Download PDF
Synlett 2014; 25(11): 1601-1605
DOI: 10.1055/s-0033-1339031
letter
© Georg Thieme Verlag Stuttgart · New York

The Preparation of Stereoisomeric Tricyclo[4.2.1.02,5]nona-7-ene-3,4-dicar­boximides and Anhydrides: Literature Corrections and New Products

Philip S. Kearns
a   Centre for Molecular Architecture, Central Queensland University, Rockhampton, Queensland 4702, Australia
,
Bryant K. Wells
a   Centre for Molecular Architecture, Central Queensland University, Rockhampton, Queensland 4702, Australia
,
Ronald N. Warrener
a   Centre for Molecular Architecture, Central Queensland University, Rockhampton, Queensland 4702, Australia
,
Davor Margetić*
b   Laboratory for Physical-organic Chemistry, Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb, Croatia   Fax: +385(1)4680195   Email: margetid@irb.hr
› Author Affiliations
Further Information

Publication History

Received: 05 March 2014

Accepted after revision: 08 April 2014

Publication Date:
20 May 2014 (online)

    Permissions and Reprints All articles of this category


Abstract

The bis-homo Diels–Alder reactions of maleimide and N-methylmaleimide with quadricyclane are shown to produce mixtures containing both the exo,anti- and exo,syn-tricyclo-[4.2.1.02,5]nona-7-ene-3,4-dicarboximides, whereas the isomeric endo,anti-adducts are available from the reaction of cyclopentadiene with the appropriate cyclobutene-3,4-dicarboximides. The related reaction of quadricyclane with maleic anhydride had been erroneously reported to form single adducts; our work shows that two stereoisomers are actually formed and these have been chemically related to the maleimide and N-methylmaleimide adducts. The proton chemical shifts of the adduct formed by reaction of cyclobutene-3,4-dicarboxylic anhydride with cyclopentadiene have also been miss-assigned. Preparation of [3] and [5] polynorbornane scaffolds with terminal succinimides have been effected by coupling the stereoisomeric adducts at the norbornene π-bond by using 2,5-bis(trifluoromethyl)-1,3,4-oxadiazole and bisepoxide. The spacer shapes and dimensions have been determined by molecular modelling.

Key words

cycloaddition - Diels–Alder reaction - quadricyclane - norbornenes - stereochemistry

Supporting Information

    for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
  • Supporting Information
 

  • References

  • 1 Aggarwal VK. Nat. Chem. 2009; 1: 433
    Crossref
  • 3 Shang M, Warrener RN, Butler DN, Margetić D, Murata Y. Mol. Diversity 2011; 15: 541
    Crossref
    • 4a Margetić D, Trošelj P, Johnston MR. Mini-Rev. Org. Chem. 2011; 8: 49
    • 4b Trošelj P, Margetić D, Đilović I, Matković-Čalogović D. J. Heterocycl. Chem. 2013; 50: 83
      Crossref
    • 5a Dohm J, Nieger M, Rissanen K, Vögtle F. Chem. Ber. 1991; 124: 915
      Crossref
    • 5b Vögtle F. Cyclophane Chemistry. Synthesis, Structures and Reactions. John Wiley and Sons; Chichester: 1993
      Google Scholar
  • 6 Butler DN, Shang M, Warrener RN. Chem. Commun. 2001; 159
  • 7 Warrener RN, Shang M, Butler DN. Tetrahedron Lett. 2000; 41: 5985
    Crossref
  • 8 All new compounds gave satisfactory 1H and 13C NMR and high-resolution mass spectra. Quadricyclane Cycloaddition; Typical Procedure for the Preparation of 18 and 19: Quadricyclane (280 mg, 30 mmol) and N-methylmaleimide (333 mg, 30 mmol) in toluene (20 mL) were heated to reflux for 18 h. Evaporation of the solvent gave an off-white solid (540 mg, 88%), that was shown (1H NMR) to be a mixture of isomers 18 (88%) and 17 (19%). A sample of this mixture (112 mg) was separated by HPLC (reverse phase) to afford the pure components. Compound 18: Yield: 52 mg; mp 100.5–101 °C. 1H NMR (300 MHz, CDCl3): δ = 1.50 (d, J = 9.7 Hz, 1 H), 1.60 (d, J = 9.7 Hz, 1 H), 2.15 (br s, 2 H), 2.71–2.72 (m, 2 H), 2.98 (br s, 2 H), 3.02 (s, 3 H), 6.04–6.05 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 25.0, 40.6, 40.9, 41.3, 44.2, 135.7, 178.9. HRMS (EI): m/z calcd for C12H13NO2: 203.0946; found: 203.0942. Compound 19: Eluted first; yield: 11 mg; mp 148–149 °C. 1H NMR (300 MHz, CDCl3): δ = 0.99 (d, J = 10.9 Hz, 1 H), 1.23 (d, J = 10.9 Hz, 1 H), 2.45–2.46 (m, 2 H), 2.93 (s, 3 H), 3.01 (d, J = 1.7 Hz, 2 H), 3.31–3.32 (m, 2 H), 6.04–6.05 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 24.8, 36.7, 37.4, 41.7, 42.1, 137.2, 178.9. HRMS (EI): m/z calcd for C12H13NO2: 203.0946; found: 203.0942.
  • 9 Warrener RN, Margetić D, Tiekink ER. T, Russell RA. Synlett 1997; 196
    Article in Thieme Connect
    • 10a Jones GA, Shephard MJ, Paddon-Row MN, Beno BR, Houk KN, Redmond K, Carpenter BK. J. Am. Chem. Soc. 1999; 121: 4334
      Crossref
    • 10b Warrener RN, Amarasekara AS. Synlett 1997; 167
      Article in Thieme Connect
    • 10c De Lucchi O, Fabris F. Synlett 1993; 275
      Article in Thieme Connect
    • 10d Warrener RN, Russell RA, Solomon R, Pitt IG, Butler DN. Tetrahedron Lett. 1987; 28: 6503
      Crossref
    • 10e Jenner G, Papadopoulos M. Tetrahedron Lett. 1985; 26: 725
      Crossref
    • 11a Jung ME, Shapiro JJ. J. Am. Chem. Soc. 1980; 102: 7862
      Crossref
    • 11b Marchand AP. Stereochemical Applications of NMR Studies in Rigid Bicyclic Systems . Verlag Chemie Int; Deerfield Beach, FL: 1982: 192
      Google Scholar
  • 12 Smith CD. J. Am. Chem. Soc. 1966; 88: 4273
    Crossref
  • 13 Tabushi I, Yamamura K, Yoshida Z. J. Am. Chem. Soc. 1972; 94: 787
    Crossref
  • 14 Warrener RN, Groundwater P, Pitt IG, Butler DN, Russell RA. Tetrahedron Lett. 1991; 32: 1885
    Crossref
  • 15 Cadogan JI. G, Cameron DK, Gosney I, Tinley EJ, Wyse SJ, Amaro A. J. Chem. Soc., Perkin Trans. 1 1991; 2081
  • 16 Warrener RN, Margetić D, Foley PJ, Butler DN, Winling A, Beales KA, Russell RA. Tetrahedron 2001; 57: 571
    Crossref