Ring-Opening Reactions of Epoxides Catalyzed by Molybdenum(VI) ­Dichloride Dioxide

Abstract

Transformation of epoxides to β-alkoxy alcohols, acetonides, and α-alkoxy ketones is achieved by using molybdenum(VI) dichloride dioxide (MoO₂Cl₂) as a catalyst. Alcohol, aldehyde, oxime, tosyl, and tert-butyldimethylsilyl functional groups are tolerated during the methanolysis and acetonidation of the functionalized epoxides. No polymerization product is observed with any of the epoxides. Direct conversion of epoxides devoid of sensitive functional groups into the corresponding α-methoxy ketone is achieved in a single step by using the MoO₂Cl₂/Oxone system.

Key words

molybdenum - catalyst - epoxides - nucleophiles - ring opening

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9

Crystallographic data for 19: CCDC # 650503. Intensity data were collected on a APEX CCD diffractometer equipped with Mo-Kα (λ = 0.7107 Å) radiation. The intensity data were corrected for Lorentzian, polarization and absorption effects. C₁₀H₁₄O₄, M = 198.21, monoclinic, a = 7.2698 (3) Å, b = 8.3209 (3) Å, c = 17.0354 (7) Å, α = 90°, β = 96.144 (2)°, γ = 90°, V = 1024.57 (7) ų, space group P2(1)/n, Z = 4, d _calcd = 1.285 g/cm³, 6905/2510 reflections collected/unique, final R indices [I > 2σ(I)] R1 = 0.0390, wR2 = 0.0998, R indices (all data) R1 = 0.0576, wR2 = 0.1119. The crystallographic data for 19 have been deposited with the Cambridge Crystallographic Data Centre. Copies of this information may be obtained free of charge from the Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [Fax: [phone], e-mail: [e-mail] or http://www.ccdc.cam. ac.uk].