Synlett 2008(18): 2773-2776  
DOI: 10.1055/s-0028-1087296
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Stereoselective Approach for the Total Synthesis of Clonostachydiol

J. S. Yadav*, T. Swamy, B. V. Subba Reddy
Division of Organic Chemistry, Indian Institute of Chemical Technology, Hyderabad 500007, India
Fax: +91(40)27160512; e-Mail: yadav@iict.res.in;
Weitere Informationen

Publikationsverlauf

Received 5 June 2008
Publikationsdatum:
21. Oktober 2008 (online)

Abstract

A stereoselective synthesis of clonostachydiol is accomplished using readily available (±)-epichlorohydrin as a precursor. The synthesis involves direct and straightforward reactions such as Sharpless asymmetric epoxidation, iodination, stereoselective opening of epoxide with allylmagnesium chloride and Sharpless asymmetric dihydroxylation.

    References and Notes

  • 1 Grabley S. Hammann P. Thiericke R. Wink J. Philipps S. Zeeck A. J. Antibiot.  1993,  46:  343 
  • 2 MacMillan J. Simpson TJ. J. Chem. Soc., Perkin Trans. 1  1973,  1487 
  • 3 Am-strutz R. Hungerbuhler E. Seebach D. Helv. Chim. Acta  198l,  64:  1796 
  • 4 Rama Rao AV. Murthy VS. Sharma GVM. Tetrahedron Lett.  1995,  36:  143 
  • 5 Bouz S. Cossy J. Tetrahedron Lett.  2006,  47:  901 
  • 6a Yadav JS. Srihari P. Tetrahedron: Asymmetry  2002,  15:  81 
  • 6b Yadav JS. Prakash SJ. Tetrahedron: Asymmetry  2005,  16:  2722 
  • 6c Yadav JS. Rajaiah G. Synlett  2004,  1743 
  • 7a Tocunaga M. Larrow JF. Kakiuchi F. Jacobson EN. Science  1997,  277:  936 
  • 7b Schaus SE. Brandes BD. Larrow JF. Tokunaga M. Hansen KB. Gould AE. Kurrow ME. Jacobsen EN. J. Am. Chem. Soc.  2002,  124:  1307 
  • 7c Yadav JS. Rajaiah G. Synlett  2004,  1743 
  • 8a Rickborn B. Lamke WE. J. Org. Chem.  1967,  32:  537 
  • 8b Murphy DK. Alumbaugh RL. Rickborn B.
    J. Am. Chem. Soc.  1969,  91:  2649 
  • 8c Kan WS. Pharmaceutical Botany   National Research Institute of Chinese Medicine; Taipei: 1979.  p.247 
  • 9a Omura K. Swern D. Tetrahedron  1978,  34:  1651 
  • 9b Marx M. Tidwell TT. J. Org. Chem.  1984,  49:  788 
  • 9c Mancuso AJ. Swern D. Synthesis  1981,  165 
  • 10 Wipf P. Lim S. J. Am. Chem. Soc.  1995,  117:  558 
  • 11a Gao Y. Hanson RM. Klunder JM. Ko SY. Masamune H. Sharpless KB. J. Am. Chem. Soc.  1987,  109:  5765 
  • 11b Carreaux F. Favre A. Carboni B. Rouaud I. Boustie J. Tetrahedron Lett.  2006,  47:  4545 
  • 12 Nicolaou K. Duggan ME. Ladduwahetty T. Tetrahedron Lett.  1984,  25:  2069 
  • 13a Lee CW. Grubbs RH. J. Org. Chem.  2001,  66:  7155 
  • 13b Deiters A. Martin S. Chem. Rev.  2004,  104:  2199 
  • 14 Yadav JS. Chandrashekar S. Sumitra G. Rajashekar K. Tetrahedron Lett.  1996,  37:  6603 
  • 15 Sharpless KB. Amberg W. Bennani YL. Crispino GA. Hartung J. Jeong K.-S. Kwong H.-L. Morikawa K. Wang Z.-M. Xu D. Zhang X.-L. J. Org. Chem.  1992,  57:  2768 
  • 16 Thomas JH. George AO. Org. Lett.  2002,  4:  4447 
  • 17 Yamaguchi M. Bull. Chem. Soc. Jpn.  1979,  52:  1989 
  • 18 Shiina I. Kubota K. Ibuka R. Tetrahedron Lett.  2002,  43:  7535 
19

Compound 15: [α]D +7.5 (c = 1, CDCl3). ¹H NMR (300 MHz, CDCl3): δ = 6.95 (dd, J = 15.8, 4.5 Hz, 1 H), 6.00 (d, J = 15.8 Hz, 1 H), 4.25 (dd, J = 6.7, 4.5 Hz, 1 H), 3.75-3.85 (m, 1 H), 3.72 (s, 3 H), 1.15 (d, J = 6.7 Hz, 3 H), 0.95 (s,
9 H), 0.10 (s, 3 H), 0.06 (s, 3 H). ¹³C NMR (50 MHz, CDCl3): δ = 166.4, 147.4, 121.6, 75.6, 70.2, 51.3, 25.6, 18.0, -4.6. IR (Neat): 3452, 2928, 2885, 1714, 1642, 1412, 1225, 915 cm. MS (ESI): m/z = 297 [M + Na+]. HRMS: m/z calcd for C13H26O4SiNa: 297.1498; found: 297.1491.
Compound 21: [α]D +7.5 (c = 0.6, CDCl3). ¹H NMR (300 MHz, CDCl3): δ = 7.22-7.35 (m, 5 H), 6.90 (dd, J = 15.6, 6.2 Hz, 1 H), 5.95 (d, J = 15.6 Hz, 1 H), 4.50-4.62 (m, 2 H), 4.45 (d, J = 6.6 Hz, 2 H), 4.06-4.15 (m, 1 H), 3.45-3.55 (m, 1 H), 3.35 (s, 3 H), 1.50-1.75 (m, 4 H), 1.20 (d, J = 6.0 Hz, 3 H). ¹³C NMR (50 MHz, CDCl3): δ = 173.4, 152.2, 130.0, 129.6, 129.4, 123.5, 97.2, 77.0, 76.1, 72.5, 55.0, 34.5, 32.2, 23.6. MS (ESI): m/z = 309 [M+ + 1], 331 [M+ + Na]. HRMS: m/z calcd for C17H24O5Na: 331.1521; found: 331.1519.
Compound 1: [α]D +101 (c = 1, MeOH). ¹H NMR (300 MHz, CDCl3): δ = 6.85 (dd, J = 14.3, 4.3 Hz, 1 H), 6.78 (dd, J = 15.1, 6.1 Hz, 1 H), 6.08 (d, J = 14.3 Hz, 1 H), 5.95 (d, J = 15.1 Hz, 1 H), 4.90-4.98 (m, 1 H), 4.15-4.25 (m, 2 H), 3.85-3.95 (m, 1 H), 1.55-1.68 (m, 4 H), 1.25 (d, J = 6.0 Hz, 3 H, Me), 1.25 (d, J = 6.0 Hz, 3 H, Me). IR (Neat): 3350, 2984, 2918, 1709, 1643, 1252, 1175 cm. LCMS: m/z = 307 [M+ + Na].