7708
F. Han et al. / Tetrahedron 59 (2003) 7703–7711
each, 1P), 20.31, 20.44, 20.47 (s each, 1P), 20.50, 20.56,
20.61 (s each, 1P); Anal. Calcd. for C70H107O19P3: C,
62.48; H, 8.02; found: C, 62.10; H, 8.02.
J¼0.9 Hz, InsC-2), 70.79 (d, J¼5.1 Hz, InsC-4), 69.85 (d,
J¼5.7 Hz), 69.52 (d, J¼5.8 Hz), 69.31 and 69.12 (2£d, J¼
7.3 Hz), 68.90 (d, J¼7.0 Hz), 68.68 (d, J¼7.0 Hz)
(ArCH2O), 37.50 (s), 34.98 (s), 29.70 (s), 24.85 (s),
23.82 (s), 23.69 (s) (cyclohexylidene); 31P NMR
(162 MHz) d: 20.23 (s), 20.27 (s), 20.46 (s). Anal.
Calcd. for C42H47O15P3: C, 57.02; H, 5.35; found: C,
56.84; H, 5.47.
3.2.2. Compound 14b. The title compound (63%) as
colorless gum. Rf¼0.66 (hexane/EtOAc¼1:3); 1H NMR
(400 MHz) d: 7.29–7.39 (m, 13H), 5.53–5.64 (complex,
2H, ArCH2O), 5.29 (t, 1H, J¼13.2 Hz, ArCH2O), 5.08–
5.28 (complex, 8H, ArCH2O, glyceryl 2-H), 4.85 (br 2£q,
1H, J¼9.0 Hz, InsH-6), 4.64–4.73 (complex, 1.5H, InsH-3,
H-2), 4.54–4.63 (complex, 2.5H, InsH-2, CH2Br), 4.40
(dd£2, 1H, J¼4.0, 9.0 Hz, InsH-5), 4.01–4.36 (complex,
6H, InsH-1, H-4, glyceryl 1-H, 3-H), 2.28 (complex, 4H, Pal
H-2), 1.82 (br, 2H, cyclohexylidene H), 1.38–1.64 (br, 12H,
Pal H-3, cycohexylidene H), 1.25 (br, 48H, Pal H4-15), 0.89
(t, 6H, J¼6.8 Hz, Pal CH3); 31P NMR (162 MHz) d: 20.20,
20.22, 20.27 (s each, 1P), 20.32, 20.45, 20.48 (s each,
1P), 20.52, 20.59, 20.63 (s each, 1P).
3.2.6. Compound 14f. The title compound (89%) as white
1
solid. Rf¼0.38 (hexane/EtOAc¼1:3); H NMR (400 MHz)
d: 7.34 (m, 14H, aromatic H), 5.28–5.37 (complex, 3H,
InsH-6 and ArCH2O), 5.06–5.19 (complex, 6H, ArCH2O),
4.56 (dt, 1H, J¼4.0, 9.2 Hz, InsH-3), 4.47 (dd, 1H, J¼4.0,
4.8 Hz, InsH-2), 4.38 and 4.36 (t£2, 1H, J¼9.2 Hz, InsH-5),
4.26 (t, 1H, J¼9.2 Hz, InsH-4), 4.12 (dd, 1H, J¼4.8, 6.8 Hz,
InsH-1), 2.67–2.76 (complex, 4H, CH2CH2), 2.15 (s, 3H,
CH3), 1.81 (complex, 2H, cyclohexylidene), 1.63 (br, 2H,
cyclohexylidene), 1.50 (br, 4H, cyclohexylidene), 1.26 (br,
2H, cyclohexylidene); 31P NMR (162 MHz) d: 0.29 (1P),
0.01 (1P).
3.2.3. Compound 14c. The title compound (88%) as
colorless gum. Rf¼0.60 (hexane/EtOAc¼1:3); 1H NMR
(400 MHz) d: 7.30–7.39 (m, 13H), 5.55–5.65 (complex,
2H, ArCH2O), 5.28 (t, 1H, J¼13.2 Hz, ArCH2O), 5.07–
5.27 (complex, 8H, ArCH2O, glyceryl 2-H), 4.85 (br 2£q,
1H, J¼9.0 Hz, InsH-6), 4.64–4.73 (complex, 1.5H, InsH-3,
H-2), 4.54 and 4.59 (2£t, 0.5H, J¼4.0 Hz, InsH-2), 4.40
(2£dd, 1H, J¼4.0, 9.0 Hz, InsH-5), 4.08–4.36 (complex,
6H, InsH-1 and H-4, glyceryl H-1, H-3), 2.28 (complex, 4H,
Oct H-2), 1.82 (br, 2H, cyclohexylidene H), 1.38–1.64 (br,
12H, Oct H-3, cycohexylidene H), 1.25 (br, 16H, Oct H3-6),
0.87 (t, 6H, J¼6.8 Hz, Oct CH3); 31P NMR (162 MHz) d:
20.25, 20.27, 20.32 (s each, 1P), 20.33, 20.46 (0.5P)
(s each, 1P), 20.58, 20.64 (s each, 1P).
3.2.7. Compound 14g. The title compound (91%) as white
solid. Rf¼0.35 (EtOAc/hexane¼4:1); mp 155.5–157.08C
(sample was obtained by chromatography); 1H NMR
(400 MHz) d: 7.35 (m, 20H, 4£C6H5), 5.26 (dd, 1H, J¼
7.4, 8.8 Hz, InsH-6), 4.50–5.19 (complex, 8H, 4£C6H5CH2),
4.44–4.50 (complex, 2H, InsH-3, H-2), 4.13–4.23 (com-
plex, 2H, InsH-4, H-5), 4.04 (dd, 1H, J¼4.8, 7.4 Hz,
InsH-1), 2.44–2.57 (complex, 4H, CH2CH2), 2.06 (s, 3H,
CH3), 1.60 (br, 2H, cyclohexylidene), 1.48 (br, 6H, cyclo-
hexylidene), 1.33 (br, 2H, cyclohexylidene); 13C NMR
(100.6 MHz) d: 206.52 (s), 172.17 (s), 136.16 (s), 136.08
(s), 136.01 (s), 135.94 (s), 128.26–129.50 (m), 112.01 (s),
79.04 (br), 76.50 (br), 75.93 (m), 74.56 (s), 73.91
(t, J¼3.3 Hz), 70.28 (s), 70.23 (s, 2C), 70.17 (s), 69.97 (d,
J¼5.5 Hz), 38.04 (s), 37.69 (s), 35.39 (s), 30.10 (s), 28.29
(s), 25.34 (br), 24.15 (s), 23.98 (s); 31P NMR (162 MHz) d:
0.45 (1P), 20.05 (1P); calcd for C45H52O14P2·0.5H2O: C,
60.87; H, 6.02; found: C, 61.02; H, 6.24.
3.2.4. Compound 14d. The title compound (89%) as
colorless gum: Rf¼0.59 (hexane/EtOAc¼1:3); 1H NMR
(400 MHz) d: 7.28–7.37 (m, 8H), 5.57–5.63 (complex, 2H,
ArCH2O), 5.30 (t, 1H, J¼13.0 Hz, ArCH2O), 5.03–5.25
(complex, 6H, ArCH2O glyceryl 2-H), 4.85 (br 2£q, 1H,
J¼8.8 Hz, InsH-6), 4.52–4.68 (complex, 2H, InsH-3, H-2),
4.42 (2£dd, 1H, J¼4.0, 8.8 Hz, InsH-5), 4.12–4.30
(complex, 6H, InsH-1 and H-4, glyceryl 1-H, 3-H), 3.79–
3.87 (complex, 3H, OMe), 2.32 (complex, Oct H-2), 1.82
(br, 2H, cycohexylidene H), 1.40–1.65 (br, 12H, Oct H-3,
cycohexylidene, H), 1.28 (br, 16H, Oct H4-6), 0.86 (t, 6H,
J¼7.2 Hz, Oct CH3); 31P NMR (162 MHz) d: 0.59, 0.54,
0.52, 0.42 (s each, 1P), 20.23, 20.28, 20.31 (s each, 1P),
20.57, 20.58, 20.63 (s each, 1P).
3.2.8. Compound 14h. The title compound (86% yield) as
colorless gum. Rf¼0.43 (hexane/AcOEt¼1:2); 1H NMR
(400 MHz) d: 7.28–7.47 (m, 28H, aromatic), 6.08 (s, 1H,
methenyl), 6.05 (s, 1H, methenyl), 5.38 (dd, 2H, J¼7.6,
9.2 Hz, InsH-6), 5.27–5.34 (complex, 2H, ArCH2O), 4.71–
5.18 (complex, 14H, ArCH2O), 4.50–4.57 (complex, 3H,
InsH-3 and InsH-2), 4.39 (dd, 1H, J¼4.0, 4.8 Hz, InsH-2),
4.28–4.36 (complex, 4H, InsH-5 and InsH-4), 4.22 (dd,
1H, J¼4.8, 7.6 Hz, InsH-1), 3.79 (dd, 1H, J¼4.8, 7.6 Hz,
InsH-1), 2.18 (s, 3H, CH3), 2.12 (s, 3H, CH3), 1.75 (br, 2H,
cyclohexylidene), 1.48–1.61 (br, 6H, cyclohexylidene),
1.31 (br, 2H, cyclohexylidene); 31P NMR (162 MHz) d:
0.36 (1P), 20.19 (1P), 20.27 (2P).
3.2.5. Compound 14e. The title compound (91%) as white
1
solid. Rf¼0.41 (hexane/EtOAc¼1:3); H NMR (400 MHz)
d: 7.31–7.39 (m, 18H), 5.53–5.62 (complex, 2H, ArCH2O),
5.30 (t, 1H, J¼13.6 Hz, ArCH2O), 5.01–5.22 (complex, 9H,
ArCH2O), 4.85 (dt, 1H, J¼7.4, 9.2 Hz, InsH-6), 4.60 (dd,
1H, J¼4.8, 9.0 Hz, InsH-3), 4.55 (t, 1H, J¼4.8 Hz, InsH-2),
4.39 (dt, 1H, J¼7.4, 9.2 Hz, InsH-5), 4.29 and 4.30 (2£t,
1H, J¼7.4, 9.0 Hz, InsH-4), 4.22 (dd, 1H, J¼4.8, 7.4 Hz,
InsH-1), 1.82 (br, 2H, cyclohexylidene H), 1.51–1.64 (br,
6H, cyclohexylidene H), 1.25 (br, 2H, cyclohexylidene H);
13C NMR (100.6 MHz) d: 135.08–135.73 (m, aromatic C),
127.92–129.21 (m, aromatic C), 112.43 (s, spiral C), 79.65
(t, J¼5.8 Hz, InsC-6), 79.23 (t, J¼5.1 Hz, InsC-5), 76.30 (d,
J¼2.2 Hz, InsC-1), 75.81 (d, J¼5.8 Hz, InsC-3), 74.09 (d,
3.2.9. Compound 14i. The title compound (86%) as
1
white solid. H NMR (400 MHz) d: 7.29–7.37 (m, 10H,
aromatic), 5.22 (dd, 1H, J¼7.2, 9.6 Hz, InsH-6), 5.01–5.15
(complex, 4H, ArCH2O), 4.83 (dd, 1H, J¼9.2, 9.6 Hz,
InsH-5), 4.51 (dt, 1H, J¼4.0, 9.2 Hz, InsH-3), 4.44 (dd, 1H,
J¼4.0, 5.0 Hz, InsH-2), 4.14 (t, 1H, J¼9.2 Hz, InsH-4), 4.10
(dd, 1H, J¼5.0, 7.2 Hz, InsH-1), 2.07 (s, 3H, CH3), 2.06 (s,
3H, CH3), 1.79 (m, 2H, cyclohexylidene), 1.63 (br, 2H,