Synlett 2020; 31(16): 1551-1554
DOI: 10.1055/s-0040-1707898
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© Georg Thieme Verlag Stuttgart · New York

Divergent Total Syntheses of Six Ganoderma Meroterpenoids: A Bioinspired Two-Phase Strategy

Fen Zhang
,
School of Chemistry and Chemical Engineering, and College of Food Engineering and Nutritional Science, Shaanxi Normal University, 620 West Chang’an Ave, Xi’an, 710119, P. R. of China   Email: ymzhao@snnu.edu.cn
› Author Affiliations
This work was supported by the National Science Foundation of China (21672134, 21971157), Fundamental Research Funds for the Central Universities (GK201905013), and the 100 Talents Program of the Shaanxi Province (Y.-M. Z.).
Further Information

Publication History

Received: 28 May 2020

Accepted after revision: 02 June 2020

Publication Date:
20 July 2020 (online)


Abstract

We briefly highlight our recent work on the total synthesis of six Ganoderma phenolic meroterpenoids: ganocins A–C, ganocochlearins A–D, and cochlearol T. Critical to this success was a bioinspired two-phase strategy that featured an early-stage rapid construction of a common planar tricyclic intermediate and late-stage highly selective transformations of this intermediate into various Ganoderma meroterpenoids. Key steps of the synthesis include a biomimetic ortho-quinone methide intramolecular hetero-Diels–Alder reaction, a Stahl-type oxidative aromatization, a nucleophilic dearomatization of a phenol, a regioselective 1,4-reduction of a dienone, a site-selective Mukaiyama hydration, and an intramolecular oxa-Michael addition/triflation cascade.

 
  • References

    • 1a Hill RA, Connolly JD. Nat. Prod. Rep. 2013; 30: 1028
    • 1b Baby S, Johnson AJ, Govindan B. Phytochemistry 2015; 114: 66
  • 2 Peng X.-R, Liu J.-Q, Wan L.-S, Li X.-N, Yan Y.-X, Qiu M.-H. Org. Lett. 2014; 16: 5262
    • 3a Peng X-R, Liu J.-Q, Wang C.-F, Han Z.-H, Shu Y, Li X.-Y, Zhou L, Qiu M.-H. Food Chem. 2015; 171: 251
    • 3b Wang X.-L, Wua Z.-H, Di L, Zhou F.-J, Yan Y.-M, Cheng Y.-X. Phytochemistry 2019; 162: 199
  • 4 Liu Y, Zhou C.-J, Li Q, Wang H. Org. Biomol. Chem. 2016; 14: 10362
  • 5 Niu X.-M, Li S.-H, Sun H.-D, Che C.-T. J. Nat. Prod. 2006; 69: 1364
  • 6 Shao H, Gao X, Wang Z.-T, Gao Z, Zhao Y.-M. Angew. Chem. Int. Ed. 2020; 59: 7419
    • 7a Mukaiyama T, Narasaka K, Banno K. Chem. Lett. 1973; 2: 1011
    • 7b Mukaiyama T, Banno K, Narasaka K. J. Am. Chem. Soc. 1974; 96: 7503

      For selected recent reviews on o-QMs, see:
    • 8a Van De Water RW, Pettus TR. R. Tetrahedron 2002; 58: 5367
    • 8b Willis NJ, Bray CD. Chem. Eur. J. 2012; 18: 9160
    • 8c Bai W.-J, David J.-G, Feng Z.-G, Weaver M.-G, Wu K.-L, Pettus T.-R. Acc. Chem. Res. 2014; 47: 3655
    • 8d Wang Z, Sun J. Synthesis 2015; 47: 3629
    • 8e Nielsen CD.-T, Abas H, Spivey AC. Synthesis 2018; 50: 4008
    • 9a Izawa Y, Pun D, Stahl S. Science 2011; 333: 209
    • 9b Diao T, Pun D, Stahl S. J. Am. Chem. Soc. 2013; 135: 8205
    • 9c Pun D, Diao T, Stahl S. J. Am. Chem. Soc. 2013; 135: 8213
  • 10 Li W, Li Y, Li Y. Org. Prep. Proced. Int. 1996; 28: 83
    • 11a Arduengo AJ. III, Dias HV. R, Calabrese JC, Davidson F. Organometallics 1993; 12: 3405
    • 11b Jurkauskas V, Sadighi JP, Buchwald SL. Org. Lett. 2003; 5: 2417
    • 11c Hughes G, Kimura M, Buchwald SL. J. Am. Chem. Soc. 2003; 125: 11253

      For metal-catalyzed olefin hydration, see:
    • 12a Isayama S, Mukaiyama T. Chem. Lett. 1989; 18: 1071
    • 12b Mukaiyama T, Isayama S, Inoki S, Kato K, Yamada T, Takai T. Chem. Lett. 1989; 18: 449
    • 12c Inoki S, Kato K, Takai T, Isayama S, Yamada T, Mukaiyama T. Chem. Lett. 1989; 18: 515
    • 12d Isayama S. Bull. Chem. Soc. Jpn. 1990; 63: 1305
    • 12e Magnus P, Payne AH, Waring MJ, Scott DA, Lynch V. Tetrahedron Lett. 2000; 41: 9725
    • 12f Magnus P, Scott DA, Fielding MR. Tetrahedron Lett. 2001; 42: 4127
    • 13a Baillargeon VP, Stille JK. J. Am. Chem. Soc. 1983; 105: 7175
    • 13b Baillargeon VP, Stille JK. J. Am. Chem. Soc. 1986; 108: 452