2526
F. Orsini, E. Di Teodoro / Tetrahedron: Asymmetry 14 (2003) 2521–2528
Anal. calcd for C12H20O8: C, 49.32%; H, 7.85%. Found:
C, 49.74%; H, 7.83%.
3H), 1.43 (s, 3H), 1.44 (s, 9H), 2.62 and 2.69 (AB
system, 2H, J=16.5 Hz), 3.96 (dd, 1H, J=7.8, 5.5 Hz),
4.03 (dd, 1H, J=7.8, 5.8 Hz), 4.07 (dd, 1H, J=7.5, 5.5
Hz), 4.13 (ddd, 1H, J=7.5, 5.8, 5.5 Hz), 4.45 (d, 1H,
J=6.0 Hz), 4.82 (dd, 1H, J=6.0, 4.5 Hz); 13C NMR
(CDCl3): 24.39 (q), 25.02 (q), 25.32 (q), 26.75 (q),
3×27.97 (q), 39.23 (t), 66.78 (t), 73.02 (d), 79.25 (d),
80.13 (d), 82.02 (s), 85.72 (d), 103.97 (s), 109.05 (s),
112.7 (s), 171.36 (s); MS m/z: 359 (M+−CH3), 302
2e.8 Colorless syrup. [h]D25: 3.6 (CHCl3, c 17.9 mg/mL);
1H NMR (CDCl3): l 1.45 (s, 9H), 2.28 (d, 1H, J=15.0
Hz), 2.73 (d, 1H, J=15.0 Hz), 3.3 (d, 1H, J=9.0 Hz),
3.60 (dd, 1H, J=10.5, 1.5 Hz), 3.68 (dd, 1H, J=9.0, 9.0
Hz), 3.73 (dd, 1H, J=10.5, 3.0 Hz), 4.30 (ddd, 1H,
J=9.0, 3.0, 1.5 Hz), 4.12 (dd, J=9.0, 9.0 Hz), 4.5–4.7
(4 H), 4.85 (d, 1H, J=12.0 Hz), 4.90 (s, 2H), 4.95 (d,
1H, J=12.0 Hz); 13C NMR (CDCl3): 3×28.07 (q), 41.59
(t), 68.81 (t), 71.39 (d), 73.42 (t), 74.85 (t), 75.30 (t),
75.61 (t), 77.46 (d), 78.62 (d), 82.27 (d), 83.18 (d), 97.22
(s), 8×127.60 (d), 4×127.79 (d), 8×128.37 (d), 1347.95
(s), 138.38 (s), 138.40 (s), 138.64 (s), 171.68 (s); MS,
m/z: 536 (M+−H2O−COOtBu), 429 (536−PhCH2O), 337
(429−PhCH2OH), 107 (PhCH2O), 91 (PhCH2). Anal.
calcd for C40H46O8: C, 73.39%; H, 7.03%. Found: C,
73.48%; H, 7.33%.
(M+−CH3−OtBu),
259
(M+−CH2COOtBu),
115
(CH2COOtBu). Anal. calcd for C18H30O8: C, 57.75%;
H, 8.02%. Found: C, 56.82%; H, 8.04%.
2c.12 Colorless syrup; [h]D25=−48.5 (CHC13, c 10.50
1
mg/mL); H NMR (CDCl3): l 1.32 (s, 3H), 1.46 (s,
3H), 1.48 (s, 9H), 2.72 and 2.78 (AB system, J=16.5
Hz), 3.94 (d, 1H, J=10.5 Hz), 4.07 (1H, dd, J=10.5,
3.4 Hz), 4.43 (d, 1H, 6. 0 Hz), 4.85 (dd, 1H, J=6.0, 3.4
Hz); 13C NMR (CDCl3): 24.80 (q), 26.23 (q), 3×28.07
(q), 39.15 (t), 72.23 (t), 80.55 (d), 82.21 (s), 85.38 (d),
104.55 (s), 112.49 (s), 171.82 (s); MS, m/z: 259 (M+−
CH3), 201 (M+−OC(CH3)), 159 (M+−CH2COOtBu), 143
(201−CH3COOCH3). Anal. calcd for C13H22O6: C,
56.93%; H, 8.03%. Found: C, 56.74%; H, 8.05%.
2e%.8 Colorless syrup. [h]D25 −10.1 (CHCl3, c 17.8 mg/
1
mL); H NMR (CDCl3): l 2.34 (d, 1H, J=16.0 Hz),
2.75 (d, 1H, J=16.0 Hz), 3.34 (d, 1H, J=8.0 Hz), 3.61
(dd, 1H, J=10.5, 2.0 Hz), 3.66 (s, 3H), 3.69 (dd, 1H,
J=9.5, 8.0 Hz), 3.73 (dd, 1H, J=10.5, 4.0 Hz), 4.01
(ddd, J=9.5, 4.0, 2.0 Hz), 4.13 (dd, 1H, J=8.0, 8.0
Hz), 4.49 and 4.56 (AB system, J=12.0 Hz), 4.59 (d,
1H, J=12.0 Hz), 4.65 (d, 1H, J=12.0 Hz), 4.84 (d, 1H,
J=12.0 Hz), 4.91 (s, 2H), 4.96 (d, 1H, J=12.0 Hz); 13C
NMR (CDCl3): 40.32 (t), 51.69 (t), 68.59 (t), 71.46 (d),
73.19 (t), 74.81 (t), 75.46 (t), 75.56 (t), 78.46 (d), 81.76
(d), 83.11 (d), 96.02 (s), 8×122.71 (d), 4×124.40 (d),
8×128.31 (d), 137.79 (s), 2×138.24 (s), 138.52 (s), 172.71
(s); MS, m/z: 594 (M+−H2O), 521 (M+−CH2COOMe),
503 (521−H2O), 91 (PhCH2). Anal. calcd for C37H40O8:
C, 72.55%; H, 6.54%. Found: C, 72.48%; H, 6.53%.
2c%. Colorless syrup; [h]2D5 −45.7 (CHC13, c 10.46 mg/
1
mL); H NMR (CDCl3): l 1.25 (s, 3H), 1.40 (s, 3H),
2.75 and 2.88 (2H, AB system, J=17.5 Hz), 3.72 (s,
3H), 3.90 (d, 1H, J=10.0 Hz), 4.0 (dd, 1H, J=10.0, 4.0
Hz), 4.43 (d, 1H, J=5.5 Hz), 4.82 (dd, 1H, J=5.5, 4. 0
Hz); 13C NMR (CDCl3): 24.78 (q), 26.16 (q), 38.29 (t),
51.87 (q), 71.22 (t), 80.52 (d), 85.13 (d), 104.38 (s),
112.54 (s), 172.49 (s); MS, m/z: 232 (M+), 217 (M+−
CH3), 201 (M+−OCH3), 159 (M+−CH2COOCH3), 73
(CH2COOCH3). Anal. calcd for C10H16O6: C, 51.72%;
H, 6.90%. Found: C, 51.74%; H, 6.53%.
1
2f.8 Colorless syrup. H NMR (CDCl3): l 1.38 (s, 9H).
2d. Colorless syrup [h]2D5 −11.6 (CHCl3, c 4.2 mg/mL);
1H NMR (CDCl3): l 1.25 (s, 3H), 1.38 (s, 3H), 1.52 (s,
6H), 2.86 and 2.87 (AA% system, J=18 Hz), 3.72 (s,
3H), 3.65–3.72 (m, 2H), 4.08 (dd, 1H, J=7.5, 4.5 Hz),
4.18 (t, 1H, J=7.5 Hz), 4.3 (ddd, 1H, J=7.5, 7.5, 7.5
Hz), 4.52 (d, 1H, J=6.0 Hz), 4.70 (dd, 1H, J=6.0, 4.5
Hz); 13C NMR (CDCl3): 24.39 (q), 25.88 (q), 38.24 (t),
51.98 (q), 63.54 (t), 70.70 (d), 78.98 (d), 80.70 (d), 86.06
(d), 103.50 (s), 113.0 (s), 172.44 (s); MS, m/z: 332 (M+),
317 (M+−CH3), 301 (M+−OCH3), 259 (M+−
CH2COOCH3), 73 (CH2COOCH3). Anal. calcd for
C15H24O8: C, 54.22%; H, 7.23%. Found: C, 54.52%; H,
7.53%.
2.35 (d, 1H, J=15.5 Hz), 2.78 (d, 1H, J=15.5 Hz), 3.48
(dd, 1H, J=9.0, 6.0 Hz), 3.59 (dd, 1H, J=9.0, 7.5 Hz),
3.77 (d, 1H, J=9.3 Hz), 4.02 (dd, 1H, J=2.5, 1.5 Hz),
4.09 (dd, 1H, J=9.3, 2.5 Hz), 4.17 (ddd, 1H, J=7.5,
6.0, 1.5 Hz), 4.40 and 4.48 (AB System, 2H, J=12.0
Hz), 4.61 (s, 2H), 4.63 (d, 1H, J=12.0 Hz), 4.95 (d, 1H,
J=12.0 Hz), 4.98 (d, 1H, J=12 Hz). 13C NMR
(CDCl3): 3×28.02 (q), 41.59 (t), 68.91 (t), 70.07 (d),
72.67 (t), 73.41 (t), 74.70 (t), 74.99 (d), 75.32 (t), 78.62
(d), 80.41 (d), 82.08 (s), 97.74 (s), 4×127.55 (d), 2×
127.71 (d), 2×127.84 (d), 4×128.18 (d), 8×128.38 (d),
2×138.12 (s), 138.53 (s), 138.81 (s), 171.86 (s); MS, m/z:
636 (M+−H2O), 536 (636−COOtBu), 337 (429−
PhCH2OH), 107 (PhCH2O), 91 (PhCH2). Anal. calcd
for C40H46O8: C, 73.39%; H, 7.03%. Found: C, 73.58%;
H, 7.43%.
2d%. Colorless syrup; [h]2D5 −14.8 (CHC13, c 3.5 mg/mL);
1H NMR (CDCl3): l 1.31 (s, 3H), 1.48 (s, 3H), 2.83 and
2.92 (AB system, 2H, J=16.6 Hz), 3.74 (s, 3H), 3.65–
3.80 (m, 2H), 4.05 (ddd, 1H, J=4.0, 4.0, 4. 0 Hz), 4.16
(dd, 1H, J=6.0, 4. 0 Hz), 4.53 (d, 1H, J=6. 0 Hz), 4.81
(dd, 1H, J=6.0,4.0 Hz); 13C NMR (CDCl3): 24.68 (q),
25.42 (q), 25.94 (q), 38.07 (t), 51.93 (q), 66.05 (t), 75.56
(d), 80.34 (d), 81.88 (d), 85.55 (d), 85.89 (d), 104.03 (s),
109.75 (s), 112.86 (s); MS, m/z: 292 (M+), 231 (M+−
CH(OH)CH2(OH)), 213 (231−H2O),107 (PhCH2O),98
(213−C(CH3)2−CH2COOCH3), 73 (CH2COOCH3).
2g. Colorless syrup. [h]2D5 +4.5 (CHC13, c 10.5 mg/mL);
1H NMR (CDCl3) l 1.1 (d, 3H, J=7.1 Hz), 1.42 (s,
9H), 2.32 (d, 1H, J=15.0 Hz), 2.76 (d, 1H, J=15.0
Hz), 3.68 (dd, 1H, J=3.0, 1.0 Hz), 3.78 (d, 1H, J=10.5
Hz), 4.18 (dd, 1H, J=10.5, 3.0 Hz), 4.19 (dq, 1H,
J=7.2, 1.0 Hz), 4.69 (d, 1H, J=12.0 Hz), 4.70 (d, 1H,
J=12.0 Hz), 4.76 (s, 2H), 4.97 (d, 1H, J=12.0 Hz),
4.99 (d, 1H, J=12.0 Hz), 7.25–7.4 (15H); 13C NMR
(CDCl3): 16.54 (q), 3×27.96 (q), 41.66 (t), 66.94 (d),