Ceric(IV)-Mediated Reaction of Methylenecyclopropanes in Organic Synthesis: A Facile Access to Dihydrofurans and Cyclobutanones

Abstract

Alkylidenecyclopropanes undergo CAN-mediated addition reactions with 1,3-dicarbonyl compounds or ring rearrangement reactions leading to dihydrofuran and cyclobutanone derivatives, respectively, in moderate yields.

Key words

methylenecyclopropanes - ammonium cerium(IV) nitrate - 1,3-dicarbonyl compounds - dihydrofuran - cyclobutanone

References

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7

X-ray crystal data for compound 3a: C₂₂H₂₀O₂, MW = 316.38, Monoclinic, space group P2₁/n, a = 9.9482 (12), b = 12.0846 (14), c = 13.6979 (16) Å, α = 90, β = 99.745 (2), γ = 90, V = 1623.0(3) ų, T = 293 (2) K, Z = 4, ρ_calcd = 1.295 Mg/m³, µ = 0.081 mm^-1, λ = 0.71073 Å, F(000) 672.00, independent reflections (R _int = 0.0794), 9396 reflections collected; refinement method, full-matrix least-squares refinement on F²; Goodness-of-fit on F² = 0.907; Final R indices [I > 2σ(I)] R1 = 0.0470, wR2 = 0.0913.

8

MCPs 1 are not very soluble in CH₃CN, therefore the co-solvent THF is required.

12

Due to the poor solubility of MCPs in H₂O, we added THF as the co-solvent (THF-H₂O, 4:1).