Efficient Higher-Order Cycloaddition Reactions of 8,8-Dicyanoheptafulvene with Dienes

Abstract

The cycloaddition reactions of 8,8-dicyanoheptafulvene with electron-rich dienes afforded the higher order cycloaddition products in excellent yields. With cyclic dienes as well as dimeth­oxybutadiene the [8+2] adducts were obtained exclusively. With methyl- and dimethylbutadienes the [6+4] adducts were the only products isolated.

Key words

cycloadditions - bicyclic compounds - polycycles - di­cyanoheptafulvene - tetrahydroazulenes

References

• 1 For a review, see: Nair V. Anilkumar G. Synlett  1998,  950 
• 2a Nozoe T. Mukai T. Osaka S. Shishido N. Bull. Chem. Soc. Jpn.  1961,  34:  1384 
• 2b Rapp KM. Daub J. Tetrahedron Lett.  1977,  25:  227 
• 2c Reichardt C. Yun K.-Y. Angew. Chem., Int. Ed. Engl.  1982,  21:  65 
• 2d Oda M. Kitahara Y. J. Chem. Soc., Chem. Commun.  1971,  367 
• 2e Rapp KM. Daub J. Tetrahedron Lett.  1976,  24:  2011 
• 2f Baier M. Daub J. Hasenhuendl A. Merz A. Rapp KM. Angew. Chem., Int. Ed. Engl.  1981,  20:  198 
• 3a Liu C.-Y. Ding S.-T. Chen S.-Y. You C.-Y. Shie H.-Y. J. Org. Chem.  1993,  58:  1628 
• 3b Oda M. Kitahara Y. Bull. Chem. Soc. Jpn.  1970,  43:  1920 
• 3c Oda M. Kitahara Y. Synthesis  1971,  367 
• 3d Kuroda S. Funamizu M. Kitahara Y. Asao T. Tetrahedron Lett.  1975,  24:  1973 
• 3e Oda M. Kitahara Y. Angew. Chem., Int. Ed. Engl.  1969,  8:  673 
• 4a Liu C.-Y. Ding S.-T. J. Org. Chem.  1992,  57:  4539 
• 4b Liu C.-Y. Shie H.-Y. Chen S.-Y. You C.-Y. Wang W.-C. Hua L.-N. Yang H.-J. Tseng C.-M. Tetrahedron  1997,  53:  17275 
• 4c Kitahara Y. Oda M. Jerusalem Symp. Quantum Chem. Biochem.  1971,  3:  284 
• 4d Ito K. Noro Y. Saito K. Takahashi K. Bull. Chem. Soc. Jpn.  1990,  63:  2573 
• 4e Ikuno K. Kobayashi T. Chin U. Noguchi M. Synthesis  1995,  518 
• 5a Nair V. Nair AG. Radhakrishnan KV. Nandakumar MV. Rath NP. Synlett  1997,  767 
• 5b Nair V. Anilkumar G. Radhakrishnan KV. Sheela KC. Tetrahedron  1997,  53:  17361 
• 5c Nair V. Anilkumar G. Radhakrishnan KV. Nandakumar MV. Kumar S. Tetrahedron  1997,  53:  15903 
• 6 Nair V. Abhilash KG. Zeimer B. Tetrahedron Lett.  2005,  46:  2307 
• 10 Takeshita H. Mori A. Kubo K. Org. Synth.  1998,  75:  210 

7

Crystal data for 3a: empirical formula C₃₂H₃₂N₄, formula weight 472.62, triclinic, space group P-1, a = 7.123(2) Å, b = 8.306(3) Å, c = 11.506(4) Å, α = 87.363(6)°, β = 81.053(7)°, γ = 83.939(6)°, V = 668.4(4) ų, Z = 1, D _calcd = 1.174 Mg/m³, λ = 0.71073 Å, absorption coefficient = 0.070 mm^-1, F(000) = 252, T = 293(2) K, crystal size = 0.22 × 0.10 × 0.06 mm. CCDC 639690 contains the supplementary crystallographic data for this compound.

8

Crystal data for 3c: empirical formula C₁₇H₁₆N₂O, formula weight 264.32, monoclinic, space group P2₁/n, a = 8.4450(12) Å, b = 13.0730(18) Å, c = 12.8118(18) Å, α = 90°, β = 99.069(3)°, γ = 90°, V = 1394.6(3) ų, Z = 4, D _calcd = 1.259 Mg/m³, λ = 0.71073 Å, absorption coefficient = 0.080 mm^-1, F(000) = 560, T = 273(2) K, crystal size = 0.30 × 0.20 × 0.12 mm. CCDC 639691 contains the supplementary crystallographic data for this compound.

9

Crystal data for 3e: empirical formula C₁₆H₁₆N₂O₂, formula weight 268.31, monoclinic, space group = P2₁/n, a = 8.0664(8) Å, b = 14.2902(15) Å, c = 13.3056(14) Å, α = 90°, β = 103.564(2)°, γ = 90°, V = 1491.0(3) ų, Z = 4, D _calcd = 1.195 Mg/m³, λ = 0.71073 Å, absorption coefficient = 0.080 mm^-1, F(000) = 568, T = 296(2) K, crystal size = 0.34 × 0.28 × 0.22 mm. CCDC 639692 contains the supplementary crystallographic data for this compound.