Strain-Induced Regioselective Ring-Opening Cross-Metathesis of Hybrid Cage Propellane Containing both Bicyclo[2.2.1]heptene and Bicyclo[2.2.2]octene Units

Abstract

Herein, we report strain-driven regioselective tandem ring-opening cross-metathesis (ROCM) of a linearly fused cage system that contains both bicyclo[2.2.1]heptene and bicyclo[2.2.2]octene units fused to the same cage system. The synthesis of novel cage propellane involves Diels–Alder cycloaddition and [2+2] photocycloaddition as key steps.

Keywords

Diels–Alder reaction - [2+2] photocycloaddition - Kushner’s dione - ring-opening cross-metathesis - Grubbs catalyst

Publikationsverlauf

Eingereicht: 20. Juni 2022

Angenommen nach Revision: 30. August 2022

Accepted Manuscript online:
30. August 2022

Artikel online veröffentlicht:
07. Oktober 2022

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• 18 Synthesis of Diels–Alder Adduct 7: Caged dione 8 (1.2 g, 5.36 mmol) and norbornadiene (5–7 equiv) were dissolved in toluene (2–4 mL) in a sealed pressure tube and heated to 240–250 °C for 8–10 h. After completion of the reaction (TLC monitoring), the solvent was evaporated under reduced pressure and the crude reaction mixture was purified by silica gel column chromatography (0.1–0.5%, EtOAc/petroleum ether) to afford 7 as a white crystalline solid. Yield: 1.18 g (70%); R_f = 0.60 (15% EtOAc /petroleum ether); mp 230–232 °C. ¹H NMR (400 MHz, CDCl₃): δ = 6.33–6.30 (m, 2 H), 6.07 (d, J = 1.0 Hz, 2 H), 2.78–2.76 (m, 4 H), 2.63 (s, 2 H), 2.53 (d, J = 1.5 Hz, 4 H), 2.40 (d, J = 8.6 Hz, 1 H), 2.14 (s, 2 H), 1.89 (d, J = 11.2 Hz, 1 H), 1.73 (d, J = 11.2 Hz, 1 H), 0.86 (dd, J = 8.7, 0.7 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 212.7, 139.4, 133.7, 55.9, 55.8, 46.4, 43.4, 42.6, 41.7, 41.1, 38.2, 35.5. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₂H₂₁O₂: 317.1541; found: 317.1540.