Ring-Rearrangement Metathetic Approach to Fused 6/5/6/5/6-Oxacyclic Ring System and Bipentalene Derivatives

Abstract

We have developed a useful synthetic route to a 6/5/6/5/6-oxacyclic ring system and bipentalene derivatives from dimeric 7-oxonorbornene derivatives by using ring-rearrangement metathesis as a key step. This method provides access to fused oxacycles containing eight stereogenic centers in just three steps and to bipentalene derivatives in two steps only.

Key words

ring-rearrangement metathesis - oxacycles - pentalenes - norbornenes - Grubbs catalysts

• References and Notes

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• 22 Bipentalene Derivatives; General ProcedureA magnetically stirred solution of the RRM precursor in anhyd CH₂Cl₂ was degassed by sequential purging with N₂ and ethylene gas for about 10 min each. The Grubbs catalyst was added in one portion at rt under C₂H₂ at 1 atm, and purging was continued for another 2–5 min. The mixture was stirred at the appropriate temperature under C₂H₂ until the reaction was complete (TLC). The crude product was purified by column chromatography (silica gel, EtOAc–PE).3,3′-Divinyl-2,2′,3,3′,4,4′,6a,6a′-octahydro-1,1′-bipentalene-3a,3a′(1H,1′H)-diol (12a)Colorless liquid; yield: 65%. ¹H NMR (500 MHz, CDCl₃): δ = 5.93–5.86 (m, 2 H), 5.69–5.68 (m, 2 H), 5.63–5.61 (m, 2 H), 5.12–5.06 (m, 4 H), 2.91–2.90 (m, 2 H), 2.69–2.65 (m, 2 H), 2.60–2.55 (m, 2 H), 2.19–2.15 (m, 2 H), 1.95–1.91 (m, 2 H), 1.85–1.81 (m, 2 H), 1.86–1.71 (m, 2 H), 1.10–1.07 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 137.7, 130.4, 129.3, 116.1, 90.0, 60.8, 55.2, 44.5, 43.0, 34.6. HRMS (ESI, Q-ToF): m/z [M + Na]⁺ calcd for C₂₀H₂₆NaO₂: 321.1825; found: 321.1823.3a,3a′-Dimethoxy-3,3′-divinyl-1,1′,2,2′,3,3′,3a,3a′,4,4′,6a,6a′-dodecahydro-1,1′-bipentalene (17)Yellow liquid; yield: 60%. ¹H NMR (500 MHz, CDCl₃): δ = 5.94–5.48 (m, 6 H), 5.15–5.03 (m, 4 H), 3.25 (s, 3 H), 3.20 (s, 3 H), 3.11–3.06 (m, 2 H), 2.84–2.68 (m, 2 H), 2.49–2.31 (m, 4 H), 2.19–1.88 (m, 4 H), 1.17–1.06 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 138.5, 135.6, 133.8, 130.8, 130.3, 127.4, 117.3, 115.5, 97.9, 95.4, 54.7, 54.6, 53.9, 51.3, 51.2, 50.9, 44.6, 42.7, 38.9, 36.8, 34.5, 34.3. HRMS (ESI, Q-ToF): m/z [M + H]⁺ calcd for C₂₂H₃₁O₂: 327.4800; found: 327.4805.