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Synlett 2008(20): 3111-3114  
DOI: 10.1055/s-0028-1087275
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Aromatics to Diquinanes: An Expeditious Synthesis of Tetramethyl­bicyclo[3.3.0]octane Framework of Ptychanolide

Vishwakarma Singh*a, Girish Chandraa, Shaikh M. Mobinb
a Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400076, India
Fax: +91(22)25723480; e-Mail: vks@chem.iitb.ac.in;
b National Single-Crystal X-ray Diffraction Facility, Indian Institute of Technology Bombay, Mumbai 400076, India
Further Information

Publication History

Received 9 August 2008
Publication Date:
26 November 2008 (online)

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Abstract

An expeditious route to methyl-7-oxo-1,4,5,8-tetra­methylbicyclo[3.3.0]octane-3-carboxylate from a simple aromatic precursor is described. Oxidative dearomatization of 2-hydroxy­methyl-3,4,6-trimethylphenol into spiroepoxycyclohexa-2,4-dienone, its cycloaddition and triplet-sensitized 1,2-acyl shift, and stereochemical inversion are the key features of our methodology.

Key words

cycloaddition - oxa-di-π-methane rearrangement - diquinanes - Diels-Alder reaction

    References and Notes

  • 1a Chanon M. Barone R. Baralotto C. Julliard M. Hendrickson JB. Synthesis  1998,  1559 
    Google Scholar
  • 1b Corey EJ. Cheng X.-M. The Logic of Chemical Synthesis   John Wiley & Sons; New York: 1989. 
    Google Scholar
  • 2 Tietze LF. Brasche G. Gericke KM. Domino Reactions in Organic Synthesis   Wiley-VCH; Weinheim: 2006. 
    Google Scholar
  • 3a Ugi I. Pure Appl. Chem.  2001,  73:  187 
    Google Scholar
  • 3b Bertozzi F. Gundersen BV. Gustafsson M. Olsson R. Org. Lett.  2003,  5:  1551 
    Google Scholar
  • 4a Magdziak D. Meek SJ. Pettus TRR. Chem. Rev.  2004,  104:  1383 ; and references therein
    Google Scholar
  • 4b Liao CC. Peddinti RK. Acc. Chem. Res.  2002,  35:  856 
    Google Scholar
  • 4c Gagnepain J. Castel F. Quideau S. Angew. Chem. Int. Ed.  2007,  46:  1533 
    Google Scholar
  • 4d Quideau S. Pouysegu L. Org. Prep. Proc. Int.  1999,  31:  617 
    Google Scholar
  • 4e Bonnarme V. Mondon M. Gesson J.-P. Cousson A. Chem. Commun.  1999,  1143 
    Google Scholar
  • 5a Takeda R. Naoki H. Iwashita T. Hirose Y. Tetrahedron Lett.  1981,  22:  5307 
    Google Scholar
  • 5b Takeda R. Naoki H. Iwashita T. Mizukawa K. Hirose Y. Isida T. Inoue M. Bull. Chem. Soc. Jpn.  1983,  56:  1125 
    Google Scholar
  • 5c Tori M. Arbiyanti H. Taira Z. Asakawa Y. Tetrahedron Lett.  1992,  33:  4011 
    Google Scholar
  • 5d Tori M. Arbiyanti Z. Taira Z. Asakawa Y. Phytochemistry  1993,  32:  335 
    Google Scholar
  • 5e Tang Y.-Q. Sattler I. Thiericke R. Grabley S. Feng S.-Z. Eur. J. Org. Chem.  2000,  2401 
    Google Scholar
  • 6a Mehta G. Srikrishna A. Chem. Rev.  1997,  97:  671 
    Google Scholar
  • 6b Paquette LA. Doherty AM. Polyquinane Chemistry   Vol. 26:  Hafner K. Rees CW. Trost BM. Lehn J.-M. Schleyer PvR. Zahradnik R. Springer; Berlin: 1987. 
    Google Scholar
  • 7a Mehmoud B. West FG. Tetrahedron Lett.  2007,  48:  5051 
    Google Scholar
  • 7b Srikrishna A. Gowri V. Tetrahedron: Asymmetry  2007,  18:  1663 
    Google Scholar
  • 7c Tzvetkov NT. Neumann B. Stammler H.-G. Mattay J. Eur. J. Org. Chem.  2006,  351 
    Google Scholar
  • 7d Khan FA. Rao CN. Tetrahedron Lett.  2006,  47:  7567 
    Google Scholar
  • 7e Wu YT. Vidovic D. Magull J. De Meijere A. Eur. J. Org. Chem.  2005,  1625 
    Google Scholar
  • 7f Srikrishna A. Dethe DH. Org. Lett.  2003,  5:  2295 
    Google Scholar
  • 7g Dhimane A. Aissa C. Malacria M. Angew. Chem. Int. Ed.  2002,  41:  3284 
    Google Scholar
  • 7h Shino M. Sato Y. Shisido K. Tetrahedron Lett.  2002,  43:  5039 
    Google Scholar
  • 7i Harrowven DC. Lucas MC. Howes PD. Tetrahedron  2001,  57:  9157 
    Google Scholar
  • 8a Hashimoto H. Abe Y. Mayuzumi Y. Karikomi M. Seki K. Haga K. Uyehara T. Tetrahedron Lett.  2002,  43:  265 
    Google Scholar
  • 8b Solaja B. Huguet J. Karpf M. Dreiding AS. Tetrahedron  1987,  43:  4875 
    Google Scholar
  • 8c Huguet J. Karpf M. Dreiding AS. Tetrahedron Lett.  1983,  24:  4177 
    Google Scholar
  • 9a Singh V. Acc. Chem. Res.  1999,  31:  324 
    Google Scholar
  • 9b Singh V. Sahu PK. Singh RB. Mobin SM. J. Org. Chem.  2007,  72:  10155 
    Google Scholar
  • 9c Singh V. Chandra G. Mobin SM. Synlett  2008,  2267 
    Google Scholar
  • 10 Andreetti GD. Böhmer V. Jordon JG. Tabatabai M. Ugozzoli F. Vogt W. Wolff A. J. Org. Chem.  1993,  58:  4023 
    CrossrefGoogle Scholar
  • 11a Adler E. Brasen S. Miyake H. Acta Chem. Scand.  1971,  25:  2055 
    Google Scholar
  • 11b Becker H.-D. Bremholt T. Adler E. Tetrahedron Lett.  1972,  13:  4205 
    Google Scholar
  • 11c Singh V. Porinchu M. Vedantham P. Sahu PK. Org. Synth.  2005,  81:  171 
    Google Scholar
  • 13a Demuth M. Hisken W. Angew. Chem., Int. Ed. Engl.  1985,  24:  973 
    Google Scholar
  • 13b Demuth M. Schaffner K. Angew. Chem., Int. Ed. Engl.  1982,  21:  820 
    Google Scholar
  • 14a Zimmerman H. E., Armesto D.; Chem. Rev.; 1996, 96: 3065
  • 14b Armesto D. Ortiz MJ. Agarrabeitia AR. CRC Handbook of Organic Photochemistry and Photobiology   Horspool W. Lenci F. CRC; Boca Raton: 2004.  p.95.1 
    Google Scholar
  • 14c Singh V. In CRC Handbook of Organic Photochemistry and Photobiology   Horspool W. Lenci F. CRC; Boca Raton: 2004.  p.78.1 
    Google Scholar
  • 15 Austin KAB. Banwell MG. Harfoot GJ. Willis AC. Tetrahedron Lett.  2006,  47:  7381 
    CrossrefGoogle Scholar
  • 16 Enholm EJ. Jia ZJ. J. Org. Chem.  1997,  62:  174 
    CrossrefPubMedGoogle Scholar
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All the compounds gave satisfactory spectral data.
Data of Compound 6
IR (neat): 1735 (br) cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 5.55 (br s, 1 H), 3.68 (s, 3 H), 3.06 (part of an AB system, J = 5.86 Hz, 1 H), 2.92 (part of an AB system, J = 5.86 Hz, 1 H), 2.77 (dd, J 1 = 10.26 Hz, J 2 = 5.87 Hz, 1 H), 2.15 (dd, J 1 = 13.19 Hz, J 2 = 10.26 Hz, 1 H), 1.87 (d, J = 1.46 Hz, 3 H), 1.74 (dd, J 1 = 12.83 Hz, J 2 = 5.87 Hz, 1 H), 1.26 (s, 3 H), 1.04 (s, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 204.3, 173.8, 146.2, 124.9, 59.1, 51.9, 50.6, 49.6, 45.2, 40.9, 36.7, 17.9, 15.7, 14.4. ESI-HRMS: m/z calcd for C14H19O4: 251.1283 [M + H]+; found: 251.1277 [M + H]+.

17

Data of Compound 14
IR (neat): 1735 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 3.68 (s, 3 H), 2.44-2.36 (m, 1 H), 2.32-2.15 (m, 2 H), 2.01 (d of AB pattern, J = 19.42 Hz, 1 H), 1.92 (d of AB pattern, J = 19.42 Hz, 1 H), 1.76-1.62 (m, 2 H), 1.09 (s, 3 H), 1.04-0.98 (m, 9 H). ¹³C NMR (100 MHz, CDCl3): δ = 219.0, 176.6, 53.2, 52.0, 50.7, 48.1, 45.6, 45.1, 36.4, 23.5, 21.4, 20.7, 14.2, 8.8. ESI-HRMS: m/z calcd for C14H23O3: 239.1647 [M + H]+; found: 239.1655 [M + H]+.

18

Data for Hydrazone Derivative 15 IR (neat): 1731 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 10.82 (br s, 1 H), 9.13 (d, J = 2.44 Hz, 1 H), 8.30 (dd, J 1 = 8.85 Hz, J 2 = 1.83 Hz, 1 H), 7.97 (d, J = 9.47 Hz, 1 H), 3.69 (s, 3 H), 2.67-2.45 (m, 1 H), 2.41-2.31 (m, 1 H), 2.30-2.25 (m, 2 H), 2.10 (d, J = 18.32 Hz, 1 H), 1.74-1.62 (m, 2 H), 1.19 (d, J = 6.72 Hz, 3 H), 1.10-1.09 (m, 6 H), 1.03 (s, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 176.6, 167.7, 145.2, 137.8, 130.1, 129.0, 123.7, 116.5, 53.4, 53.4, 52.0, 48.3, 47.9, 45.7, 35.8, 35.4, 20.9, 20.8, 14.3, 11.1. ESI-HRMS: m/z calcd for C20H27O6N4: 419.1931 [M + H]+; found: 419.1939 [M + H]+.
Crystal Data of Hydrazone Derivative 15
C20H26N4O6, M 418.45, space group, monoclinic, P 21/c, a = 20.475 (4), b = 14.245 (2), c = 7.3712 (12) Å, α = 90, β = 99.326 (19), γ = 90.0, U = 2121.5 (6)A³, Z = 4, D c  = 1.310 g/m³, T = 150 (2) K, F(000) = 888, size = 0.21 × 0.18 × 0.15 mm. Reflections/collected/unique 10087/3694 [R(int) = 0.1809], final R indices [I > 2σ(I)] = R 1 =  = 0.0732, wR 2 = 0.1210 R indices (all data) R 1 = 0.2346, wR 2 = 0.1622. The complete crystal data can be obtained free of charge from The Cambridge Crystallographic data Centre via www.ccdc.cam.ac.uk/data_request/cif quoting the CCDC number 694681.

19

Data of Compound 18 IR (neat): 1736 (br) cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 3.70 (s, 3 H), 2.58-2.50 (dd with structure, J 1 = 18 Hz, J 2 = 9 Hz, 1 H), 2.41-2.34 (d with structure, J = 9 Hz, 1 H), 2.24-2.16 (m, 2 H), 2.00-1.86 (m, 3 H), 1.03 (d, partly merged with a s, J = 7.33 Hz, 3 H), 1.02 (s, 3 H), 1.00 (s, 3 H), 0.99 (d, partly merged with s, J = 6.72 Hz, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 220.3, 176.3, 53.2, 51.9, 50.9, 50.6, 49.0, 47.3, 46.1, 44.2, 23.7, 18.9, 15.2, 11.9. ESI-HRMS: m/z calcd for C14H23O3: 239.1647 [M + H]+; found: 239.1655 [M + H]+.