2960
S.-H. Son et al.
LETTER
(10) (a) Bah, M.; Pereda-Miranda, R. Tetrahedron 1996, 52,
13063. (b) Bah, M.; Pereda-Miranda, R. Tetrahedron 1997,
42, 9007.
128.2, 128.0, 102.3, 99.5, 86.1, 84.1, 83.2, 82.2, 76.5, 75.8,
75.6, 75.5, 75.1, 71.5, 70.9, 35.3, 35.0, 34.6, 32.5, 31.6, 29.8,
28.4, 28.1, 27.3, 25.7, 25.4, 23.4, 23.1, 18.4, 14.6. HRMS–
FAB: m/z calcd for C56H72O11 [M + Na]+: 943.4995; found:
943.4995.
(11) (a) Hasegawa, J.; Hamada, M.; Miyamoto, T.; Nishide, K.;
Kajimoto, T.; Uenishi, J.; Node, M. Carbohydr. Res. 2005,
340, 2360. (b) Matsui, H.; Furukawa, J.; Awano, T.; Nishi,
N.; Sakairi, N. Chem. Lett. 2000, 326. (c) Son, S.-H.; Tano,
C.; Furukawa, J.; Furuike, T.; Sakairi, N. Org. Biomol.
Chem. 2008, 6, 1441. (d) Son, S.-H.; Tano, C.; Furuike, T.;
Sakairi, N. Tetrahedron Lett. 2008, 49, 5289. (e) Son,
S.-H.; Tano, C.; Furuike, T.; Sakairi, N. Carbohydr. Res.
2009, 344, 285.
Compound 12: [a]D –7.2 (c 0.76, CHCl3). 1H NMR (300
MHz, acetone-d6): d = 7.40–7.25 (m, 10 H, 2 CHarom), 5.40
(t, 1 H, J3¢,4¢ = 8.9 Hz, H-3¢), 4.97–4.57 (m, 6 H, PhCH2,
Cl3CCH2), 4.82 (d, 1 H, J1¢,2¢ = 10.0 Hz, H-1¢), 4.73 (t, 1 H,
J2¢,3¢ = 9.6 Hz, H-2¢), 4.22 (d, 1 H, J1,2 = 8.1 Hz, H-1), 4.03
(dd, 1 H, J = 2.2 Hz, J4,5 = 6.0 Hz, H-4), 4.00–3.96 (m, 1 H,
H-3), 3.91 (dd, 1 H, J = 2.1, 6.5 Hz, H-5), 3.86–3.75 (m, 4
H, H-4¢, H-5¢, H-6¢a, H-6¢b), 3.63–3.60 (m, 1 H, CHO), 3.35
(t, 1 H, J2,3 = 7.6 Hz, H-2), 2.85–2.65 (m, 2 H, SCH2), 2.33–
2.20 (m, 2 H, CH2COO), 1.52–1.28 [m, 53 H, H-6, C(CH3)2,
22 × CH2], 0.91–0.86 (m, 6 H, 2 × CH3). Column
(12) Lönn, H. Carbohydr. Res. 1985, 139, 115.
(13) Mootoo, D. R.; Konradsson, P.; Udodong, U.; Fraser-Reid,
B. J. Am. Chem. Soc. 1988, 110, 5583.
(14) All new compounds had satisfactory data for elemental
analysis or high resolution mass spectrum.
chromatography of the mixture gave crude 12 contaminated
with small amount of an unknown product in ca. 60% yield
and a mixture of 11 its 3-O-Troc derivative. Repeated
column chromatography gave pure 12 in 12% yield.
Compound 13: [a]D +2.1 (c 0.33, CHCl3). 1H NMR (300
MHz, acetone-d6): d = 7.44–7.29 (m, 10 H, CHarom), 5.48 (t,
1 H, J3¢,4¢ = 8.6 Hz, H-3¢), 5.36 (d, 1 H, J1¢,2¢ = 7.6 Hz, H-1¢),
5.08–4.63 (m, 6 H, PhCH2, Cl3CCH2), 4.57 (dd, 1 H, J = 7.6
Hz, J2¢,3¢ = 8.8 Hz, H-2¢), 4.23 (d, 1 H, J1,2 = 8.4 Hz, H-1),
4.11 (dd, 1 H, J = 5.3 Hz, J4,5 = 7.0 Hz, H-4), 4.05 (dd, 1 H,
J = 2.0 Hz, J3,4 = 5.3 Hz, H-3), 3.95–3.84 (m, 5 H, H-2, H-5,
H-4¢, H-6¢a, H-6¢b), 3.71–3.65 (m, 1 H, H-5¢), 3.55–3.49 (m,
1 H, CHO), 2.33–2.00 (m, 2 H, CH2COO), 1.53–1.24 [m, 33
H, H-6, C(CH3)2, 12 × CH2], 0.86 (t, 3 H, J = 6.8 Hz,
CH2CH3). 13C NMR (75.5 MHz, acetone-d6): d = 171.8,
153.4, 139.1, 138.8, 128.6, 128.3, 128.2, 128.0, 127.7,
109.6, 101.5, 97.0, 95.3, 81.2, 80.5, 80.2, 77.0, 76.9, 75.5,
75.1, 74.7, 74.5, 73.5, 68.6, 68.3, 35.4, 35.2, 34.5, 32.1, 31.1,
30.1, 29.9, 29.6, 29.3, 29.1, 28.8, 28.6, 28.3, 28.2, 27.9, 27.4,
26.3, 25.4, 25.1, 24.2, 22.8, 16.7, 13.9. HRMS–FAB: m/z
calcd for C48H67Cl3O13 [M + Na]+: 979.3545; found:
979.3542.
Selected Physical Data
Compound (R,S)-5: 1H NMR (300 MHz, CDCl3): d = 8.02–
7.25 (m, 20 H, CHarom), 5.45 (t, 1 H, J3¢,4¢ = 9.4 Hz, H-3¢),
5.19 (t, 1 H, J2¢,3¢ = 9.8 Hz, H-2¢), 4.97–4.61 (m, 6 H,
PhCH2), 4.57 (d, 1 H, J1¢,2¢ = 10.0 Hz, H-1¢), 4.25 (d, 1 H,
J1,2 = 7.1 Hz, H-1), 3.61–3.48 (m, 4 H, H-2, H-3, H-5¢,
OCH), 3.41–3.33 (m, 2 H, H-5, H-4¢), 3.20 (t, 1 H, J4,5 = 8.6
Hz, H-4), 2.69–2.63 (m, 2 H, SCH2), 2.26 (s, 1 H, OH), 2.09
(t, 2 H, J = 7.3 Hz, CH2COO), 1.57–0.85 (m, 56 H, H-6, H-
6¢, 22 × CH2, 2 × CH3). Although (R)-5 and (S)-5 were not
distinguished by both 1H NMR and 13C NMR spectra, the
diastereomeric ratio of almost 1:1 was deduced by careful
HPTLC (Merck) analysis on silica gel using hexane–EtOAc
(2:1).
Compound (R)-6: [a]D +13.3 (c 1.05, CHCl3). 1H NMR (300
MHz, CDCl3): d = 7.90–7.19 (m, 20 H, CHarom), 5.41 (t, 1 H,
J3¢,4¢ = 8.6 Hz, H-3¢), 5.23 (t, 1 H, J2¢, 3¢ = 7.7 Hz, H-2¢), 5.14
(d, 1 H, J1¢,2¢ = 7.7 Hz, H-1¢), 4.75–4.48 (m, 6 H, PhCH2),
4.39 (d, 1 H, J1,2 = 7.7 Hz, H-1), 3.85–3.76 (m, 2 H, H-2,
OCH), 3.53–3.45 (m, 1 H, H-5¢), 3.42 (t, 1 H, J4¢,5¢ = 9.2 Hz,
H-4¢), 3.41 (t, 1 H, J3,4 = 8.5 Hz, H-3), 3.29–3.22 (m, 1 H, H-
5), 3.11 (t, 1 H, J4,5 = 9.1 Hz, H-4), 2.29–2.08 (m, 2 H,
CH2COO), 1.67–1.21 (m, 30 H, H-6, H-6¢, 12 × CH2), 0.88
(t, 3 H, J = 6.7 Hz, CH2CH3). 13C NMR (75.5 MHz, CDCl3):
d = 172.4, 165.4, 138.5, 138.1, 133.4, 130.2, 130.1, 129.0,
128.8, 128.4, 128.4, 128.2, 128.0, 99.6, 95.6, 86.4, 84.4,
82.9, 81.0, 76.2, 75.8, 75.6, 75.4, 74.9, 71.2, 71.1, 34.9, 34.5,
34.5, 32.6, 31.2, 29.4, 28.3, 28.0, 27.9, 26.9, 23.1, 18.5, 18.4,
14.6. HRMS–FAB: m/z calcd for C56H72O11 [M + Na]+:
943.4995; found: 943.4995.
Compound 19: [a]D –20.5 (c 0.064, CHCl3). 1H NMR (600
MHz, acetone-d6): d = 7.41–7.20 (m, 25 H, CHarom), 5.06 (d,
1 H, J1¢, 2¢ = 7.4 Hz, H-1¢), 5.01 (s, 1 H, H-1¢¢), 5.01 (t, 1 H,
J2¢¢,3¢¢ = 4.5 Hz, H-2¢¢), 5.01–4.61 (m, 10 H, PhCH2), 4.45 (t,
1 H, J3,4 = 6.3 Hz, H-3), 4.42 (d, 1 H, J1,2 = 6.4 Hz, H-1),
4.12 (dd, 1 H, J = 2.0 Hz, J4,5 = 5.7 Hz, H-4), 3.98–3.91 (m,
1 H, H-5), 3.94 (t, 1 H, J2,3 = 6.4 Hz, H-2), 3.80–3.74 (m, 2
H, H-6¢a, 6¢b), 3.69 (t, 1 H, J3¢,4¢ = 7.7 Hz, H-3¢), 3.64 (m, 1
H, H-3¢¢), 3.61 (t, 1 H, J2¢,3¢ = 7.4 Hz, H-2¢), 3.58 (t, 1 H,
Compound (S)-6: [a]D +25.6 (c 0.20, CHCl3). 1H NMR (300
MHz, CDCl3): d = 7.92–7.17 (m, 20 H, CHarom), 5.42 (t, 1 H,
J4¢,5¢ = 7.3 Hz, H-4¢), 3.56 (m, 2 H, H-5¢¢, CHO), 3.46–3.42
(m, 1 H, H-5¢), 3.32 (t, 1 H, J4¢¢, 5¢¢ = 9.1 Hz, H-4¢¢), 2.13 (t, 2
H, J = 7.6 Hz, CH2COO), 1.70–0.85 [m, 39 H, H-6, H-6¢¢,
12 × CH2, C(CH3)2, CH2CH3]. 13C NMR (75.5 MHz,
acetone-d6): d = 172.6, 138.9, 138.7, 138.5, 138.3, 129.0,
128.9, 128.8, 128.6, 128.5, 128.3, 128.2, 128.1, 127.9,
127.6, 110.2, 102.9, 100.8, 83.8, 78.7, 77.7, 75.9, 75.8, 75.6,
75.5, 75.4, 74.0, 72.0, 68.8, 36.6, 35.4, 34.5, 32.5, 30.2, 30.1,
29.4, 28.2, 28.1, 28.0, 26.9, 25.5, 23.1, 18.7, 17.3, 14.6.
HRMS–FAB: m/z calcd for C72H96O15 [M + H]+: 1199.6672;
found: 1199.6640.
J3¢,4¢ = 8.6 Hz, H-3¢), 5.23 (t, 1 H, J2¢,3¢ = 8.3 Hz, H-2¢), 5.07
(d, 1 H, J1¢,2¢ = 7.6 Hz, H-1¢), 4.75–4.46 (m, 6 H, PhCH2),
4.24 (d, 1 H, J1,2 = 7.8 Hz, H-1), 3.82 (dd, 1 H, J = 8.0 Hz,
J2,3 = 9.3 Hz, H-2), 3.53–3.46 (m, 2 H, H-5¢, OCH), 3.40 (t,
1 H, J4¢,5¢ = 9.2 Hz, H-4¢), 3.40 (t, 1 H, J3,4 = 8.4 Hz, H-3),
3.31–3.26 (m, 1 H, H-5), 3.11 (t, 1 H, J4,5 = 9.2 Hz, H-4),
2.19 (s, 2 H, CH2COO), 1.59–1.22 (m, 30 H, H-6, H-6¢,
12 × CH2), 0.89 (t, 3 H, J1,2 = 6.4 Hz, CH2CH3). 13C NMR
(75.5 MHz, CDCl3): d = 172.4, 165.5, 138.5, 138.2, 133.4,
130.2, 130.1, 129.0, 128.9, 128.8, 128.4, 128.3, 128.3,
Synlett 2009, No. 18, 2957–2960 © Thieme Stuttgart · New York