Biogenesis-Inspired Synthesis of Penicillitone

Abstract

The biogenesis-inspired synthesis of the structurally unique 15(14→11)abeo-steroid penicillitone starting from commercially available ergosterol is reported. Key to the strategy is an intramolecular vinylogous aldol reaction of a 14,15-secoergostane obtained from the previously reported 14,15-secosteroid platform. Since a similar intermediate has been employed to access the strophasterol class of natural products, this work points at a possible biosynthetic connection between penicillitone and the strophasterols.

Key words

abeo-steroids - biogenesis-inspired synthesis - intramolecular vinylogous aldol reaction - penicillitone - strophasterol

Publikationsverlauf

Eingereicht: 04. Januar 2023

Angenommen nach Revision: 19. Januar 2023

Artikel online veröffentlicht:
23. Februar 2023

• References

• 1 World Health Organization; World Health Organization Model List of Essential Medicines – 22nd list; 2021; https://www.who.int/publications/i/item/WHO-MHP-HPS-EML-2021.02
• 2 Fieser LF, Fieser M. Steroids . Reinhold Publishing Coorperation; New York: 1959
• 3 Noack F, Heinze RC, Heretsch P. Synthesis 2019; 51: 2039
• 4 Duecker FL, Reuß F, Heretsch P. Org. Biomol. Chem. 2019; 17: 1624
• 5a Heinze RC, Heretsch P. J. Am. Chem. Soc. 2019; 141: 1222
• 5b Duecker FL, Heinze RC, Heretsch P. J. Am. Chem. Soc. 2020; 142: 104
• 5c Alekseychuk M, Adrian S, Heinze RC, Heretsch P. J. Am. Chem. Soc. 2022; 144: 11574
• 6a Wang Y, Ju W, Tian H, Tian W, Gui J. J. Am. Chem. Soc. 2018; 140: 9413
• 6b Wang Y, Tian H, Gui J. J. Am. Chem. Soc. 2021; 143: 19576
• 6c Li X, Zhang Z, Fan H, Miao Y, Tian H, Gu Y, Gui J. J. Am. Chem. Soc. 2021; 143: 4886
• 6d Miao Y, Li X, Zhang M, Fan H, Gui J. Org. Lett. 2022; 24: 1684
• 7 Huang J, Cao T, Zhang Z, Yang Z. J. Am. Chem. Soc. 2022; 144: 2479
• 8 Long X, Li J, Gao F, Wu H, Deng J. J. Am. Chem. Soc. 2022; 144: 16292
• 9a Sato S, Fukuda Y, Ogura Y, Kwon E, Kuwahara S. Angew. Chem. Int. Ed. 2017; 56: 10911
• 9b Sato S, Kuwahara S. Org. Lett. 2020; 22: 1311
• 10 Heinze RC, Lentz D, Heretsch P. Angew. Chem. Int. Ed. 2016; 55: 11656
• 11 Alekseychuk M, Heretsch P. J. Am. Chem. Soc. 2022; 144: 21867
• 12a Wu J, Tokuyama S, Nagai K, Yasuda N, Noguchi K, Matsumoto T, Hirai H, Kawagishi H. Angew. Chem. Int. Ed. 2012; 51: 10820
• 12b Aung HT, Porta A, Clericuzio M, Takaya Y, Vidari G. Chem. Biodivers. 2017; 14: e1600421
• 12c Kikuchi T, Isobe M, Uno S, In Y, Zhang J, Yamada T. Bioorg. Chem. 2019; 89: 103011
• 13 Xue J, Wu P, Xu L, Wei X. Org. Lett. 2014; 16: 1518
• 14 McMorris TC, Patil PA. J. Org. Chem. 1993; 58: 2338
• 15 Burgess EM, Penton HR, Taylor EA. J. Org. Chem. 1973; 38: 26
• 16 Fukuyama T, Lin SC, Li L. J. Am. Chem. Soc. 1990; 112: 7050
• 17 Hosoda H, Yamashita K, Chino N, Nambara T. Chem. Pharm. Bull. 1976; 24: 1860
• 18 Ghobril C, Sabot C, Mioskowski C, Baati R. Eur. J. Org. Chem. 2008; 4104
• 19 Hammar P, Ghobril C, Antheaume C, Wagner A, Baati R, Himo F. J. Org. Chem. 2010; 75: 4728
• 20 Chidambaram N, Chandrasekaran S. J. Org. Chem. 1987; 52: 5048
• 21 We would like to thank X. Wei for providing us with the original spectra of penicillitone.