The High Stereoselectivity of the Tandem Sequence Diels-Alder Reaction/Ireland­-Claisen Rearrangement Starting from Substituted O-(E)-Buta-1,3-dienyl Ketene Acetals and Cyclic Dienophiles

Abstract

A new tandem reaction leads to bicyclic cyclohexene derivatives with complete control of the relative configuration of the four chiral centers formed. The high diastereoselectivity is the consequence of an endo-selective Diels-Alder reaction followed by an Ireland-Claisen rearrangement that proceeds via a boat-like transition state.

cycloaddition - Diels-Alder reaction - rearrangement - stereoselectivity - tandem reaction

References

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7

Crystal structure analysis of 2f: C₂₀H₂₅NO₄Si, M _r = 371.50, monoclinic, space group P2₁, a = 8.191(1), b = 23.442(2), c = 11.342(1) Å, β = 105.12(1)°, V = 2102.4(3) ų, Z = 4, ρ_calcd = 1.174 g cm^-3, T = 223(2) K, µ = 1.34 cm^-1, λ = 0.71073 Å, 1.65 ≤ θ ≤ 26.05°, Stoe IPDS diffractometer, crystal dimensions 0.65 × 0.40 × 0.15 mm; 7956 independent reflections, 3934 observed reflections with [I > 2σ(I)]; R-values [I > 2σ(I)]: R ₁ = 0.0658, wR ₂ = 0.1409.
Crystal structure analysis of 4: C₂₄H₁₈N₂O₆, M _r = 430.40, triclinic, space group P, a = 7.894(2), b = 11.426(3), c = 12.057(4)Å, α = 101.78(4), β = 97.43(4), χ = 98.91(3)°, V = 1037.2(5) ų, Z = 2, ρ_calcd = 1.378 g cm^-3, T = 293(2) K, µ = 1.01 cm^-1, λ = 0.71073 Å, 1.65 ≤ θ ≤ 26.05°, Stoe IPDS diffractometer, crystal dimensions 0.70 × 0.50 × 0.40 mm; 3738 independent reflections, 2453 observed reflections with [I > 2σ(I)]; R-values [I > 2σ(I)]: R ₁ = 0.0328, wR ₂ = 0.0816.
Crystal structure analysis of 5: C₂₄H₁₈N₂O₆·CHCl₃, M _r = 549.77, triclinic, space group P, a = 10.261(3), b = 11.610(3), c = 11.818(4)Å, α = 76.81(3), β = 67.38(3), χ = 87.40(2)°, V = 1263.9(7) ų, Z = 2, ρ_calcd = 1.445 g cm^-3, µ = 1.34 cm^-1, λ = 0.71073 Å, 2.00 ≤ θ ≤ 25.50°, Stoe AED2 diffractometer, crystal dimensions 0.65 × 0.49 × 0.23 mm; 4709 independent reflections, 3504 observed reflections with [I > 2σ(I)]; R-values [I > 2σ(I)]: R ₁ = 0.0701, wR ₂ = 0.1669.
All three structures were refined with full-matrix block least squares on F ²; all non-hydrogen atoms were anisotropically refined. Crystallographic data (excluding structure factors)for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-118778 for 1f, CCDC-629878 for 2f, CCDC-629879 for 3c, CCDC-629880 for 4 and CCDC-629881 for 5. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: [phone]; e-mail: [e-mail].

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