Practical Preparation of Diosphenols by Ring Opening of α,β-Epoxyketones Catalyzed by Silica Gel Supported Acids

Rui Zhu; Lixin Xing; Xinyan Wang; Chuanjie Cheng; Bo Liu; Yuefei Hu

doi:10.1055/s-2007-985584

LETTER

Practical Preparation of Diosphenols by Ring Opening of α,β-Epoxyketones Catalyzed by Silica Gel Supported Acids

Rui Zhu, Lixin Xing, Xinyan Wang, Chuanjie Cheng, Bo Liu, Yuefei Hu*
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China
Fax: +86(10)62771149; e-Mail: yfh@mail.tsinghua.edu.cn;

Abstract

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Abstract

The mixed acid (H₂SO₄-HOAc) catalyzed ring opening of α,β-epoxyketone was the most used method for the preparation of diosphenols, but it seriously suffered from poor yields and tedious workup operations. By using silica gel supported mixed acid (H₂SO₄-HOAc), a variety of α,β-epoxyketones were converted into the corresponding diosphenols in unprecedented high yields within a few minutes.

Key words

supported catalysis - regioselective - peroxides - ring opening - green chemistry

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Typical Procedure for the Preparation of 3d: The mixture of substrate 4d (1.0 g), the mixed acid [2.0 mL, H₂SO₄-HOAc (1:2 wt/wt)] and silica gel (8.0 g) in THF (10 mL) was rotaevaporated in vacuum (<15 mmHg) at 70 °C. After the solvent had been removed, the reaction was continued for another 3 min. The resultant non-stick solid was then washed with CH₂Cl₂ and the combined organic layers were washed with aq Na₂CO₃, brine and dried over Na₂SO₄. Removal of the solvent yielded the crude product, which was purified by chromatography to give the pure product 3d (0.81 g, 81%) as white crystals; mp 88-90 °C (EtOAc-PE); [α]_D ²⁰ +277.86° (c = 1.20, CHCl₃). IR: 3386, 2958, 2937, 2871, 1739, 1661 cm^-1. ¹H NMR: δ = 6.17 (s, 1 H), 3.02-3.06 (m, 1 H), 2.61-2.75 (m, 4 H), 2.39-2.46 (m, 1 H), 2.07-2.09 (m, 1 H), 1.90-1.92 (m, 1 H), 1.32 (s, 3 H). ¹³C NMR: δ = 217.4, 193.7, 141.3, 137.2, 48.4, 35.7, 31.7, 29.6, 21.1, 20.7. MS: m/z (%) = 180 (100), 152 (21), 137 (19), 110 (19), 109 (35), 95 (18), 81 (31), 67 (34), 55 (23), 39 (28). Anal. Calcd for C₁₀H₁₂O₃: C, 66.65; H, 6.71. Found: C, 66.58; H, 6.70. The same proce-dure was efficiently used to convert the substrates 4a-j into the corresponding products 3a-j (see Table [2] ). Products 3a-j are known compounds and their ¹H NMR and ¹³C NMR spectra are available upon request from the authors.