko YD, Sarlah D. Nat. Prod. Rep. 2022; 58 DOI: 10.1039/d2np00042c.
    CrossrefPubMed
  • 10 Suzuki T, Sasaki A, Egashira N, Kobayashi S. Angew. Chem. Int. Ed. 2011; 50: 9177
    CrossrefPubMed
  • 11 Lin S, Song C.-X, Cai G.-X, Wang W.-H, Shi Z.-J. J. Am. Chem. Soc. 2008; 130: 12901
    CrossrefPubMed
  • 12 Hethcox JC, Shockley SE, Stoltz BM. Angew. Chem. Int. Ed. 2016; 55: 16092
    CrossrefPubMed
    • 13a Fernández González D, Brand JP, Waser J. Chem. Eur. J. 2010; 16: 9457
      CrossrefPubMed
    • 13b Long R, Huang J, Shao W, Liu S, Lan Y, Gong J, Yang Z. Nat. Commun. 2014; 5: 5707
      CrossrefPubMed
  • 14 Abelman MM, Overman LE, Tran VD. J. Am. Chem. Soc. 1990; 112: 6959
    CrossrefPubMed

      • The step count here is based on the literature definition [A reaction step is defined as one in which a substrate is converted into a product in a single reaction flask (irrespective of the number of transformations) without intermediate workup or purification], see:
    • 15a Kawamura S, Chu H, Felding J, Baran PS. Nature 2016; 532: 90
      CrossrefPubMed
    • 15b Chu H, Smith JM, Felding J, Baran PS. ACS Cent. Sci. 2017; 3: 47
      CrossrefPubMed
    • 16a Hoffmann RW. Synthesis 2006; 3531
      Artikel in Thieme Connect
    • 16b Young IS, Baran PS. Nat. Chem. 2009; 1: 193
    • 16c Saicic RN. Tetrahedron 2014; 70: 8183
    • 16d Protecting-Group-Free Organic Synthesis: Improving Economy and Efficiency. Fernandes RA. Wiley-VCH; Weinheim: 2018
      Google Scholar
    • 16e Hui C, Chen F, Pu F, Xu J. Nat. Rev. Chem. 2019; 3: 85

      For our other syntheses of caged natural products, see:
    • 17a Guo L.-D, Chen Y, Xu J. Acc. Chem. Res. 2020; 53: 2726
    • 17b Chen Y, Hu J, Guo L.-D, Zhong W, Ning C, Xu J. Angew. Chem. Int. Ed. 2019; 58: 7390
    • 17c Guo L.-D, Hou J, Tu W, Zhang Y, Zhang Y, Chen L, Xu J. J. Am. Chem. Soc. 2019; 141: 11713
    • 17d Guo L.-D, Hu J, Zhang Y, Tu W, Zhang Y, Pu F, Xu J. J. Am. Chem. Soc. 2019; 141: 13043
    • 17e Guo L.-D, Zhang Y, Hu J, Ning C, Fu H, Chen Y, Xu J. Nat. Commun. 2020; 11: 3538
    • 17f Zhang Y, Chen Y, Song M, Tan B, Jiang Y, Yan C, Jiang Y, Hu X, Zhang C, Chen W, Xu J. J. Am. Chem. Soc. 2022; 144: 16042
    • 17g Xie S, Ning C, Yu Q, Hou J, Xu J. Chin. J. Chem. 2021; 39: 137
      Crossref
    • 17h Zhao N, Yin S, Xie S, Yan H, Ren P, Chen G, Chen F, Xu J. Angew. Chem. Int. Ed. 2018; 57: 3386
      CrossrefPubMed
    • 17i Hu J, Guo L.-D, Chen W, Jiang Y, Pu F, Ning C, Xu J. Org. Lett. 2022; 24: 7416