Synthesis 2023; 55(02): 341-346
DOI: 10.1055/a-1700-3520
paper
Special Issue dedicated to Prof. Alain Krief

Stereoselective Total Synthesis of (+)-Brevipolide H from d-Galactal

Ziyang Zhao
a   State Key Laboratory of Environmental Chemistry and Eco-Toxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Science, Beijing 100085, P. R. of China
b   School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, P. R. of China
,
Qingwei Lv
a   State Key Laboratory of Environmental Chemistry and Eco-Toxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Science, Beijing 100085, P. R. of China
b   School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, P. R. of China
,
Jialin Geng
b   School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, P. R. of China
,
Yang Liu
a   State Key Laboratory of Environmental Chemistry and Eco-Toxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Science, Beijing 100085, P. R. of China
b   School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, P. R. of China
,
Chao Hu
a   State Key Laboratory of Environmental Chemistry and Eco-Toxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Science, Beijing 100085, P. R. of China
,
Yuguo Du
a   State Key Laboratory of Environmental Chemistry and Eco-Toxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Science, Beijing 100085, P. R. of China
b   School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, P. R. of China
,
Jun Liu  ∗
a   State Key Laboratory of Environmental Chemistry and Eco-Toxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Science, Beijing 100085, P. R. of China
b   School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, P. R. of China
› Author AffiliationsThis work was supported by the STS Project of Chinese Academy of Sciences (KFJ-STS-QYZD-201-5-1) and the National Key Research and Development Program of China (2019YFC1605802).
› Further Information
    Permissions and Reprints All articles of this category


Abstract

An efficient and concise synthesis of cytotoxic 5,6-dihydro-α-pyrone (+)-brevipolide H has been accomplished in 12 long linear steps in 8.65% overall yield from readily available chiral synthons, d-galactal and ethyl l-lactate. The features of this synthesis are highly diastereoselective Simmons–Smith cyclopropanation and carbohydrate-based chiron approach to rapid access to key 5,6-dihydro-α-pyrone skeleton.

Key words

(+)-brevipolide H - total synthesis - 5,6-dihydro-α-pyrone - d-galactal - chiron approach

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1700-3520.
  • Supporting Information


Publication History

Received: 26 October 2021

Accepted after revision: 17 November 2021

Accepted Manuscript online:
17 November 2021

Article published online:
12 January 2022

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

  • References

  • 1 Hegde VR, Pu H, Patel M, Das PR, Strizki J, Gullo VP, Chou C.-C, Buevich AV, Chan T.-M. Bioorg. Med. Chem. Lett. 2004; 14: 5339
    CrossrefPubMed
  • 2 Deng Y, Balunas MJ, Kim J.-A, Lantvit DD, Chin Y.-W, Chai H, Sugiarso S, Kardono LB. S, Fong HH. S, Pezzuto JM, Swanson SM, Carcache de Blanco EJ, Kinghorn AD. J. Nat. Prod. 2009; 72: 1165
    CrossrefPubMed
  • 3 Suárez-Ortiz GA, Cerda-García-Rojas CM, Hernández-Rojas A, Pereda-Miranda R. J. Nat. Prod. 2013; 76: 72
    CrossrefPubMed
  • 4 Sheng Y.-H, Leu W.-J, Chen C.-N, Hsu J.-L, Liu Y.-T, Hsu L.-C, Hou D.-R, Guh J.-H. Molecules 2020; 25: 2929
    CrossrefPubMed
  • 5 For a recent review, see: Kurniawan YD, Rosyidah A. Beilstein J. Org. Chem. 2021; 17: 2399
    CrossrefPubMed
  • 6 Lin JW, Kurniawan YD, Chang WJ, Leu WJ, Chan SH, Hou DR. Org. Lett. 2014; 16: 5328
    CrossrefPubMed
  • 7 Chen CN, Hou DR. Org. Biomol. Chem. 2016; 14: 6762
    CrossrefPubMed
  • 8 Kumaraswamy G, Jayaprakash N, Rambabu D, Ganguly A, Banerjee R. Org. Biomol. Chem. 2014; 12: 1793
    CrossrefPubMed
  • 9 Mohapatra DK, Kanikarapu S, Naidu PR, Yadav JS. Tetrahedron Lett. 2015; 56: 1041
    Crossref
  • 10 Liu YX, Liu J, Zhao CF, Du YG. Org. Lett. 2021; 23: 3264
    CrossrefPubMed
  • 11 Yu S, Liu YX, Shang CX, Du YG, Liu J. Tetrahedron Lett. 2021; 70: 153072
    Crossref
  • 12 Chang CZ, Geng JL, Liu YX, Du YG, Liu J, Dong ZB. Synthesis 2020; 52: 1576
    Article in Thieme Connect
  • 13 Lv QW, Chang CZ, Li Y, Du YG, Liu J. Tetrahedron 2020; 76: 131290
    Crossref
  • 14 The known allylic alcohol 14 was easily prepared in 74% yield over two steps from ethyl l-lactate, see: Liu J, Gao YG, Wang LL, Du YG. Tetrahedron 2017; 73: 6443
    Crossref
  • 15 Liu J, Liu Y, Zhang X, Zhang C, Gao Y, Wang L, Du Y. J. Org. Chem. 2012; 77: 9718
    CrossrefPubMed
  • 16 Corkran HM, Munneke S, Dangerfield EM, Stocker BL, Timmer MS. M. J. Org. Chem. 2013; 78: 9791
    CrossrefPubMed
  • 17 Bernet B, Vasella A. Helv. Chim. Acta 1979; 62: 1990
    Crossref
  • 18 Wender PA, Bi FC, Buschmann N, Gosselin F, Kan C, Kee J.-M, Ohmura H. Org. Lett. 2006; 8: 5373
    CrossrefPubMed
  • 19 Still WC, Gennari C. Tetrahedron Lett. 1983; 24: 4405
    Crossref
  • 20 Charette AB, Lebel H. J. Org. Chem. 1995; 60: 2966
    Crossref
  • 21 Chatterjee AK, Choi TL, Sanders DP, Grubbs RH. J. Am. Chem. Soc. 2003; 125: 11360
    CrossrefPubMed
  • 22 Garber SB, Kingsbury JS, Gray BL, Hoveyda AH. J. Am. Chem. Soc. 2000; 122: 8168
    Crossref
  • 23 Dess DB, Martin JC. J. Am. Chem. Soc. 1991; 113: 7277
    CrossrefPubMed
  • 24 Inanaga J, Hirata K, Saeki H, Katsuki T, Yamaguchi M. Bull. Chem. Soc. Jpn. 1979; 52: 1989
    CrossrefPubMed
  • 25 See Supporting Information for the detailed comparisons of 1H and 13C NMR of natural and synthetic (+)-brevipolide H.