Download PDF
Synlett 2009(13): 2129-2132  
DOI: 10.1055/s-0029-1217556
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Stereoselective Total Synthesis of Stagonolide C and Formal Total Synthesis of Modiolide A

Debendra K. Mohapatra*, Uttam Dash, P. Ramesh Naidu, J. S. Yadav*
Organic Chemistry Division-I, Indian Institute of Chemical Technology (CSIR), Uppal Road, Hyderabad 500007, India
Fax: +91(40)27160512; e-Mail: mohapatra@iict.res.in;
Further Information

Publication History

Received 6 May 2009
Publication Date:
15 July 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

The influence of protecting groups at C4 and C7 on a ring-closing metathesis reaction was investigated. Matched induction led to the total synthesis of stagonolide C and the formal total synthesis of modiolide A.

Key words

decanolide - stagonolide C - modiolide A - ring-closing metathesis - Sharpless asymmetric epoxidation

    References and Notes

  • For reviews on synthetic, biosynthetic, and pharmacological aspects of decanolides, see:
  • 1a Dräger G. Kirschning A. Thiericke R. Zerlin M. Nat. Prod. Rep.  1996,  13:  365 
    Google Scholar
  • 1b Ferraz HMC. Bombonato FI. Longo LS. Synthesis  2007,  3261 
    Google Scholar
  • 1c Riatto VB. Pilli RA. Victor MM. Tetrahedron  2008,  64:  2279 
    Google Scholar
  • 2 Yuzikhin O. Mitina G. Berestetskiy A. J. Agric. Food Chem.  2007,  55:  7707 
    CrossrefPubMedGoogle Scholar
  • 3a Evidente A. Cimmino A. Berestetskiy A. Mitina G. Andolfi A. Motta A. J. Nat. Prod.  2008,  71:  31 
    Google Scholar
  • 3b Evidente A. Cimmino A. Berestetskiy A. Andolfi A. Motta A. J. Nat. Prod.  2008,  71:  1897 
    Google Scholar
  • 3c Tsuda M. Mugishima T. Komatsu K. Sone T. Tanaka M. Mikami Y. Kobayashi J. J. Nat. Prod.  2003,  66:  412 
    Google Scholar
  • 4a Gradillas A. Pérez-Castells J. Angew. Chem. Int. Ed.  2006,  45:  6086 
    Google Scholar
  • 4b Deiters A. Martin SF. Chem. Rev.  2004,  104:  2199 
    Google Scholar
  • 4c Grubbs RH. Tetrahedron  2004,  60:  7117 
    Google Scholar
  • 4d Prunet J. Angew. Chem. Int. Ed.  2003,  42:  2826 
    Google Scholar
  • 4e Love JA. In Handbook of Metathesis   Grubbs RH. Wiley-VCH; Weinheim: 2003.  p.296 
    Google Scholar
  • 4f Trnka TM. Grubbs RH. Acc. Chem. Res.  2001,  34:  18 
    Google Scholar
  • 4g Fürstner A. Angew. Chem. Int. Ed.  2000,  39:  3012 
    Google Scholar
  • 4h Maier ME. Angew. Chem. Int. Ed.  2000,  39:  2073 
    Google Scholar
  • 4i Grubbs RH. Chang S. Tetrahedron  1998,  54:  4413 
    Google Scholar
  • 4j Armstrong SK. J. Chem. Soc., Perkin Trans. 1  1998,  371 
    Google Scholar
  • 4k Gerlach K. Quitschalle M. Kalesse M. Tetrahedron Lett.  1999,  40:  3553 
    Google Scholar
  • 4l Nevalainen M. Koskinen AMP. Angew. Chem. Int. Ed.  2001,  40:  4060 
    Google Scholar
  • 5 Perepogu AK. Raman D. Murty USN. Rao VJ. Bioorg. Chem.  2009,  37:  46 
    CrossrefGoogle Scholar
  • 6a Mohapatra DK. Sahoo G. Ramesh DK. Sastry GN. Chem. Eur. J.  2009,  submitted
    Google Scholar
  • 6b Ghosh S. Rao RV. Tetrahedron Lett.  2007,  48:  6937 
    Google Scholar
  • 6c Mohapatra DK. Ramesh DK. Giardello MA. Chorghade MS. Gurjar MK. Grubbs RH. Tetrahedron Lett.  2007,  48:  2621 
    Google Scholar
  • 6d Fürstnet A. Nagano T. Müller C. Seidel G. Müller O. Chem. Eur. J.  2007,  13:  1452 
    Google Scholar
  • 6e Prasad KR. Penchalaiah K. Choudhary A. Anbarsan P. Tetrahedron Lett.  2007,  48:  309 
    Google Scholar
  • 6f Sharma GVM. Cherukupalli GR. Tetrahedron: Asymmetry  2006,  17:  1081 
    Google Scholar
  • 6g Garćia-Fortanet J. Murga J. Falomir E. Carda M. Marco JA. J. Org. Chem.  2005,  70:  9822 
    Google Scholar
  • 6h Matsuda M. Yamazaki T. Fuhshuku K. Sugai T. Tetrahedron  2007,  63:  8752 
    Google Scholar
  • 6i Gurjar MK. Karmakar S. Mohapatra DK. Tetrahedron Lett.  2004,  45:  4525 
    Google Scholar
  • 6j Salaskar A. Sharma A. Chattopadhyay S. Tetrahedron: Asymmetry  2006,  17:  325 
    Google Scholar
  • 6k Boruwa J. Gogoi N. Barua NC. Org. Biomol. Chem.  2006,  4:  3521 
    Google Scholar
  • 6l Nanda S. Tetrahedron Lett.  2005,  46:  3661 
    Google Scholar
  • 6m Arai M. Morita N. Aoyagi S. Kibayashi C. Tetrahedron Lett.  2000,  41:  1199 
    Google Scholar
  • 7a Guindon Y. Yoakim C. Bernstein MA. Morton HE. Tetrahedron Lett.  1985,  26:  1185 
    Google Scholar
  • 7b Takemura T. Nishi Y. Takahashi S. Kobayashi J. Nakata T. Tetrahedron  2002,  58:  6359 ; and references therein
    Google Scholar
  • 8 Gao Y. hanson RM. Klunder JM. Ko SY. Masamune H. Sharpless KB. J. Am. Chem. Soc.  1987,  109:  5765 
    CrossrefGoogle Scholar
  • 9 Reddy LVR. Sagar R. Shaw AK. Tetrahedron Lett.  2006,  47:  1753 
    CrossrefGoogle Scholar
  • 10 Rama Rao AV. Murthy VS. Sharma GVM. Tetrahedron Lett.  1995,  36:  139 
    CrossrefGoogle Scholar
  • 12 Ravelo JL. Rodriguez CM. Martin VS. J. Organomet. Chem.  2006,  691:  5326 ; and references therein
    CrossrefGoogle Scholar
  • 13 Frigerio M. Santagostino M. Tetrahedron Lett.  1994,  35:  8019 
    CrossrefGoogle Scholar
  • 14a Balkrishna SB. Childers WE. Pinnick HW. Tetrahedron  1981,  37:  2091 
    Google Scholar
  • 14b Dalcanale E. Montanari F. J. Org. Chem.  1986,  51:  567 
    Google Scholar
11

Analytical and spectral data of 17: [α]D ²7 -30.4 (c 1.8, CHCl3); IR (KBr): 3456, 2922, 2853, 1616, 1513, 1247
cm-¹; ¹H NMR (300 MHz, CDCl3): δ = 7.16 (d, J = 9.0 Hz, 2 H), 6.73 (d, J = 9.0 Hz, 2 H), 5.80-5.68 (m, 1 H), 5.23-5.14 (m, 2 H), 4.51-4.48 (m, 1 H), 4.48 (d, J = 11.3 Hz, 1 H), 4.19 (d, J = 11.3 Hz, 1 H), 4.01-3.94 (m, 1 H), 3.73 (s, 3 H), 1.67-1.50 (m, 2 H), 1.07 (d, J = 6.8 Hz, 3 H); ¹³C NMR (75 MHz, CDCl3): δ = 159.2, 138.1, 129.4, 128.6, 117.1, 113.8, 77.6, 69.9, 64.6, 55.2, 43.5, 23.3; MS (ESI): m/z = 237 [M + H]+, 259 [M + Na]+; HRMS (ESI): m/z [M + H]+ calcd for C14H20O3Na: 259.1310; found: 259.1318.

15

Analytical and spectral data of 18: [α]D ²7 -30.5 (c 2.7, CHCl3); IR (KBr): 3426, 2929, 2865, 1709, 1610, 1513, 1455, 1250 cm-¹; ¹H NMR (300 MHz, CDCl3): δ = 7.16 (d, J = 8.7 Hz, 2 H), 6.8 (d, J = 8.7 Hz, 2 H), 5.77-5.65 (m, 1 H), 5.25-5.2 (m, 2 H), 4.51 (d, J = 11.4 Hz, 1 H), 4.25 (d, J = 11.4 Hz, 1 H), 3.77 (s, 3 H), 3.77-3.70 (m, 1 H), 2.41 (t, J = 7.3 Hz, 2 H), 1.91-1.78 (m, 2 H); ¹³C NMR (75 MHz, CDCl3): δ = 179.4, 159.0, 138.0, 130.2, 129.3, 117.6, 113.6, 78.7, 69.7, 55.1, 30.0, 29.9; MS (ESI): m/z = 273 [M + Na]+; HRMS (ESI): m/z [M + H]+ calcd for C14H18O4Na: 273.1102; found: 273.1101.

16

Analytical and spectral data of 15: [α]D ²7 -55.3 (c 1.9, CHCl3); IR (KBr): 2923, 2853, 1729,1613, 1513, 1377, 1248 cm-¹; ¹H NMR (300 MHz, CDCl3): δ = 7.28-7.24 (m, 4 H), 6.91-6.85 (m, 4 H), 5.80-5.68 (m, 2 H), 5.29-5.13 (m, 5 H), 4.54 (d, J = 11.5 Hz, 1 H), 4.51 (d, J = 11.3 Hz, 1 H), 4.27 (d, J = 11.3 Hz, 1 H), 4.21 (d, J = 11.5 Hz, 1 H), 3.82 (s, 3 H), 3.80 (s, 3 H), 3.80-3.72 (m, 2 H), 2.41-2.18 (m, 2 H), 1.96-1.67 (m, 4 H), 1.21 (d, J = 6.2 Hz, 3 H); ¹³C NMR (75 MHz, CDCl3): δ = 172.8, 159.0, 138.5, 138.3, 130.5, 130.3, 129.6, 129.3, 117.5, 117.0, 113.7, 79.1, 76.3, 69.9, 69.8, 67.6, 55.2, 42.2, 30.5, 30.4, 20.5; MS (ESI): m/z = 491 [M + Na]+; HRMS (ESI): m/z [M + H]+ calcd for C28H36O6Na: 491.2409; found: 491.2413.

17

Analytical and spectral data of 3: [α]D ²7 +46.2 (c 1.0, CHCl3); IR (KBr): 3443, 2923, 2855, 1717, 1647, 1448, 1368, 1243 cm-¹; ¹H NMR (300 MHz, CDCl3): δ = 5.58 (dd, J = 15.6, 9.2 Hz, 1 H), 5.41 (dd, J = 15.6, 9.0 Hz, 1 H), 5.14 (dq, J = 11.1, 6.4 Hz, 1 H), 4.15-4.05 (m, 2 H), 2.32-2.25 (m, 1 H), 2.04 (m, 3 H), 1.92-1.71 (m, 2 H), 1.22 (d, J = 6.4 Hz, 3 H); ¹³C NMR (75 MHz, CDCl3): δ = 174.6, 135.8, 132.8, 74.3, 71.8, 67.8, 43.2, 34.3, 31.5, 21.3; MS (ESI): m/z = 223 [M + Na]+.

18

Analytical and spectral data of 33: [α]D ²7 +14.7 (c 1.4, EtOH); IR (KBr): 2931, 2859, 1731, 1645, 1461, 1370, 1248 cm-¹; ¹H NMR (300 MHz, CDCl3): δ = 5.45 (dd, J = 15.8, 9.0 Hz, 1 H), 5.30 (dd, J = 15.8, 8.6 Hz, 1 H), 5.14-5.03 (m, 1 H), 4.08-3.97 (m, 2 H), 2.26-2.20 (m, 1 H), 2.05-1.96 (m, 2 H), 1.95-1.84 (m, 1 H), 1.78-1.71 (m, 2 H), 1.18 (d, J = 6.6 Hz, 3 H), 0.86 (s, 9 H), 0.85 (s, 9 H), 0.04 (s, 6 H), 0.02 (s, 6 H); ¹³C NMR (75 MHz, CDCl3): δ = 174.4, 135.1, 132.4, 75.3, 73.0, 67.5, 44.8, 35.5, 31.5, 25.7, 21.4, 18.1,
-4.3, -4.4, -4.7; MS (ESI): m/z = 429 [M + H]+; HRMS (ESI): m/z [M + H]+ calcd for C22H44O4NaSi2: 451.2675; found: 451.2675.