Synthesis 2006(15): 2535-2542  
DOI: 10.1055/s-2006-942467
PAPER
© Georg Thieme Verlag Stuttgart · New York

Stereocontrolled Synthesis of gem-Difluoromethylenated Goniodiols and Goniothalamin Epoxides Based on Ring-Closing Metathesis

Zheng-Wei Youa, Xingang Zhanga, Feng-Ling Qinga,b
a Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, 354 Fenglin Lu, Shanghai 200032, P. R. of China
b Institute of Biological Sciences and Biotechnology, Donghua University, 2999 North Renmin Lu, Shanghai 201620, P. R. of China
Fax: +86(21)64166128; e-Mail: flq@mail.sioc.ac.cn;
Further Information

Publication History

Received 27 February 2006
Publication Date:
04 July 2006 (online)

Abstract

An efficient and general method to stereoselectively synthesize gem-difluoromethylenated goniodiols and goniothalamin epoxides has been developed. The introduction of a gem-difluoro­methyl-containing group was achieved by the reaction of aldehydes with 3-bromo-3,3-difluoropropene in the presence of indium. The gem-difluoromethylenated α,β-unsaturated-δ-lactone moiety was constructed through the ring-closing metathesis of highly electron-deficient gem-difluoromethylenated acryloyl esters by Grubbs’ II catalyst in toluene at reflux.

    References

  • 1a Blázquez MA. Bermejo A. Zafra-Polo MC. Cortes D. Phytochem. Anal.  1999,  10:  161 
  • 1b Surivet J.-P. Vatèle J.-M. Tetrahedron  1999,  55:  13011 
  • 1c Mereyala HB. Joe M. Curr. Med. Chem.: Anti-Cancer Agents  2001,  1:  293 
  • 1d Zhong L. Lou L.-G. Xu B. Zhongliu  2003,  23:  162 
  • 1e Wang Q.-Z. He M.-F. Liang J.-Y. Zhongcaoyao  2003,  34:  277 
  • 1f Umar-Tsafe N. Mohamed-Said MS. Rosli R. Din LB. Lai LC. Mutat. Res.  2004,  562:  91 ; and references cited therein
  • 2 Mu Q. Tang W. Li C. Lu Y. Sun H. Zheng H. Hao X. Zheng Q. Wu N. Lou L. Xu B. Heterocycles  1999,  12:  2969 
  • 3 Lan Y.-H. Chang F.-R. Yu J.-H. Yang Y.-L. Chang Y.-L. Lee S.-J. Wu Y.-C. J. Nat. Prod.  2003,  66:  487 ; and references cited therein
  • For a review, see:
  • 4a Zhang X.-X. Li W.-D. Chin. J. Org. Chem.  2003,  23:  1177 
  • For recent examples, see:
  • 4b Yamashita Y. Saito S. Ishitani H. Kobayashi S. J. Am. Chem. Soc.  2003,  125:  3793 
  • 4c Ruiz P. Murga J. Carda M. Marco JA. J. Org. Chem.  2005,  70:  713 
  • For examples of the synthesis of 7-epi-goniodiol, see:
  • 4d Chen J. Lin G.-Q. Wang Z.-M. Liu H.-Q. Synlett  2002,  1265 
  • 4e Chen J. Lin G.-Q. Liu H.-Q. Tetrahedron Lett.  2004,  45:  8111 
  • 4f Liu Z.-Y. Ji J.-X. Li B.-G. J. Chem. Res.  2004,  61 
  • For examples of the synthesis of isogoniothalamin epoxide, see:
  • 4g Sam TW. Sew-Yeu C. Matsjeh S. Gan EK. Razak D. Mohamed AL. Tetrahedron Lett.  1987,  28:  2541 
  • 4h Fuganti C. Pedrocchi-Fantoni G. Sarra A. Servi S. Tetrahedron: Asymmetry  1994,  5:  1135 
  • 4i Goh SH. Ee GCL. Chuah CH. Wei C. Aust. J. Chem.  1995,  48:  199 
  • 4j Peng X. Li A. Shen H. Wu T. Pan X. J. Chem. Res.  2002,  7:  330 
  • 5 Peris E. Estornell E. Cabedo N. Cortes D. Bermejo A. Phytochemistry  2000,  54:  311 
  • 6a Shimizu M. Hiyama T. Angew. Chem. Int. Ed.  2005,  44:  214 
  • 6b Strunecka A. Patocka J. Connett P. J. Appl. Biomed.  2004,  2:  141 ; and references cited therein
  • 7a Percy JM. Chem. Today  2004,  22:  18 
  • 7b Tozer MJ. Herpin TF. Tetrahedron  1996,  52:  8619 ; and references cited therein
  • 8a Grubbs RH. Chang S. Tetrahedron  1998,  54:  4413 
  • 8b Grubbs RH. Acc. Chem. Res.  2001,  34:  18 
  • 8c Schrock RR. Hoveyda AH. Angew. Chem. Int. Ed.  2003,  42:  4592 
  • 8d Ghosh AK. Cappiello J. Shin D. Tetrahedron Lett.  1998,  39:  4651 
  • 8e Carda M. Castillo E. Rodríguez S. Uriel S. Marco JA. Synlett  1999,  1639 
  • For examples, see:
  • 9a Percy JM. Pintat S. Chem. Commun.  2000,  607 
  • 9b Salim SS. Bellingham RK. Satcharoen V. Brown RCD. Org. Lett.  2003,  5:  3403 
  • 9c Marhold M. Buer A. Hiemstra H. Maarseveen JH. Haufe G. Tetrahedron Lett.  2004,  45:  57 
  • 9d Audouard C. Fawcett J. Griffiths GA. Percy JM. Org. Biomol. Chem.  2004,  2:  528 
  • 9e Matteis VD. Delft FL. Gelder R. Tiebes J. Rutjes FPJT. Tetrahedron Lett.  2004,  45:  959 
  • 10 You Z.-W. Wu Y.-Y. Qing F.-L. Tetrahedron Lett.  2004,  45:  9479 
  • 11a Kolb HC. VanNieuwenhze MS. Sharpless KB. Chem. Rev.  1994,  94:  2483 
  • 11b Denis J.-N. Correa A. Greene AE. J. Org. Chem.  1990,  55:  1957 
  • 11c Bianchi P. Roda G. Riva S. Danieli B. Zabelinskaja-Mackova A. Griengl H. Tetrahedron  2001,  57:  2213 
  • 12 Luca LD. Giacomelli G. Porcheddu A. Org. Lett.  2001,  3:  3041 
  • 13a Kirihara M. Takuwa T. Takizawa S. Momose T. Nemoto H. Tetrahedron  2000,  56:  8275 
  • 13b Zhang X. Xia H. Dong X. Meng W.-D. Qing F.-L. J. Org. Chem.  2003,  68:  9026 
  • 14a Gao Y. Hanson RM. Klunder JM. Ko SY. Masamune H. Sharpless KB. J. Am. Chem. Soc.  1987,  109:  5765 
  • 14b Yadav JS. Rajaiah G. Raju AK. Tetrahedron Lett.  2003,  44:  5831 
  • 15a Caron M. Sharpless KB. J. Org. Chem.  1985,  50:  1557 
  • 15b Chong JM. Sharpless KB. J. Org. Chem.  1985,  50:  1560