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U. Ladziata et al. / Tetrahedron Letters 47 (2006) 6301–6304
2.49 (m, 1H), 2.12 (m, 2H), 1.91 (m, 1H); 13C NMR
134.9, 134.7, 131.9, 131.8, 131.7, 131.3, 129.8, 129.7, 129.6,
128.9, 128.7, 128.6, 128.5, 128.4, 128.3, 127.7, 126.0, 125.3,
60.3, 59.8, 51.9, 51.8, 39.7, 39.6, 30.6, 28.8, 26.8, 26.5;
APCI-MS: m/z (%) 466.64 (28) [M]+. Compound 13:
(125 MHz, CDCl3): d 171.6, 169.5, 138.9, 138.4, 135.8,
130.5, 129.0, 128.4, 127.4, 126.2, 122.8, 90.6, 61.1, 50.6,
27.8, 25.5; APCI-MS: m/z (%) 420.64 (100) [M]+. Com-
25
25
pound 10: Mp 200–201 °C; ½aꢀD +135.8 (c 1.0, MeOH); IR
Mixture of rotamers; Mp 157–159 °C; ½aꢀD ꢁ13.7 (c 1.0,
tmax (NaCl) cmꢁ1 2959, 1664, 1626, 1467, 1419, 1382,
MeOH); IR tmax (NaCl) cmꢁ1 2949, 1675, 1613, 1575,
1422, 1204, 1067, 1005, 777, 726; 1H NMR (500 MHz,
CD3OD): d 6.95–8.25 (m, 13H), 5.50 (d, 1J = 15.0 Hz,
1
1272, 1113, 1056, 1019, 777, 743, 725, 701, 653; H NMR
3
4
(500 MHz, CDCl3): d 7.96 (dd, J = 6.5 Hz, J = 1.5 Hz,
1H), 7.93 (dd, 3J = 6.6 Hz, 4J = 1.1 Hz, 1H), 7.57 (m, 2H),
1H), 4.54 (d, J = 15.0 Hz, 1H), 4.25 (t, J = 7.5 Hz, 1H),
3.75–3.50 (m, 2H), 2.51–1.69 (m, 4H); 13C NMR
(125 MHz, CDCl3): d 176.2, 174.8, 172.0, 171.0, 151.6,
140.4, 137.4, 136.7, 135.3, 133.3, 133.2, 132.7, 132.4, 132.3,
132.0, 130.8, 129.7, 129.6, 129.0, 128.8, 128.7, 128.3, 123.5,
122.8, 60.6, 60.4, 55.2, 54.5, 51.9, 30.8, 30.7, 29.1, 26.9,
26.5; APCI-MS: m/z (%) 620.64 (68) [M]+.
1
3
7.50 (td, J = 7.5 Hz, 4J = 1.0 Hz, 1H), 7.40 (m, 3H), 7.10
3
(td, 3J = 7.5 Hz, 4J = 1.1 Hz, 1H), 4.42 (t, 3J = 7.4 Hz,
1H), 3.69 (m, 1H), 3.47 (m, 1H), 3.25 (s, 3H), 2.17 (m, 1H),
2.07 (m, 2H), 1.70 (m, 1H); 13C NMR (125 MHz, CDCl3):
d 172.3, 169.2, 145.7, 139.7, 136.4, 130.9, 130.1, 130.0,
129.9, 128.1, 127.3, 98.8, 57.4, 50.4, 36.5, 30.1, 25.7; APCI-
MS: m/z (%) 434.54 (11) [M]+. Compound 11: Mp 115–
11. General procedure for oxidation with amides 12 and 13. To
a stirred solution of an alcohol (1.0 mmol) or a sulfide
(1.0 mmol) in 2.0 ml of dry MeCN was added chiral
oxidant 12 or 13 (0.25 mmol or 0.50 mmol), and the
reaction mixture was stirred at rt for 1 h, and at 65 °C for
3 h. Then, the organic solvent was removed under reduced
pressure and the residue was separated by flash chroma-
tography (hexanes/EtOAc or hexanes/CHCl3) to give the
product. Optical rotation of the obtained sample was
determined and the % ee was calculated.
25
116 °C; ½aꢀD +84.5 (c 1.0, MeOH); IR tmax (NaCl) cmꢁ1
2970, 1672, 1650, 1615, 1572, 1470, 1422, 1395, 1271, 1245,
1202, 1075, 1011, 787, 776, 723; 1H NMR (500 MHz,
CDCl3): d 7.96 (dd, 3J = 7.5 Hz, 4J = 1.5 Hz, 1H), 7.59
3
(m, 2H), 7.51 (dd, J = 6.5 Hz,4J = 1.5 Hz, 1H), 7.49 (m,
5H), 7.31 (td, 3J = 8.0 Hz, 4J = 1.5 Hz, 1H), 7.19 (m, 2H),
7.07 (td, 3J = 8.0 Hz, 4J = 1.5 Hz, 1H), 5.76 (d,
1J = 15.0 Hz, 1H), 4.41 (t, 3J = 7.5 Hz, 1H), 4.02 (d,
1J = 15.0 Hz, 1H), 3.72 (m, 1H), 3.50 (m, 1H), 2.23 (m,
1H), 2.11 (m, 2H), 1.72 (m, 1H); 13C NMR (125 MHz,
CDCl3): d 172.5, 169.2, 143.0, 139.8, 136.4, 135.3, 132.7,
131.6, 131.5, 131.1, 130.6, 130.1, 129.5, 128.2, 127.3, 121.3,
99.3, 57.6, 51.3, 50.4, 30.1, 25.8; APCI-MS: m/z (%) 588.36
(34) [M]+. Compound 12: Mixture of rotamers; Mp 167–
25
12. For 14: 33% ee based on measured ½aꢀD +14.1 (c 0.5,
25
EtOH); lit.: ½aꢀD +41.2 (c 0.5, EtOH; 95% ee (R)) (a)
Matharu, D. S.; Morris, D. J.; Kawamoto, A. M.;
Clarkson, G. J.; Willsa, M. Org. Lett. 2005, 24, 5489;
25
For 16: 41% ee based on measured ½aꢀD ꢁ66.0 (c 1.0,
25
25
169 °C; ½aꢀD ꢁ139.6 (c 1.0, MeOH); IR tmax (NaCl) cmꢁ1
MeOH); lit.: ½aꢀD ꢁ65 (c 1.0, MeOH; 40% ee (R))
2975, 1618, 1567, 1409, 1323, 1245, 1164, 1113, 1024, 777,
(b) Pesch, J.; Harms, K.; Bach, T. Eur. J. Org. Chem.
25
1
723; H NMR (500 MHz, CD3OD): d 7.28–8.23 (m, 9H),
2004, 2025; For 18: 29% ee based on measured ½aꢀD +44.1
25
4.34 (t, 3J = 7.2 Hz, 1H), 3.77–3.31 (m, 5H), 2.49–1.95 (m,
4H); 13C NMR (125 MHz, CDCl3): d 175.6, 174.9, 171.8,
171.0, 151.0, 146.6, 142.9, 142.2, 138.4, 137.3, 136.9, 135.9,
(c 1.2, EtOH); lit.: ½aꢀD +151 (c 1.2, EtOH; 100% ee (R))
(c) Puchot, C.; Samuel, O.; Duach, E.; Zhao, S.; Agami,
C.; Kagan, H. B. J . Am. Chem. Soc. 1986, 108, 2353.