Download PDF
Synlett 2012(2): 263-266  
DOI: 10.1055/s-0031-1290090
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Concise Formal Synthesis of (+)-Englerin A and Total Synthesis of (-)-Orientalol F: Establishment of the Stereochemistry of the Organocatalytic [4+3]-Cycloaddition Reaction

Chao-Lei Wanga,b, Bing-Feng Sun*a, Shu-Guang Chena,c, Rui Dinga, Guo-Qiang Lin*a, Jin-Yi Xu*b, Yong-Jia Shangc
a CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Road, Shanghai 200032, P. R. of China
Fax: +86(21)54925081; e-Mail: bfsun@sioc.ac.cn; e-Mail: lingq@sioc.ac.cn.;
b Department of Medicinal Chemistry, School of Pharmacy, China Pharmaceutical University, 24 Tongjiaxiang, Nanjing 210009, P. R. of China
e-Mail: jinyixu@china.com;
c College of Chemistry and Materials Science, Anhui Normal University, Beijing East Road No. 1, Wuhu 241000, P. R. of China
Further Information

Publication History

Received 11 October 2011
Publication Date:
05 December 2011 (online)

    Permissions and Reprints All articles of this category

Corrected by:

Concise Formal Synthesis of (+)-Englerin A and Total Synthesis of (-)-Orientalol F: Establishment of the Stereochemistry of the Organocatalytic [4+3]-Cycloaddition ReactionSynlett 2012; 2012(08): 1266-1266
DOI: 10.1055/s-0031-1290674

Abstract

The enantioselective formal synthesis of (+)-englerin A and the total synthesis of (-)-orientalol F were successfully accomplished via a triene. The success enabled establishment of the relative as well as absolute stereochemistry of the organocatalytic [4+3]-cycloaddition reaction.

Key words

asymmetric synthesis - chemoselectivity - regioselectivity - natural product - cycloaddition

    References

  • For reviews, see:
  • 1a Jacobsen EN. MacMillan DWC. Proc. Natl. Acad. Sci. U.S.A.  2010,  107:  20618 ; and references cited therein
    Google Scholar
  • 1b MacMillan DWC. Nature (London)  2008,  455:  304 ; and references cited therein
    Google Scholar
  • 1c Berkessel A. Groeger H. Asymmetric Organocatalysis   Wiley-VCH; Weinheim: 2005. 
    Google Scholar
  • For reviews and selected examples, see:
  • 2a Jones SB. Simmons B. Mastracchio A. MacMillan DWC. Nature (London)  2011,  475:  183 
    Google Scholar
  • 2b Grondal C. Jeanty M. Enders D. Nat. Chem.  2010,  2:  167 
    Google Scholar
  • 2c Jakubec P. Cockfield DM. Dixon DJ. J. Am. Chem. Soc.  2009,  131:  16632 
    Google Scholar
  • 2d Jones SB. Simmons B. MacMillan DWC. J. Am. Chem. Soc.  2009,  131:  13606 
    Google Scholar
  • 3a Harmata M. Ghosh SK. Hong X. Wacharasindhu S. Kirchhoefer P. J. Am. Chem. Soc.  2003,  125:  2058 
    Google Scholar
  • For general and stereochemical aspects of the [4+3]-cycloaddition reaction, see:
  • 3b Krenske EH. Houk KN. Harmata M. Org. Lett.  2010,  12:  444 
    Google Scholar
  • 3c Hartung IV. Hoffmann HMR. Angew. Chem. Int. Ed.  2004,  43:  1934 
    Google Scholar
  • 3d Hoffmann HMR. Angew. Chem., Int. Ed. Engl.  1973,  12:  819 
    Google Scholar
  • 4 Ohno M. Mori K. Hattori T. Eguchi S. J. Org. Chem.  1990,  55:  6086 
    Google Scholar
  • 5a Ratnayake R. Covell D. Ransom TT. Gustafson KR. Beutler JA. Org. Lett.  2009,  11:  57 
    Google Scholar
  • 5b Beutler JA, Ratnayake R, Covell D, and Johnson TR. inventors; WO  2009/088854. 
  • 6a Willot M. Radtke L. Könning D. Fröhlich R. Gessner VH. Strohmann C. Christmann M. Angew. Chem. Int. Ed.  2009,  48:  9105 
    Google Scholar
  • 6b Zhou Q. Chen X. Ma D. Angew. Chem. Int. Ed.  2010,  49:  3513 
    Google Scholar
  • 6c Molawi K. Delpont N. Echavarren AM. Angew. Chem. Int. Ed.  2010,  49:  3517 
    Google Scholar
  • 6d Nicolaou KC. Kang Q. Ng SY. Chen DY.-K. J. Am. Chem. Soc.  2010,  132:  8219 
    Google Scholar
  • 6e Xu J. Caro-Diaz EJE. Theodorakis EA. Org. Lett.  2010,  12:  3708 
    Google Scholar
  • 6f Sun B.-F. Wang C.-L. Ding R. Xu J.-Y. Lin G.-Q. Tetrahedron Lett.  2011,  52:  2155 
    Google Scholar
  • 6g Chan KP. Chen DY.-K. ChemMedChem  2011,  6:  420 
    Google Scholar
  • 6h Ushakov DB. Navickas V. Ströbele M. Maichle-Mössmer C. Sasse F. Maier ME. Org. Lett.  2011,  13:  2090 
    Google Scholar
  • 6i Radtke LR. Willot M. Sun H. Ziegler S. Sauerland S. Strohmann C. Fröhlich R. Habenberger P. Waldmann H. Christmann M. Angew. Chem. Int. Ed.  2011,  50:  3998 
    Google Scholar
  • 6j Li Z. Nakashige M. Chain WJ. J. Am. Chem. Soc.  2011,  133:  6553 
    Google Scholar
  • 7a Peng G.-P. Tian G. Huang X.-F. Lou F.-C. Phytochemistry  2003,  63:  877 
    Google Scholar
  • For related guaianes from the same source, see:
  • 7b Yoshikawa M. Yamaguchi S. Matsuda H. Kohda Y. Ishikawa H. Tanaka N. Yamahara J. Murakami N. Chem. Pharm. Bull.  1994,  42:  1813 
    Google Scholar
  • 7c Yoshikawa M. Hatakeyama S. Tanaka N. Fukuda Y. Murakami N. Yamahara J. Chem. Pharm. Bull.  1992,  40:  2582 
    Google Scholar
  • 8 Huang S.-X. Yang J. Xiao W.-L. Zhu Y.-L. Li R.-T. Li L.-M. Pu J.-X. Li X. Li S.-H. Sun H.-D. Helv. Chim. Acta  2006,  89:  1169 
    Google Scholar
  • 9 For the synthesis of orientalol F and pubinernoid B using the gold-catalyzed cycloaddition of functionalized ketoenynes, see: Jiménez-Núñez E. Molawi K. Echavarren AM. Chem. Commun.  2009,  7327 
    Google Scholar
  • 10a Traylor TG. Baker AW. J. Am. Chem. Soc.  1963,  85:  2746 
    Google Scholar
  • 10b Brown HC. Kawakami JH. J. Am. Chem. Soc.  1973,  95:  8665 
    Google Scholar
  • 10c Sokolova TN. Kartashov VR. Vasil’eva OV. Grishin YK. Russ. Chem. Bull.  1993,  42:  1583 
    Google Scholar
  • For examples of the steric factor, see:
  • 11a Brown HC. Geoghegan JP. J. Org. Chem.  1970,  35:  1844 
    Google Scholar
  • For examples of the electronic factor, see:
  • 11b Factor A. Traylor TG. J. Org. Chem.  1968,  33:  2607 
    Google Scholar
  • 11c Krow G. Rodebaugh R. Grippi M. Carmosin R. Synth. Commun.  1972,  2:  211 
    Google Scholar
  • 11d Mayo P. Orlova G. Goddard JD. Tam W. J. Org. Chem.  2001,  66:  5182 
    Google Scholar