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(a) Into a solution of 2-acetoxymethyl ketones (3a–e,g,
5 mmol) in ethanol (5 ml), Novozyme 435 (50 mg) was added.
The reaction mixture was shaken (250 rpm) at room temper-
ature (1.5 h for 3a–d, and 32 h for 3g). The enzyme was filtered
off from the reaction mixture and washed with acetone (2 ×
5 ml). The combined filtrates were evaporated, and the residue
was purified by column chromatography (silica gel, CH2Cl2–
acetone 9 : 1v/v) giving 4a–e as white solids or 4g as a colorless
oil in the yields shown in Table 1. (b) Into a solution of
1-acetoxypropan-2-one (3f, 1 mmol) in MeOH-d4 (1 ml),
Novozyme 435 (10 mg) was added. The reaction mixture was
shaken (250 rpm) at room temperature for 24 h. After removing
the enzyme by filtration, the residue was analyzed by NMR as
such.
All data of the known hydroxymethyl ketones [4a (mp, IR,
1H NMR and 13C NMR);46 4b mp,47 (IR and 1H NMR);48
4c (mp and 1H NMR);49 4f (1H NMR and 13C NMR);50 4g (IR,
1H NMR and 13C NMR)51] agreed with the published results.
Additional spectral data for known compounds: 4b: δC 65.83,
129.53, 129.94, 132.52, 132.76, 197.93; 4c: νmax(KBr)/cmϪ1 3424,
1676, 1552, 1288, 1172, 1104, 1008; δC 65.79, 112.44, 113.35,
123.47, 124.19, 126.66, 128.70, 150.37, 155.60, 183.72.
Data for new compounds: 4d (Found: C, 47.12; H, 2.67; Br,
31.44. Calc. for C10H7BrO3: C, 47.09; H, 2.77; Br, 31.33%); mp
156 ЊC; νmax(KBr)/cmϪ1 3432, 1680, 1544, 1440, 1292, 1168,
1112, 1008; δH (DMSO-d6) 4.71 (2H, d), 5.43 (1H, t, OH), 7.64
(1H, dd), 7.69 (1H, d), 7.84 (1H, s), 8.04 (1H, d); δC (DMSO-d6)
65.33, 113.00, 114.36, 116.24, 125.98, 128.86, 131.00, 151.22,
153.52, 190.18. 4e: (Found: C, 54.25; H, 3.18; N, 6.36. Calc. for
C10H7NO5: C, 54.31; H, 3.19; N, 6.33%); mp 160 ЊC; νmax(KBr)/
cmϪ1 3424, 3104, 1680, 1624, 1528, 1440, 1344, 1264, 1176,
1072, 1008, 832; δH (MeOH-d4) 4.74 (2H, s), 7.97 (1H, d), 8.07
(1H, s), 8.38 (1H, d), 8.81 (1H; s); δC (MeOH-d4) 65.41, 113.36,
114.27, 120.41, 123.44, 127.23, 144.34, 152.64, 157.22, 190.12.
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Acknowledgements
The authors thank the Hungarian OTKA (T-033112) for finan-
cial support. The Agora Fundation is gratefully acknowledged
for short-term fellowships (to Cs. P. and C. M.).
37 R. H. Levin, B. J. Magerlin, A. V. Jr. McIntosh, A. R. Hanze,
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