Diels-Alder Reactions of Substituted Cyclohexa-2,4-dienones with Alkenes and Alkynes

Abstract

Substituted cyclohexa-2,4-dienones, generated in situ by pyrolysis of the appropriate dimer, participated in Diels-Alder reactions with various dienophiles to afford bicyclo[2.2.2]octenone and bicyclo[2.2.2]octadienone derivatives in high yields.

Key words

masked o-benzoquinone - spiroepoxycyclohexa-2,4-dienone - retro-Diels-Alder reaction - Diels-Alder reaction - tandem reaction

References

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Undergraduate Research Participant, Spring 2004.

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Representative Experimental Procedure.Synthesis of 4a: A mixture of dimer 3a (0.39 g, 1.0 mmol), styrene (1.0 g, 9.62 mmol) in o-xylene (3 mL) was heated at 230 °C for 43 h in a sealed tube. The solvent was evaporated and the residue was chromatographed on silica gel (CH₂Cl₂ as eluant) to afford cycloadduct 4a as colorless oil (0.57 g, 95% yield). ¹H NMR (400 MHz, CDCl₃): δ = 1.65 (ddd, J = 2.8, 6.6, 13.2 Hz, 1 H), 1.81 (dd, J = 8.0, 14.2 Hz, 1 H), 2.35 (dd, J = 6.1, 14.2 Hz, 1 H), 2.61 (ddd, J = 2.8, 9.6, 10.1 Hz, 1 H), 3.04 (dd, J = 6.7, 9.6 Hz, 1 H), 3.19-3.21 (m, 1 H), 3.37 (s, 3 H), 3.42 (s, 3 H), 4.78-4.82 (m, 1 H), 4.91-4.94 (m, 1 H), 5.66-5.78 (m, 1 H), 6.00 (d, J = 8.1 Hz, 1 H), 6.62 (dd, J = 7.2, 8.1 Hz, 1 H), 7.08-7.19 (m, 5 H). ¹³C NMR (100 MHz, CDCl₃): δ = 33.4, 34.4, 38.9, 44.7, 49.7, 50.3, 56.0, 94.0, 117.8, 126.9, 128.3, 128.9, 134.5, 134.6, 143.1, 202.4. Anal. Calcd for C₁₉H₂₂O₃ (298.38): C, 76.48; H, 7.44. Found: C, 76.24; H, 7.52.
Synthesis of 4b: A mixture of dimer 3b (0.48 g, 2.0 mmol), styrene (1.00 g, 9.62 mmol) in o-xylene (3 mL) was heated at 230 °C for 43 h in a sealed tube. The solvent was evaporated and the residue was chromatographed on silica gel (CH₂Cl₂ as eluant) to afford cycloadduct 4b as colorless oil (0.47 g, 52% yield). ¹H NMR (250 MHz, CDCl₃): δ = 1.82-1.90 (m, 1 H), 2.61-2.74 (m, 2 H), 2.89 (d, J = 6.4 Hz, 1 H), 3.20 (d, J = 6.1 Hz, 1 H), 3.42-3.53 (m, 2 H), 6.18-6.24 (m, 1 H), 6.70-6.76 (m, 1 H), 7.16-7.33 (m, 5 H). ¹³C NMR (63 MHz, CDCl₃): δ = 30.5, 38.9, 40.3, 52.8, 54.9, 126.7, 127.1, 127.5, 128.3, 135.4, 143.4, 204.4. Anal. Calcd for C₁₅H₁₄O₂ (226.28): C, 79.62; H, 6.25. Found: C, 79.44; H, 6.40.