Tackling the Challenge of the Total Synthesis of Periploside A

Xiaheng Zhang; Biao Yu

doi:10.1055/s-0037-1610152

Synlett, Table of Contents

Synlett 2018; 29(13): 1683-1692
DOI: 10.1055/s-0037-1610152

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Tackling the Challenge of the Total Synthesis of Periploside A

Xiaheng Zhang

State Key Laboratory of Bioorganic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, P. R. of China Email: byu@sioc.ac.cn

,

Biao Yu*

State Key Laboratory of Bioorganic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, P. R. of China Email: byu@sioc.ac.cn

› Author Affiliations

Abstract

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Abstract

Periploside A is the prototypical congener of the pregnane glycosides occurring in the Chinese medicinal plant Periploca sepium, featuring a unique seven-membered formyl acetal bridged spiro-orthoester (FABO) sugar linkage and potent immunosuppressive activities. This account details our efforts on the stereoselective construction of the FABO motif that has led to a successful total synthesis of periploside A.

1 Introduction

2 Attempts at Construction of the FABO Motif

2.1 Intermolecular Condensation and Transacetalation

2.2 Intramolecular Hydrogen Atom Transfer (HAT) Reaction

3 Synthesis of the FABO Motif Bearing the Unnatural Anomeric Configuration

4 Synthesis of the FABO Motif Bearing the Natural Anomeric Configuration

4.1 Unsuccessful Attempts

4.2 Final Solution

5 Conclusion

Key words

orthoester - formacetal - deoxysaccharides - dioxocarbenium - conformation - pregnane glycosides - glycosylation

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References

References
1 Oshima Y. Hirota T. Hikino H. Heterocycles 1987; 26: 2093

2a Itokawa H. Xu JP. Takeya K. Watanabe K. Shoji J. Chem. Pharm. Bull. 1988; 36: 982
2b Itokawa H. Xu JP. Takeya K. Chem. Pharm. Bull. 1988; 36: 2084
2c Itokawa H. Xu JP. Takeya K. Chem. Pharm. Bull. 1988; 36: 4441

3a Feng J. Zhang R. Zhou Y. Chen Z. Tang W. Liu Q. Zuo J. Zhao W. Phytochemistry 2008; 69: 2716
3b Wang L. Chen Z. Zhou Y. Tang W. Zuo J. Zhao W. Phytochemistry 2011; 72: 2230
3c Wang L. Chen Z. Zhou Y. Tang W. Zuo J. Zhao W. Phytochemistry 2013; 95: 445

4a Wang L. Qin J. Chen Z. Zhou Y. Tang W. Zuo J. Zhao W. J. Nat. Prod. 2017; 80: 1102
4b Qin J. Lin Z. Xu Y. Ren J. Zuo J. Zhao W. Bioorg. Med. Chem. Lett. 2018; 28: 330

5a Zhu Y. Zhao W. Yang Y. Liu Q. Zhou Y. Tian J. Ni J. Fu Y. Zhong X. Tang W. Zhou R. He P. Li X. Zuo J. J. Pharmacol. Exp. Ther. 2006; 316: 662
5b Zhu Y. Zhong X. Feng J. Yang Y. Fu Y. Ni J. Liu Q. Tang W. Zhao W. Zuo J. J. Pharmacol. Exp. Ther. 2006; 318: 1153
5c Zhao W. Zuo J. Liu Q. Zhu Y. Zou J. Yang Y. Tian J. Zhou Y. WO2007036113A1, 2007

6 Zhang X. Ph.D. Thesis. University of Chinese Academy of Sciences; Beijing: 2015
7 Zhang X. Zhou Y. Zuo J. Yu B. Nat. Commun. 2015; 6: 5879

8a Li Y. Yang Y. Yu B. Tetrahedron Lett. 2008; 49: 3608
8b Li Y. Yang X. Liu Y. Zhu C. Yang Y. Yu B. Chem. Eur. J. 2010; 16: 1871
8c Ma Y. Li Z. Shi H. Zhang J. Yu B. J. Org. Chem. 2011; 76: 9748
8d Zhang J. Shi H. Ma Y. Yu B. Chem. Commun. 2012; 48: 8679
8e Zhu Y. Yu B. Angew. Chem. Int. Ed. 2011; 50: 8329
8f Tang Y. Li J. Zhu Y. Li Y. Yu B. J. Am. Chem. Soc. 2013; 135: 18396
8g Zhang S. Ma Y. Li J. Ma J. Yu B. Xie X. Proc. Natl. Acad. Sci. U.S.A. 2014; 111: 14571
8h Yu B. Acc. Chem. Res. 2018; 51: 507

9 Yu B. Sun J. Chem. Commun. 2010; 46: 4668
10 Liao S.-G. Chen H.-D. Yue J.-M. Chem. Rev. 2009; 109: 1092

11a Yoshimura J. Tamaru M. Carbohydr. Res. 1979; 72: C9
11b Horito S. Asano K. Umemura K. Hashimoto H. Yoshimura J. Carbohydr. Res. 1983; 121: 175

12a Ohtake H. Iimori T. Ikegami S. Tetrahedron Lett. 1997; 38: 3413
12b Ohtake H. Ichiba N. Ikegami S. J. Org. Chem. 2000; 65: 8164

13a Powell NA. Roush WR. Org. Lett. 2001; 3: 453
13b Savall BM. Blanchard N. Roush WR. Org. Lett. 2003; 5: 377
13c Durham TB. Blanchard N. Savall BM. Powell NA. Roush WR. J. Am. Chem. Soc. 2004; 126: 9307

14a Bodenbenner K. Liebigs Ann. Chem. 1959; 623: 183
14b Collins DJ. Downes LM. Jhingran AG. Rutschmann SB. Sharp GJ. Aust. J. Chem. 1989; 42: 1235
14c Collins DJ. Jhingran AG. Rutschmann SB. Aust. J. Chem. 1989; 42: 1769

15 Praly J.-P. Descotes G. Tetrahedron Lett. 1982; 23: 849

16a Martín A. Martín IP. Quintanal LM. Suárez E. Org. Lett. 2007; 9: 1785
16b Francisco CG. Herrera AJ. Kennedy AR. Martín A. Melián D. Martín IP. Quintanal LM. Suárez E. Chem. Eur. J. 2008; 14: 10369

17 Crich D. Yang F. Angew. Chem. Int. Ed. 2009; 48: 8896

18a Matteucci M. Tetrahedron Lett. 1990; 31: 2385
18b Jones RJ. Lin K.-Y. Milligan JF. Wadwani S. Matteucci M. J. Org. Chem. 1993; 58: 2983
18c Sawada D. Ito Y. Tetrahedron Lett. 2001; 42: 2501

19a Jaurand G. Beau J.-M. Sinaÿ P. J. Chem. Soc., Chem. Commun. 1982; 701
19b Beau J.-M. Jaurand G. Esnault J. Sinaÿ P. Tetrahedron Lett. 1987; 28: 1105
19c Trumtel M. Tavecchia P. Veyrières A. Sinaÿ P. Carbohydr. Res. 1990; 202: 257

20a Nicolaou KC. Mitchell HJ. Fylaktakidou KC. Suzuki H. Rodríguez RM. Angew. Chem. Int. Ed. 2000; 39: 1089
20b Nicolaou KC. Rodríguez RM. Fylaktakidou KC. Suzuki H. Mitchell HJ. Angew. Chem. Int. Ed. 1999; 38: 3340
20c Nicolaou KC. Mitchell HJ. Fylaktakidou KC. Rodríguez RM. Suzuki H. Chem. Eur. J. 2000; 6: 3116

21a Ayala L. Lucero CG. Romero JA. C. Tabacco SA. Woerpel KA. J. Am. Chem. Soc. 2003; 125: 15521
21b Chamberland S. Ziller JW. Woerpel KA. J. Am. Chem. Soc. 2005; 127: 5322
21c Yang MT. Woerpel KA. J. Org. Chem. 2009; 74: 545

22 Deslongchamps P. Stereoelectronic Effects in Organic Chemistry . Pergamon; New York: 1983: 209
23 One reviewer of this manuscript suggests that the preference of conformations of the seven-membered FABO rings (in 63 and 64) may be a factor determining the stereoselectivity if the orthoester formation reaction proceeds through a late stage (product-like) transition state.
24 Jürs S. Thiem J. Synthesis 2006; 2117

25a Pilgrim W. Murphy PV. Org. Lett. 2009; 11: 939
25b Fujiwara K. Suzuki Y. Koseki N. Aki Y.-i. Kikuchi Y. Murata S.-i. Yamamoto F. Kawamura M. Norikura T. Matsue H. Murai A. Katoono R. Kawai H. Suzuki T. Angew. Chem. Int. Ed. 2014; 53: 780

26a Yamada H. Nakatani M. Ikeda T. Marumoto Y. Tetrahedron Lett. 1999; 40: 5573
26b Ikeda T. Yamada H. Carbohydr. Res. 2000; 329: 889
26c Yamada H. Tanigakiuchi K. Nagao K. Okajima K. Mukae T. Tetrahedron Lett. 2004; 45: 5615
26d Okada Y. Nagata O. Taira M. Yamada H. Org. Lett. 2007; 9: 2755

27a Lemieux RU. Morgan AR. Can. J. Chem. 1965; 43: 2205
27b Kiss J. Arnold W. Helv. Chim. Acta 1975; 58: 297
27c Tius MA. Bush-Petersen J. Tetrahedron Lett. 1994; 35: 5181
27d Hosoya T. Ohashi Y. Matsumoto T. Suzuki K. Tetrahedron Lett. 1996; 37: 663
27e Tamura S. Abe H. Matsuda A. Shuto S. Angew. Chem. Int. Ed. 2003; 42: 1021
27f Jensen HH. Bols M. Acc. Chem. Res. 2006; 39: 259

28a Crich D. Smith M. J. Am. Chem. Soc. 2001; 123: 9015
28b Lian G. Zhang X. Yu B. Carbohydr. Res. 2015; 403: 13