Synthesis of (–)- and (+)-Gummiferol via Asymmetric Synthesis of Glycidic Amides

Abstract

An efficient synthesis of the natural product (–)-gummiferol is achieved according to a novel asymmetric methodology of epoxide formation based on a new class of chiral sulfonium salts. This new methodology allows the rapid and efficient construction of the diepoxide system contained within the natural product.

Key words

asymmetric synthesis - glycidic amides - chiral sulfonium salts - natural products - diepoxides

• References

• 1 Fullas F, Brown DM, Wani MC, Wall ME. J. Nat. Prod. 1995; 58: 1625
• 2 Takamura H, Wada H, Lu N, Kadota I. Org. Lett. 2011; 13: 3644
• 3 Katsuki T, Sharpless KB. J. Am. Chem. Soc. 1980; 102: 5974
• 4 Siemsen P, Livingston RC, Diederich F. Angew. Chem. Int. Ed. 2000; 39: 2632
• 5 Takamura H, Wada H, Lu N, Ohno O, Suenaga K, Kadota I. J. Org. Chem. 2013; 78: 2443
• 6 Sarabia F, Chammaa S, García-Castro M, Martín-Gálvez F. Chem. Commun. 2009; 5763
• 7 Sarabia F, Vivar-García C, García-Castro M, García-Ruiz C, Martín-Gálvez F, Sánchez-Ruiz A, Chammaa S. Chem. Eur. J. 2012; 18: 15190
• 8 Sarabia F, Martín-Gálvez F, García-Ruiz C, Sánchez-Ruiz A, Vivar-García C. J. Org. Chem. 2013; 78: 5239; and references therein
• 9 Sarabia F, Chammaa S, García-Ruiz C. J. Org. Chem. 2011; 76: 2132
• 10 Sarabia F, Vivar-García C, García-Ruiz C, Sánchez-Ruiz A, Pino-González MS, García-Castro M, Chammaa S. Eur. J. Org. Chem. 2014; 3847
• 11 García-Ruiz C, Cheng-Sánchez I, Sarabia F. Org. Lett. 2015; 17: 5558
• 12 CCDC 1473694 (2) and 1473695 (ent-2) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 13 Xu R, Gramlich V, Frauenrath H. J. Am. Chem. Soc. 2006; 128: 5541
• 14a Ohira S. Synth. Commun. 1989; 19: 561
• 14b Muller S, Liepold B, Roth G, Bestmann J. Synlett 1996; 521
• 15 Ramachandran PV, Liu H, Ram Reddy MV, Brown HC. Org. Lett. 2003; 5: 3755
• 16 Bhunia N, Das B. Synthesis 2015; 47: 1499
• 17 Parikh JR, Doering WE. J. Am. Chem. Soc. 1967; 89: 5505
• 18 Corey EJ, Fuchs PL. Tetrahedron Lett. 1972; 36: 3769