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K. Mori, Y. Masuda / Tetrahedron Letters 44 (2003) 9197–9200
References
3310 (br.m, O-H), 1620 (m, CꢁO), 1545 (w), 1120 (w),
1060 (w), 960(w), 720 (w). HRFABMS m/z (M+H)+:
calcd for C48H96NO5, 766.7210; found, 766.7269. (b)
(2S,3R,4E,6S)-1%; mp 115.0–118.5°C. IR wmax (Nujol)
cm−1: 3350 (br.m, N-H, O-H), 1660 (m, CꢁO), 1550 (w),
1140 (w), 1075 (w), 1020 (w), 975 (w), 720 (w).
HRFABMS m/z (M+H)+: calcd for C48H96NO5,
1. Hamanaka, S.; Suzuki, M.; Suzuki, A.; Yamakawa, T.
Proc. Japan Acad. Ser. B 2001, 77, 51–56.
2. Robson, K. J.; Stewart, M. E.; Michelsen, S.; Lazo, N.
D.; Downing, D. T. J. Lipid Res. 1994, 35, 2060–2068.
3. Kolter, T.; Sandhoff, K. Angew. Chem., Int. Ed. 1999, 38,
1532–1568.
4. Chung, J.; Byun, H.-S.; Bittman, R. J. Org. Chem. 2003,
68, 348–354.
5. Yadav, J. S.; Geetha, V.; Raju, A. K.; Gnaneshwar, D.;
Chandrasekhar, S. Tetrahedron Lett. 2003, 44, 2983–
2985.
6. Mori, K.; Matsuda, H. Liebigs Ann. Chem. 1991, 529–
535.
7. Garner, P.; Park, J. M. J. Org. Chem. 1987, 52, 2361–
2364.
8. Garner, P.; Park, J. M.; Malecki, E. J. Org. Chem. 1988,
53, 4395–4398.
9. Review: Liang, X.; Andersch, J.; Bols, M. J. Chem. Soc.,
Perkin Trans. 1 2001, 2136–2157.
766.7210; found, 766.7269. (c) (2S,3R,4E,6R)-2; [h]D22
+
2.3 (c=0.90, CHCl3). IR wmax (Nujol) cm−1: 3310 (br.w,
N-H), 1740 (s, CꢁO), 1650 (m, NCO), 1540 (w), 1240 (m),
1040 (w), 975 (w), 720 (w). NMR lH (500 MHz, CDCl3/
D2O): 0.86 (3H, t, J=6.9 Hz, 18-H3), 1.21–1.40 (72H, m,
8ꢀ17-H2, 3%ꢀ28%-H2), 1.54–1.60 (4H, m, 7-, 29%-H2),
2.02, 2.03, 2.04, 2.05 (12H, each s, OAc), 2.12–2.17 (2H,
m, 2%-H2), 3.98 (1H, dd, J=11.6, 4.6 Hz, 1-Ha), 4.02 (2H,
t, J=6.7 Hz, 30%-H2), 4.21 (1H, dd, J=11.6, 6.4 Hz,
1-Hb), 4.46 (1H, dd, J=6.4, 4.6 Hz, 2-H), 5.15 (1H, dt,
J=6.5, 6.4 Hz, 6-H), 5.32 (1H, t-like, J=5.8 Hz, 3-H),
5.60 (1H, dd, J=15.6, 6.4 Hz, 4-H), 5.69 (1H, dd, J=
15.6, 6.5 Hz, 5-H). These spectral data are in good
agreement with the reported values at 600 MHz; 5.15
(1H, dt, J=6.5, 6.3 Hz, 6-H), 5.60 (1H, ddd, J=15.6, 6.6,
0.9 Hz, 4-H), 5.69 (1H, ddd, J=15.6, 6.6, 0.7 Hz, 5-H).2
NMR lC (126 MHz, CDCl3): 14.1, 21.0, 22.8, 25.9, 28.5,
29.21, 29.24, 29.31, 29.33, 29.36, 29.48, 29.50, 29.52,
29.55, 29.62, 29.65, 29.69, 31.89, 36.8, 50.3, 55.2, 62.4,
64.6, 72.7, 73.6, 126.5, 133.7, 169.8, 170.4, 170.8, 171.2,
172.9. HRFABMS m/z (M+H)+: calcd for C56H104NO9,
934.7711; found, 934.7709. (d) (2S,3R,4E,6S)-2%; [h]D22
−11.6 (c=0.90, CHCl3). IR wmax (Nujol) cm−1: 3305
(br.w, N-H), 1735 (s, CꢁO), 1650 (m, NCO), 1545 (w),
1245 (m), 1050 (w), 720 (w). NMR lH (500 MHz, CDCl3/
D2O): 0.86 (3H, t, J=7.0 Hz, 18-H3), 1.21–1.40 (72H, m,
8ꢀ17-H2, 3%ꢀ28%-H2), 1.53–1.60 (4H, m, 7-, 29%-H2),
2.02, 2.03, 2.04, 2.05 (12H, each s, OAc), 2.10–2.14 (2H,
m, 2%-H2), 3.98–4.04 (3H, m, 1-Ha, 30%-H2), 4.23 (1H, dd,
J=11.4, 6.3 Hz, 1-Hb), 4.32–4.48 (1H, m, 2-H), 5.12 (1H,
dt, J=6.4, 6.2 Hz, 6-H), 5.33 (1H, t-like, J=5.3 Hz, 3-H),
5.61 (1H, dd, J=15.6, 5.7 Hz, 4-H), 5.66 (1H, dd, J=
15.6, 5.9 Hz, 5-H). NMR lC (126 MHz, CDCl3): 14.1,
20.7, 22.6, 25.0, 25.6, 25.8, 29.2, 29.3, 29.37, 29.47, 29.50,
29.53, 29.55, 29.57, 29.63, 29.65, 29.69, 31.9, 34.1, 36.7,
50.2, 62.4, 64.6, 72.4, 74.0, 126.4, 133.5, 169.7, 170.5,
170.9, 171.2, 172.9. HRFABMS m/z (M+H)+: calcd for
C56H104NO9, 934.7711; found, 934.7714.
10. Review on the use of lipases and other biocatalysis in
synthesis: Mori, K. In Stereoselective Biocatalysis; Patel,
R. N., Ed. Chemoenzymatic synthesis of pheromones,
terpenes, and other bioregulators; Marcel Dekker: New
York, 1999; pp. 59–85.
11. All the new compounds in this letter were characterized
1
by consistent spectral (IR, H, and 13C NMR) and ana-
lytical (combustion or HRMS) data.
12. Allevi, P.; Ciuffreda, P.; Anastasia, M. Tetrahedron:
Asymmetry 1997, 8, 93–99.
13. Literature data. (a) Bittmann4 (R)-11, mp 40–41°C, [h]2D5
+2.60 (c=1.0, CHCl3); (S)-11, mp 40–41°C, [h]2D5 −2.59
(c=1.0, CHCl3); (b) Yadav.5 (R)-11, mp not reported,
[h]D +1.3 (c=1.05, CHCl3); (S)-11, mp 36–36.5°C, [h]D
−1.8 (c=1.6, CHCl3).
14. The diastereoselectivity of this addition reaction was anti/
syn=4.2:1. Bittman and co-workers reported that the
addition of TBS-protected (R)-11 to (S)-15 in THF gave
an 8:1 anti/syn mixture, and addition of HMPA further
improved the ratio to >20:1.4 cf. Gruza, H.; Kiciak, K.;
Krasinski, A.; Jurczak, J. Tetrahedron: Asymmetry 1997,
8, 2627–2631.
15. Mori, K.; Uenishi, K. Liebigs Ann. Chem. 1994, 41–48.
16. Physical data for 1, 1%, 2, and 2%. (a) (2S,3R,4E,6R)-1; mp
113.5–117.0°C. IR wmax (Nujol) cm−1: 3470 (w, N-H),