LETTER
Practical Preparation of Diosphenols by Ring Opening of a,b-Epoxyketones
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(11) 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); [a]D20 +277.86°
(c = 1.20, CHCl3). IR: 3386, 2958, 2937, 2871, 1739, 1661
cm–1. 1H NMR: d = 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: d = 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.
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Synlett 2007, No. 14, 2267–2271 © Thieme Stuttgart · New York