6
T. Miura et al. / Tetrahedron: Asymmetry 16 (2005) 3–6
255; (c) Filippov, D. V.; Zoelen, D. J.; Oldfield, S. P.;
Marel, G. A.; Overkleeft, H. S.; Drijfhout, J. W.; Boom, J.
10.3 Hz, 1H), 3.70 (dd, J = 6.2, 10.3 Hz, 1H), 3.89 (dd,
J = 2.1, 9.6 Hz, 1H), 3.94 (m, 2H), 3.97 (t, J = 6.2 Hz, 1H),
4.01 (m, 2H), 4.28 (m, 1H), 4.40 (d, J = 8.2 Hz, 1H), 4.42
(d, J = 11.7 Hz, 1H), 4.48 (d, J = 11.7 Hz, 1H), 4.55 (d, J =
11.7 Hz, 1H), 4.67 (d, J = 11.7 Hz, 1H), 4.72 (d,
J = 11.7 Hz, 1H), 4.77 (d, J = 11.7 Hz, 1H), 4.78 (d, J =
4.1 Hz, 1H), 4.82 (d, J = 11.7 Hz, 1H), 4.92 (d,
J = 11.7 Hz, 1H), 5.01 (dd, J = 3.4, 10.3 Hz, 1H), 5.14
(m, 1H), 5.20 (m, 1H), 5.42 (d, J = 3.4 Hz, 1H), 5.80 (m,
1H), 7.32 (m, 20H); 13C NMR (150 MHz, CDCl3): d =
20.61, 20.67, 20.79, 67.07, 67.84, 69.13, 69.16, 69.80, 71.04,
71.79, 73.22, 73.36, 73.52, 74.72, 75.13, 76.43, 78.81, 98.79,
99.99, 117.20, 127.47, 127.57, 127.63, 127.72, 127.82,
128.09, 128.20, 128.36, 133.46, 138.01, 138.42, 138.57,
138.77, 169.49, 170.03, 170.31; HRMS (ESI-TOF): calcd
for C49H56O14Na (M+Na+): 891.3562. Found: 891.3522.
H. Tetrahedron Lett. 2002, 43, 7809; (d) Pardo, J.; Cobas,
´
A.; Guitlan, E.; Castedo, L. Org. Lett. 2001, 3, 3711; (e)
Luo, Z.; Williams, J.; Read, R. W.; Curran, D. P. J. Org.
Chem. 2001, 66, 4261.
7. (a) Miura, T.; Hirose, Y.; Ohmae, M.; Inazu, T. Org. Lett.
2001, 3, 3947; (b) Miura, T.; Inazu, T. Tetrahedron Lett.
2003, 44, 1819; (c) Miura, T.; Goto, K.; Waragai, H.;
Matsumoto, H.; Hirose, Y.; Ohmae, M.; Ishida, H.-K.;
Satoh, A.; Inazu, T. J. Org. Chem. 2004, 69, 5348.
8. (a) Miura, T.; Goto, K.; Hosaka, D.; Inazu, T. Angew.
Chem., Int. Ed. 2003, 42, 2047; (b) Mizuno, M.; Goto, K.;
Miura, T.; Hosaka, D.; Inazu, T. Chem. Commun. 2003,
972; (c) Mizuno, M.; Goto, K.; Miura, T.; Matsuura, T.;
Inazu, T. Tetrahedron Lett. 2004, 45, 972; (d) Goto, K.;
Miura, T.; Hosaka, D.; Matsumoto, H.; Mizuno, M.;
Ishida, H.-K.; Inazu, T. Tetrahedron 2004, 60, 8845; (e)
Goto, K.; Miura, T.; Mizuno, M.; Takaki, H.; Imai, N.;
Murakami, Y.; Inazu, T. Synlett 2004, 2221.
25
1
17b (b isomer): ½a ¼ ꢀ12:6 (c 0.87, CHCl3); H NMR
D
(600 MHz, CDCl3): d = 1.97 (s, 3H), 2.04 (s, 3H), 2.10 (s,
3H), 3.47 (dd, J = 2.8, 9.6 Hz, 1H), 3.53 (m, 3H), 3.74 (m,
1H), 3.79 (t, J = 8.2 Hz, 1H), 3.87 (m, 3H), 3.93 (m, 1H),
4.24 (m, 1H), 4.38 (d, J = 8.2 Hz, 1H), 4.39 (d, J =
11.7 Hz, 1H), 4.41 (d, J = 8.2 Hz, 1H), 4.43 (d, J =
11.7 Hz, 1H), 4.60 (d, J = 11.7 Hz, 1H), 4.69 (d,
J = 11.7 Hz, 1H), 4.72 (d, J = 11.7 Hz, 1H), 4.75(d,
J = 11.0 Hz, 1H), 4.89 (d, J = 11.0 Hz, 1 H), 4.93 (d, J =
11.7 Hz, 1H), 4.99 (dd, J = 3.4, 10.3 Hz, 1H), 5.10 (d,
J = 10.3 Hz, 1H), 5.15 (d, J = 17.2 Hz, 1H), 5.21 (dd, J =
8.2, 11.0 Hz, 1H), 5.37 (d, J = 3.4 Hz, 1H), 5.71 (m, 1H),
7.31 (m, 20H); 13C NMR (150 MHz, CDCl3): d = 20.61,
20.70, 20.80, 67.73, 68.04, 68.57, 69.05, 69.81, 71.03, 72.88,
72.95, 73.32, 73.53, 74.52, 75.14, 79.43, 81.98, 99.97,
103.89, 117.18, 127.52, 127.55, 127.57, 127.83, 127.93,
128.14, 128.18, 128.30, 128.35, 128.46, 133.33, 137.79,
138.41, 138.59, 138.74, 169.51, 170.07, 170.27; HRMS
(ESI-TOF): Calcd for C49H56O14Na (M+Na+): 891.3562.
Found: 891.3550.
9. Greene, T. W.; Wuts, P. G. M. Protective Groups in
Organic Synthesis, 3rd ed.; John Wiley and Sons: New
York, 1999; p 173.
´
`
10. Campo, F. D.; Lastecoueres, D.; Vincent, J.-M.; Verlhac,
J.-B. J. Org. Chem. 1999, 64, 4969.
11. The fluorocarbon solvent (FC-72, bp 56 °C, formally
called FluorinertTM FC-72) is commercially available
and consists of perfluorohexane isomers (C6F14).
12. The fluorocarbon solvent (EtOC4F9, NovecTM HFE-7200)
is commercially available.
13. The a and b isomers (17a and 17b) were separated by silica
gel column chromatography and the anomeric ratio was
25
determined to be a:b = 40:60. 17a (a isomer): ½a ¼ þ7:7
(c 0.96, CHCl3); 1H NMR (600 MHz, CDCl3): dD= 1.98 (s,
3H), 2.05(s, 3H), 2.06 (s, 3H), 3.47 (dd, J = 6.2, 9.6 Hz,
1H), 3.54 (dd, J = 6.2, 9.6 Hz, 1H), 3.62 (dd, J = 6.2,