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Helvetica Chimica Acta – Vol. 93 (2010)
aq. layer was extracted with Et2O (3 ꢂ 15 ml). The org. phases were combined and dried (Na2SO4). A
yellow, viscous residue was obtained after concentration. The residue was purified through CC on silica
gel (petroleum ether/AcOEt/CH2Cl2 6 :1:0.4) to give white crystals of (2R3R)-1,1,4,4-tetra(naphthalen-
1-yl)butane-1,2,3,4-tetrol (5; 9.8 g, 52%; based on diethyl (2R,3R)-tartrate). M.p. 273 – 2758. [a]2D5 ¼ þ360
(c ¼ 1, CHCl3). IR: 3410vs (br., OH), 3045m (ArꢀH), 2926m (CꢀH), 1646m, 1635m, 1509m (Ar
1
backbone), 1385s (CꢀH), 1114s (CꢀO), 802m, 775s (ArꢀH). H-NMR: 8.73 – 8.72 (m, 2 arom. H);
8.46 – 8.43 (m, 2 arom. H); 7.83 (d, J ¼ 7.2, 4 arom. H); 7.71 – 7.56 (m, 8 arom. H); 7.43 – 7.38 (m, 2 arom.
H); 7.28 (s, 2 arom. H); 7.23 – 7.20 (m, 2 arom. H); 7.18 – 7.07 (m, 2 arom. H); 6.86 (s, 2 arom. H); 6.64 –
6.62 (m, 2 arom. H); 6.03 (d, J ¼ 3, 2 arom. H); 5.02 (s, 2 OH); 4.86 (s, 2 OH); 4.61 (s, 2 HꢀC). 13C-NMR
(CDCl3, 75 MHz): 135.1; 129.6; 129.4; 128.8; 128.5; 126.9; 125.4; 124.9; 124.4; 83.5; 72.0. LC/MS: 625 (24,
[M ꢀ 1]þ), 431 (26, [M ꢀ Arꢀ 4 OH]þ).
By similar procedures, other 1,1,4,4-tetrasubstituted butanetetraols were obtained.
(2S,3S)-1,1,4,4-Tetraphenylbutane-1,2,3,4-tetraol (1). Yield 48%. M.p. 149 – 1508. [a]2D5 ¼ ꢀ156.6 (c ¼
1.1, CHCl3). IR: 3437, 3058, 2916, 1598, 1492, 1447, 1062, 698. 1H-NMR: 7.37 – 7.13 (m, 20 arom. H); 4.63
(d, J ¼ 4.8, 2 OH, disappeared after adding D2O); 4.42 (d, J ¼ 4.5, 2 HꢀC); 3.69 (d, J ¼ 4.8, 2 OH,
disappeared after adding D2O). 13C-NMR: 143.8; 142.7; 134.6; 131.5; 129.3; 128.3; 128.2; 127.9; 127.5;
126.7; 125.5; 81.1; 69.7.
(2R,3R)-1,1,4,4-Tetraphenylbutane-1,2,3,4-tetraol (2). Yield 43%. M.p. 150 – 1518 ([4]: 148 – 1518).
[a]2D5 ¼ þ154 (c ¼ 1.2, CHCl3; [4]: [a]D ¼ þ164 (c ¼ 0.51, CHCl3)). IR: 3436, 3058, 2916, 1598, 1492, 1447,
1063, 698. 1H-NMR: 7.37 – 7.13 (m, 20 arom. H); 4.65 (d, J ¼ 7.2, 2 OH, disappeared after adding D2O);
4.41 (d, J ¼ 4.7, 2 HꢀC); 3.77 (d, J ¼ 5.3, 2 OH, disappeared after adding D2O). 13C-NMR (CDCl3,
75 MHz): 143.8; 142.7; 134.6; 131.5; 129.3; 128.3; 128.2; 127.9; 127.5; 126.7; 125.5; 81.3, 69.7.
(2R,3R)-1,1,4,4-Tetrakis(3-methylphenyl)butane-1,2,3,4-tetraol (3). Yield 54%. M.p. 239 – 2418.
1
[a]2D5 ¼ þ374 (c ¼ 1, CHCl3). H-NMR: 7.26 – 7.10 (m, 12 arom. H); 7.05 – 7.00 (m, 4 arom. H); 4.56 (s,
2 OH, disappeared after adding D2O); 4.48 (d, J ¼ 4.5, 2 HꢀC); 3.69 (d, J ¼ 5.1, 2 OH, disappeared after
adding D2O); 2.35 (s, 2 Me); 2.23 (s, 2 Me). 13C-NMR (CDCl3, 75 MHz): 141.6; 141.4; 136.9; 129.4; 129.2;
126.0; 125.1; 81.58; 72.38; 21.31; 21.30. LC/MS: 505 (24, [M þ Na]þ).
(2R,3R)-1,1,4,4-Tetrakis(2-methylphenyl)butane-1,2,3,4-tetraol (4). Yield 54%. M.p. 232 – 2348.
[a]2D5 ¼ þ362 (c ¼ 1, CHCl3). 1H-NMR: 7.40 – 6.90 (m, 12 arom. H); 4.48 (s, 2 OH, disappeared after
adding D2O); 4.24 (d, J ¼ 4.5, 2 HꢀC); 4.41 (d, J ¼ 5.1, 2 OH, disappeared after adding D2O); 1.95 (s,
4 Me). 13C-NMR (CDCl3, 75 MHz): 140.4; 138.8; 132.9; 132.5; 129.1; 127.8; 126.9; 126.0; 124.8; 82.95;
70.34; 21.47. LC/MS: 481 (52, [M ꢀ 1]þ).
(8R,9R)-7,10-Dihexylhexadecane-7,8,9,10-tetraol (6). Yield 43%. M.p. 71 – 728. [a]2D5 ¼ þ4.3 (c ¼ 1,
1
CHCl3). IR: 3410, 2953, 2922, 2859, 1462. H-NMR: 4.03 (d, J ¼ 3.6, 2 OH, disappeared after adding
D2O); 3.65 (d, J ¼ 2.7, 2 HꢀC); 2.96 (s, 2 OH, disappeared after adding D2O); 1.57 – 0.89 (m, 52 HꢀC).
13C-NMR (CDCl3, 75 MHz): 78.2; 72.2; 35.0; 34.5; 32.0; 31.9; 30.1; 30.0; 23.5; 23.4; 22.9; 22.8; 14.2. LC/
MS: 457 (52, [M ꢀ 1]þ).
(6R,7R)-5,8-Dibutyldodecane-5,6,7,8-tetraol (7). Yield 41%. M.p. 80 – 828. [a]2D5 ¼ þ6.2 (c ¼ 1,
CHCl3). IR: 3412, 2954, 2928, 2860, 2872, 1466. 1H-NMR: 4.07 (s, 2 OH, disappeared after adding
D2O); 3.65 (s, 2 HꢀC); 3.00 (d, 2 H, J ¼ 5.1, OH, disappeared after adding D2O); 1.69 – 0.92 (m,
36 HꢀC). 13C-NMR (CDCl3, 75 MHz): 78.1; 72.2; 34.7; 34.2; 25.8; 25.7; 23.5; 23.4; 14.3. LC/MS: 345
(100, [M ꢀ 1]þ).
The work was supported by the National Natural Science Foundation of China (20672083 and
20872115). The authors also thank Assoc. Prof. Z.-G. Shi and L. Z. Zhu for their help.
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