Concise Seven-Membered Oxepene/Oxepane Synthesis – Structural Motifs in Natural and Synthetic Products

Abstract

This work outlines a suitable method for the synthesis of oxepane skeleton using iterative C-glycoside technology on the oxepene intermediate, which was synthesized utilizing Wilkinson’s catalyst [Rh(PPh₃)₃Cl] to generate the isomerized product in a linear synthetic manner. The central core of the oxepene motif was achieved via an olefin metathesis reaction using the Grubbs second-generation and Schrock catalysts. The synthesis of the functionalized oxepane having the desired adriatoxin E-ring relative stereochemistry was achieved starting from commercially available homopropargylic alcohol.

Key words

oxepane - oxepene - Wilkinson’s catalyst - metathesis - adriatoxin - yessotoxin - epoxidation

• References

• 1 Present Address: Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana.
• 2 Belen’kll LI. In Comprehensive Heterocyclic Chemistry II, Vol. 9. Katritzky AR, Rees CW, Scriven EF. Elsevier; Amsterdam: 1996: 45-66
• 3 Kanojia RM, Chin E, Smith C, Chen R, Rowand E, Levine SD, Wachter MP, Adams RE, Hahn D. J. Med. Chem. 1985; 28: 796
• 4 Nicolaou KC, Claremon DA, Barnette WE. J. Am. Chem. Soc. 1980; 102: 6611
• 5 Kane VV. US Patent 4384126, 1983
• 6 Shinya Y, Ichio S. Patent WO2005079785 A1, 2005
• 7 Cloos PA. C. Patent WO2004039773 A2, 2004
• 8 Fukuzawa A, Masamune T. Tetrahedron Lett. 1981; 22: 4081
• 9 Dembitsky VM, Tolstikov AG, Tolstikov GA. Chem. Sustainable Develop. 2003; 11: 329
• 10 Guella G, Pietra F. Helv. Chim. Acta 1991; 74: 47
• 11a Scheuer PJ, Takahashi W, Tsutsumi J, Yoshida T. Science 1967; 155: 1267
• 11b Murata M, Legrand AM, Yasumoto T. Tetrahedron Lett. 1989; 30: 3793
• 12 Poli MA, Musser SM, Dickey RW, Eilers PP, Hall S. Toxicon 2000; 38: 981
• 13 Bourdelais AJ, Jacocks HM, Wright JL. C, Bigwarfe PM. Jr, Baden DG. J. Nat. Prod. 2005; 68: 2
• 14a Osei Akoto C, Rainier JD. Angew. Chem. Int. Ed. 2008; 47: 8055
• 14b Konishi M, Yang X, Li B, Fairchild CR, Shimizu R. J. Nat. Prod. 2004; 67: 1309
• 14c Osei Akoto C. Ph.D. Dissertation . University of Utah; USA: 2009
• 15 Zhao Y, Slepkov AD, Osei Akoto C, McDonald R, Hegmann FA, Tykwinski RR. Chem. Eur. J. 2005; 11: 321
• 16 Meta CT, Koide K. Org. Lett. 2004; 6: 1785
• 17 Gao Y, Hanson RM, Klunder JM, Ko SY, Masamune H, Sharpless KB. J. Am. Chem. Soc. 1987; 109: 5765
• 18 Caron M, Sharpless KB. J. Org. Chem. 1985; 50: 1557
• 19a Fujiwara K, Saka K, Takaoka D, Murai A. Synlett 1999; 1037
• 19b Winkler JD, Rouse MB, Greaney MF, Harrison SJ, Jeon YT. J. Am. Chem. Soc. 2002; 124: 9726

For reviews on RCM, see:
• 20a Fürstner A. Angew. Chem. Int. Ed. 2000; 39: 3012
• 20b Grubbs RH, Chang S. Tetrahedron 1998; 54: 4413
• 21 Schrock RR, Murdzek JS, Bazan GC, Robbins J, DiMare M, O’Regan MB. J. Am. Chem. Soc. 1990; 112: 3875
• 22 Corey EJ, Suggs JW. J. Org. Chem 1973; 38: 3224
• 23 Perrin DD, Armarego WL. F. Purification of Common Laboratory Chemicals . Pergamon Press; Oxford: 1966