Synthesis 2008(17): 2719-2728  
DOI: 10.1055/s-2008-1067203
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Studies on Cycloaddition of Cyclohexa-2,4-dienones and Transformation of Adducts: A General, Stereoselective Route to Multifunctional Bicyclo[2.2.2]octanes and Diquinanes

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

Publication History

Received 11 March 2008
Publication Date:
24 July 2008 (online)

Abstract

The cycloaddition of in situ generated cyclohexa-2,4-dienones with vinyl ethers, vinyl acetate, and phenyl vinyl sulfone leading to variously functionalized bicyclo[2.2.2]octanes has been examined. Functional group manipulation in the resulting adducts gave bicyclo[2.2.2]octanes endowed with a β,γ-enone chromophore. Triplet-sensitized irradiation of bicyclooctenones followed by reductive cleavage provided a stereoselective route to diquinane frameworks having diverse functionalities.

    References:

  • 1a Carruthers W. Cycloaddition Reactions in Organic Synthesis   Pergamon Press; Oxford: 1990. 
  • 1b Nicolaou KC. Snyder SA. Montagnon T. Vassilikogiannakis G. Angew. Chem. Int. Ed.  2002,  41:  1668 
  • 1c Stocking EM. Williams RM. Angew. Chem. Int. Ed.  2003,  42:  3078 
  • 1d Oikawa H. Tokiwano T. Nat. Prod. Rep.  2004,  21:  321 
  • 1e Takao K. Munakata R. Tadano K. Chem. Rev.  2005,  105:  4779 
  • 2a Lebrasseur N. Gagnepain J. Ozanne-Beaudenon A. Leger J.-M. Quideau S. J. Org. Chem.  2007,  72:  6280 
  • 2b Gagnepain J. Castel F. Quideau S. Angew. Chem. Int. Ed.  2007,  46:  1533 
  • 2c Quideau S. Pouysegu L. Org. Prep. Proced. Int.  1999,  31:  617 
  • 2d Magdziak D. Meek SJ. Pettus TRR. Chem. Rev.  2004,  104:  1383 ; and references therein
  • 3a Liao C.-C. Pure Appl. Chem.  2005,  77:  1211 
  • 3b Chang SY. Huang S.-L. Villarante NR. Liao C.-C. Eur. J. Org. Chem.  2006,  4648 
  • 3c Chittimalla SK. Hsiao F.-Y. Liao C.-C. Org. Biomol. Chem.  2006,  4:  2267 
  • 3d Liao C.-C. Wei CP. Tetrahedron Lett.  1989,  30:  2255 
  • 4a Bonnarme V. Bachmann C. Cousson A. Mondon M. Gesson J.-P. Tetrahedron  1999,  55:  433 
  • 4b Bonnarme V. Mondon M. Cousson A. Gesson J.-P. Chem. Commun.  1999,  1143 
  • 4c Gesson J.-P. Hervaud L. Mondon M. Tetrahedron Lett.  1993,  34:  2941 
  • 5a Singh V. Acc. Chem. Res.  1999,  32:  324 
  • 5b Singh V. Pal S. Mobin SM. J. Org. Chem.  2006,  71:  3014 
  • 5c Singh V. Pal S. Tosh DK. Mobin SM. Tetrahedron  2007,  63:  2446 
  • 6a Toyota M. Asano T. Ihara M. Org. Lett.  2005,  7:  3929 
  • 6b Banwell MG. Edwards AJ. Harfoot GJ. Jolliffe KA. Tetrahedron  2004,  60:  535 
  • 6c Srikrishna A. Satyanarayana G. Org. Lett.  2004,  6:  2337 
  • 6d Hagiwara H. Morii A. Yamada Y. Hoshi T. Suzuki T. Tetrahedron Lett.  2003,  44:  1595 
  • 6e Paquette LA. Guevel R. Sakamoto S. Kim IH. Crawford J. J. Org. Chem.  2003,  68:  6096 
  • 6f Spiegel DA. Njardarson JT. Wood JL. Tetrahedron  2002,  58:  6545 
  • 6g Tisdale EJ. Chowdhury C. Vong BG. Li H. Theodorakis EA. Org. Lett.  2002,  4:  909 
  • 7a Kim M. Gais H.-J. J. Org. Chem.  2006,  71:  4642 
  • 7b Sheddan NA. Mulzer J. Org. Biomol. Chem.  2006,  4:  4127 
  • 7c Sheddan NA. Mulzer J. Org. Lett.  2006,  8:  3101 
  • 7d Sheddan NA. Mulzer J. Org. Lett.  2005,  7:  5115 
  • 8a Bergen MV. Gais H.-J. J. Am. Chem. Soc.  2002,  124:  4321 
  • 8b Lerm M. Gais H.-J. Cheng K. Vermeeren C. J. Am. Chem. Soc.  2003,  125:  9653 
  • 8c Okamoto S. Subburaj K. Sato F. J. Am. Chem. Soc.  2000,  122:  11244 
  • 9a Das S. Chandrashekhar S. Yadav JS. Gree R. Chem. Rev.  2007,  107:  3286 
  • 9b Schinzer D. Carbacyclins: Stable Analogues of Prostacyclins, In Organic Synthesis Highlights II   Waldman HE. VCH; New York: 1995.  p.301 
  • 9c Collins PW. Djuric SW. Chem. Rev.  1993,  93:  1533 
  • 10a Paquette LA. Doherty AM. Polyquinane Chemistry   Vol. 26:  Hafner K. Rees CW. Trost BM. Lehn J.- M. Schleyer PvR. Zahradnik R. Springer Verlag; Berlin: 1987. 
  • 10b Mehta G. Srikrishna A. Chem. Rev.  1997,  97:  671 
  • 10c Jung ME. Maderna A. Tetrahedron Lett.  2005,  46:  5057 
  • 10d Hagiwara H. Endou S. Fukushima M. Hoshi T. Suzuki T. Org. Lett.  2004,  6:  1115 
  • 10e Kraus GA. Kim J. Tetrahedron Lett.  2004,  45:  1457 
  • 11a Ito H. Hasegawa M. Takenaka Y. Kobayashi J. Iguchi K. J. Am. Chem. Soc.  2004,  126:  4520 
  • 11b Anderson RJ. Taglialatela-Scafati O. Deo-Jangra U. Campbell N. Roberge M. Org. Lett.  2002,  4:  4085 
  • 12a Adler E. Brasen S. Miyake H. Acta Chem. Scand.  1971,  25:  2055 
  • 12b Adler E. Holmberg K. Acta Chem. Scand., Sect. B  1974,  28:  465 
  • 12c Singh V. Bedekar AV. Synth. Commun.  1989,  19:  107 
  • 15a Demuth M. Hisken W. Angew. Chem., Int. Ed. Engl.  1985,  24:  973 
  • 15b Demuth M. Schaffner K. Angew. Chem., Int. Ed. Engl.  1982,  21:  820 
  • 15c Yates P. Burnell DJ. Freer VJ. Sawyer JF. Can. J. Chem.  1987,  65:  69 
  • 15d Padwa A. Zhi L. Fryxel GE. J. Org. Chem.  1991,  56:  1077 
  • 16a Zimmerman HE. Armesto D. Chem. Rev.  1996,  96:  3065 
  • 16b Armesto D. Ortiz MJ. Agarrabeitia AR. In CRC Handbook of Organic Photochemistry and Photobiology   Horspool W. Lenci F. CRC Press; Boca Raton FL: 2004.  p.95.1 
  • 17 Singh V. In CRC Handbook of Organic Photochemistry and Photobiology   Horspool W. Lenci F. CRC Press; Boca Raton FL: 2004.  p.78.1 
  • 18 Enholm EJ. Jia ZJ. J. Org. Chem.  1997,  62:  174 
  • 19a Park H. Lee YS. Bull. Korean Chem. Soc.  1993,  14:  86 
  • 19b Node M. Inoue T. Araki M. Nakamura D. Nishide K. Tetrahedron Lett.  1995,  36:  2255 
13

Crystal data 7b: C13H19O3Cl, MW 258.09, space group, monoclinic, P21/c, a = 10.256(2), b = 7.6274(12), c = 15.360(7) Å, α = 90.0, β = 107.44(3), γ = 90.0˚, U = 1146.3(6) A³, Z = 4, D c = 1.218 g/m³, T = 293(2) K, F(000) = 456, size = 0.26 × 0.16 × 0.12 mm. Reflections/collected/unique 10532/2012 [R(int) = 0.0258], final R indices [I >2σ(I)] = R1 = 0.0369, wR2 = 0.105c, R indices (all data) R1 = 0.0554, wR2 = 0.1107. 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 674959.

14

Crystal data 11c: C17H19ClO4S, MW 354.83, space group, monoclinic, P21/c, a = 8.3197(6), b = 23.0608(19), c = 15.360(7) Å, α = 90.0, β = 96.045(6), γ = 90.0˚, U = 1600.8(2) A³, Z = 4, D c = 1.472 mg/m³, T = 120(2) K, F(000) = 744, size = 0.33 × 0.27 × 0.21 mm. Reflections/collected/unique 8932 / 2801 [R(int) = 0.0732], final R indices [I >2σ(I)] = R1 = 0.0826, wR2 = 0.2139, R indices (all data) R1 = 0.0965, wR2 = 0.2226. 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 674960.