Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2013; 24(3): 369-374
DOI: 10.1055/s-0032-1318114
DOI: 10.1055/s-0032-1318114
letter
Total Synthesis of Dihydrocodeine and Hydrocodone via a Double Claisen Rearrangement and C-10/C-11 Closure Strategy
Further Information
Publication History
Received: 06 December 2012
Accepted after revision: 04 January 2013
Publication Date:
21 January 2013 (online)

Abstract
Dihydrocodeine and hydrocodone were synthesized from bromobenzene in 16 and 17 transformations, respectively. The key steps involved the toluene dioxygenase-mediated dihydroxylation of bromobenzene by whole-cell fermentation with E. coli JM109(pDTG601A), Kazmaier–Claisen rearrangement of glycinate ester, Claisen rearrangement to set the C-13 quaternary center, and C-10–C-11 closure. Experimental procedures are provided for the key steps.
-
References and Notes
- 1a Gates M, Tschudi G. J. Am. Chem. Soc. 1952; 74: 1109
- 1b Gates M, Tschudi G. J. Am. Chem. Soc. 1956; 78: 1380
- 2a Rinner U, Hudlicky T. Top. Curr. Chem. 2012; 309: 33
- 2b Zezula J, Hudlicky T. Synlett 2005; 388
- 2c Taber DF, Neubert TD, Schlecht MF In Strategies and Tactics in Organic Synthesis . Vol. 5. Harmata M. Elsevier; London: 2004: 353
- 2d Hudlicky T. J. Heterocycl. Chem. 2000; 37: 535
- 2e Novak BH, Hudlicky T, Reed JW, Mulzer J, Trauner D. Curr. Org. Chem. 2000; 4: 343
- 2f Hudlicky T, Butora G, Fearnley S, Gum A, Stabile M In Studies in Natural Products Chemistry . Vol. 18. Atta-ur-Rahman Elsevier; Amsterdam: 1996: 43
- 2g Maier M In Organic Synthesis Highlights II . Waldmann H. VCH; Weinheim: 1995: 357
- 3 Rice KC. J. Org. Chem. 1980; 45: 3135
- 4a Duchek J, Piercy G, Gilmet J, Hudlicky T. Can. J. Chem. 2011; 89: 709
- 4b Leisch H, Omori AT, Finn KJ, Gilmet J, Bissett T, Ilceski D, Hudlicky T. Tetrahedron 2009; 65: 9862
- 4c Omori AT, Finn KJ, Leisch H, Carroll RJ, Hudlicky T. Synlett 2007; 2859
- 5a Tanimoto H, Saito R, Chida N. Tetrahedron Lett. 2008; 49: 358
- 5b Butora G, Hudlicky T, Fearnley SP, Stabile MR, Gum AG, Gonzalez D. Synthesis 1998; 665
- 5c Evans DA, Mitch CH. Tetrahedron Lett. 1982; 23: 285
- 5d Ichiki M, Tanimoto H, Miwa S, Saito R, Saito T, Chida N. Chem. Eur. J. 2013; 19: 264
- 6 Gonzalez D, Schapiro V, Seoane G, Hudlicky T, Abboud K. J. Org. Chem. 1997; 62: 1194
- 7 Ireland RE, Wipf P, Xiang J. J. Org. Chem. 1991; 56: 3572
- 8 Hudlicky T, Price JD, Rulin F, Tsunoda T. J. Am. Chem. Soc. 1990; 112: 9439
- 9a Zylstra GJ, Gibson DT. J. Biol. Chem. 1989; 264: 14940
- 9b Endoma MA, Bui VP, Hansen J, Hudlicky T. Org. Process Res. Dev. 2002; 6: 525
- 10 Gonzalez D. PhD Dissertation. University of Florida; USA: 1999. Diss. Abstr. 1999.9945971
- 11 Hudlicky, T.; Gonzalez, G. unpublished observations. The following reactivity was observed upon treatment of acid i with PPA or TsOH (Scheme 4).
- 12 Yasuda M, Onishi Y, Ueba M, Miyai T, Baba A. J. Org. Chem. 2001; 66: 7741
- 13a Hong CY, Kado N, Overman LE. J. Am. Chem. Soc. 1993; 115: 11028
- 13b Labidalle S, Min ZY, Reynet A, Moekowitz H, Vierfond J, Miocque M, Bucourt R, Thal C. Tetrahedron 1988; 44: 1171
- 14 Mulzer J, Bats JW, List B, Opatz T, Trauner D. Synlett 1997; 441
- 15 Iijima I, Rice KC, Silverton JV. Heterocycles 1977; 6: 1157
- 16a White JD, Hrnciar P, Stappenbeck F. J. Org. Chem. 1999; 64: 7871
- 16b Taber DF, Neubert TD, Rheingold AL. J. Am. Chem. Soc. 2002; 124: 12416
- 16c Uchida K, Yokoshima S, Kan T, Fukuyama T. Org. Lett. 2006; 8: 5311
- 16d Parker KA, Fokas D. J. Org. Chem. 2006; 71: 449
- 17 Van Duin CF, Robinson R, Smith JC. J. Chem. Soc. 1926; 903
- 18 Bobbitt J, Weiss U, Hanessian D. J. Org. Chem. 1959; 24: 1582
- 19 Trauner D, Bats JW, Werner A, Mulzer J. J. Org. Chem. 1998; 63: 5908
For reviews of morphine alkaloid synthesis, see:
For medium-scale preparation of 1 and other diene cis-diols by fermentation, see: