5490 J . Org. Chem., Vol. 62, No. 16, 1997
Dondoni et al.
column chromatography (80:20 hexane-diethyl ether): 1.31 g,
method A. Isolated by column chromatography (80:20 hex-
1
70%; oil; [R]D ) -12.2 (c 2.30, CHCl3); H NMR δ 1.34 (s, 3
ane-diethyl ether): 1.42 g, 66%; oil; [R]D ) -54.8 (c 1.36,
1
H), 1.46 (s, 3 H), 3.04 (s, 3 H), 3.64 (d, 1 H, J ) 13.0 Hz), 3.72
(d, 1 H, J ) 13.0 Hz), 3.93 (d, 1 H, J ) 11.0 Hz), 4.58 (d, 1 H,
J ) 6.1 Hz), 4.75 (dd, 1 H, J ) 11.0, 1.0 Hz), 4.88 (s, 1 H), 4.97
(s, 1 H, ex D2O), 5.16 (dd, 1 H, J )6.1, 1.0 Hz), 6.39 (dd, 1 H,
J ) 3.3, 0.7 Hz), 6.43 (dd, 1 H, J ) 3.3, 1.8 Hz), 7.22-7.34 (m,
5 H), 7.47 (dd, 1 H, J ) 1.8, 0.7 Hz); 13C NMR δ 25.2, 26.5,
55.1, 62.0, 65.4, 82.5, 85.1, 86.0, 109.5, 110.4, 110.4, 112.4,
CHCl3); H NMR δ 1.24 (s, 3 H), 1.33 (s, 3 H), 1.47 (s, 3 H),
1.57 (s, 3 H), 3.60 (d, 1 H, J ) 13.4 Hz), 3.66 (d, 1 H, J ) 13.4
Hz), 3.84 (dd, 1 H, J ) 8.1, 1.2 Hz), 4.32 (dd, 1 H, J ) 5.1, 2.4
Hz), 4.42 (d, 1 H, J ) 10.5 Hz), 4.46 (dd, 1 H, J ) 10.5, 1.2
Hz), 4.56 (dd, 1 H, J ) 8.1, 2.4 Hz), 5.08 (bs, 1 H, ex D2O),
5.64 (d, 1 H, J ) 5.1 Hz), 6.38-6.44 (m, 2 H), 7.26-7.38 (m, 5
H), 7.46-7.50 (m, 1 H); 13C NMR δ 24.3, 25.0, 25.9, 25.9, 60.3,
62.9, 67.0, 70.7, 70.9, 71.1, 97.0, 108.8, 109.4, 110.2, 110.4,
127.4, 128.3, 129.3, 137.5, 142.2, 150.4. Anal. Calcd for C20
-
H25NO6: C, 63.99; H, 6.71; N, 3.73. Found: C, 63.84; H, 6.80;
N, 3.79.
127.0, 128.0, 129.5, 138.0, 142.4, 150.0. Anal. Calcd for C23-
H29NO7: C, 64.02; H, 6.77; N, 3.25. Found: C, 63.88; H, 6.81;
N, 3.18.
Meth yl N-Ben zyl-5-deoxy-5-(2-fu r yl)-5-(h ydr oxyam in o)-
2,3-O-isop r op ylid n e-â-L-gu lo-1,4-p en t ofu r a n osid e (8a ).
From the nitrone 4 (1.54 g, 5 mmol) by method A. Isolated by
column chromatography (80:20 hexane-diethyl ether): 1.20 g,
N -Be n zyl-6-d e oxy-1,2:3,4-d i-O-isop r op ylid e n e -6-(2-
fu r yl)-6-(h yd r oxya m in o)-r-D-glycer o-D-ga la cto-1,5-h ex-
op yr a n ose (10b). From the nitrone 6 (1.82 g, 5 mmol) by
method B. Isolated by column chromatography (80:20 hex-
ane-diethyl ether): 1.94 g, 90%; white solid; mp 184-186 °C;
[R]D ) -73.2 (c 0.25, CHCl3); 1H NMR δ 1.29 (s, 3 H), 1.38 (s,
6 H), 1.58 (s, 3 H), 3.80 (ABq, 2 H, J ) 13.7 Hz, ∆δ ) 0.02),
4.26 (dd, 1 H, J ) 5.1, 2.2 Hz), 4.29 (d, 1 H, J ) 10.2 Hz), 4.32
(bs, 1 H, ex D2O), 4.42 (dd, 1 H, J ) 10.2, 1.5 Hz), 4.62 (dd, 1
H, J ) 8.1, 2.2 Hz), 4.66 (dd, 1 H, J ) 8.1, 1.5 Hz), 5.44 (d, 1
H, J ) 5.1 Hz), 6.40 (dd, 1 H, J ) 3.2, 1.0 Hz), 6.42 (dd, 1 H,
J ) 3.2, 1.7 Hz), 7.26-7.39 (m, 5 H), 7.47 (dd, 1 H, J ) 1.7,
1.0 Hz); 13C NMR δ 24.5, 25.0, 26.0, 26.1, 62.2, 62.4, 66.7, 70.8,
71.0 (x2), 96.8, 108.6, 109.0, 110.3, 110.7, 127.20, 128.1, 129.3,
137.6, 142.3, 150.0. Anal. Calcd for C23 H29NO7: C, 64.02;
H, 6.77; N, 3.25. Found: C, 63.82; H, 6.60; N, 3.34.
1
64%; oil; [R]D ) +31.4 (c 1.20, CHCl3); H NMR δ 1.19 (s, 3
H), 1.39 (s, 3 H), 3.38 (s, 3 H), 3.75 (s, 2 H), 4.43 (dd, 1 H, J )
5.8, 3.2 Hz), 4.47 (d, 1 H, J ) 10.2 Hz), 4.51 (d, 1 H, J ) 5.8
Hz), 4.62 (dd, 1 H, J ) 10.2, 3.2 Hz), 4.99 (s, 1 H), 5.12 (s, 1 H,
ex D2O), 6.37 (d, 1 H, J ) 3.4 Hz), 6.41 (dd, 1 H, J ) 3.4, 1.7
Hz), 7.20-7.40 (m, 5 H), 7.45 (d, 1 H, J ) 1.7 Hz); 13C NMR δ
25.0, 26.1, 54.8, 60.8, 62.3, 78.3, 80.1, 84.5, 107.5, 110.0, 110.3,
112.6, 127.1, 128.2, 129.5, 137.8, 142.2, 150.0. Anal. Calcd
for C20H25NO6: C, 63.99; H, 6.71; N, 3.73. Found: C, 64.16;
H, 6.95; N, 3.95.
Meth yl N-Ben zyl-5-deoxy-5-(2-fu r yl)-5-(h ydr oxyam in o)-
2,3-O-isopr opyliden e-r-D-ma n n o-1,4-pen tofu r an oside (8b).
From the nitrone 4 (1.54 g, 5 mmol) by method B. Isolated by
column chromatography (80:20 hexane-diethyl ether): 1.33 g,
71%; white solid; mp 67-69 °C; [R]D ) +24.7 (c 1.60, CHCl3);
1H NMR δ 1.32 (s, 3 H), 1.33 (s, 3 H), 3.22 (s, 3 H), 3.71 (d, 1
H, J ) 13.1 Hz), 3.82 (d, 1 H, J ) 13.1 Hz), 4.38 (d, 1 H, J )
9.9 Hz), 4.53 (d, 1 H, J ) 5.8 Hz), 4.56 (dd, 1 H, J ) 9.9, 3.2
Hz), 4.77 (bs, 1 H, ex D2O), 4.80 (s, 1 H), 4.88 (dd, 1 H, J )
5.8, 3.2 Hz), 6.40 (dd, 1 H, J ) 3.1, 0.9 Hz), 6.43 (dd, 1 H, J )
3.1, 1.9 Hz), 7.24-7.37 (m, 5 H), 7.45 (dd, 1 H, J ) 1.9, 0.9
Hz); 13C NMR δ 25.2, 26.1, 54.3, 61.4, 62.2, 78.5, 79.8, 84.7,
106.9, 110.2, 110.3, 112.3, 127.3, 128.1, 129.5, 137.4, 142.4,
150.4. Anal. Calcd for C20H25NO6: C, 63.99; H, 6.71; N, 3.73.
Found: C, 64.08; H, 6.86; N, 3.50.
N-Ben zyl-3-O-ben zyl-5-deoxy-5-(2-fu r yl)-5-(h ydr oxyam i-
n o)-1,2-O-isopr opyliden e-â-L-ido-1,4-pen tofu r an oside (9a).
From the nitrone 5 (1.92 g, 5 mmol) by method A. Isolated by
column chromatography (60:40 hexane-diethyl ether): 1.90 g,
84%; white solid; mp 58-60 °C; [R]D ) -35.6 (c 1.30, CHCl3);
1H NMR δ 1.31 (s, 3 H), 1.52 (s, 3 H), 3.65 (d, 1 H, J ) 2.8
Hz), 3.68 (d, 1 H, J ) 13.4 Hz), 3.82 (d, 1 H, J ) 13.4 Hz), 4.09
(d, 1 H, J ) 11.4 Hz), 4.37 (d, 1 H, J ) 11.4 Hz), 4.47 (d, 1 H,
J ) 10.0 Hz), 4.53 (d, 1 H, J ) 3.6 Hz), 4.90 (dd, 1 H, J )
10.0, 2.8 Hz), 5.13 (bs, 1 H, ex D2O), 6.02 (d, 1 H, J ) 3.6 Hz),
6.34 (d, 1 H, J ) 3.2 Hz), 6.40 (dd, 1 H, J ) 3.2, 1.7 Hz), 7.15-
7.40 (m, 10 H), 7.44 (d, 1 H, J ) 1.7 Hz); 13C NMR δ 26.3,
26.9, 61.4, 62.7, 72.2, 79.2, 81.7, 82.4, 105.4, 109.9, 110.3, 111.7,
127.1, 127.6, 127.8, 128.1, 128.3, 129.4, 137.3, 137.8, 142.0,
150.1. Anal. Calcd for C26 H29NO6: C, 69.16; H, 6.47; N, 3.10.
Found: C, 68.94; H, 6.40; N, 3.08.
N-Ben zyl-3-O-ben zyl-5-deoxy-5-(2-fu r yl)-5-(h ydr oxyam i-
n o)-1,2-O-isopr opyliden e-â-D-glu co-1,4-pen tofu r an ose (9b).
From the nitrone 5 (1.92 g, 5 mmol) by method B. Isolated by
column chromatography (60:40 hexane-diethyl ether): 1.76 g,
78%; white solid; mp 95-97 °C; [R]D ) -22.9 (c 1.52, CHCl3);
1H NMR δ 1.29 (s, 3 H), 1.50 (s, 3 H), 3.71 (s, 2 H), 4.19 (d, 1
H, J ) 2.9 Hz), 4.42 (s, 1 H, ex D2O), 4.50 (d, 1 H, J ) 10.0
Hz), 4.57 (d, 1 H, J ) 3.7 Hz), 4.65 (d, 1 H, J ) 11.7 Hz), 4.71
(d, 1 H, J ) 11.7 Hz), 4.83 (dd, 1 H, J ) 10.0, 2.9 Hz), 5.87 (d,
1 H, J ) 3.7 Hz), 6.43 (dd, 1 H, J ) 3.2, 1.7 Hz), 6.45 (dd, 1 H,
J ) 3.2, 0.7 Hz), 7.21-7.23 (m, 5 H), 7.30-7.33 (m, 5 H), 7.49
(dd, 1 H, J ) 1.7, 0.7 Hz); 13C NMR δ 26.3, 26.9, 61.4, 62.3,
72.5, 79.3, 81.8, 82.0, 105.0, 110.3, 110.7, 111.6, 127.3, 127.4,
127.8, 128.2, 128.4, 129.3, 137.5, 137.9, 142.5, 150.1. Anal.
Calcd for C26 H29NO6: C, 69.16; H, 6.47; N, 3.10. Found: C,
69.32; H, 6.49; N, 3.25.
2,5-An h yd r o-N-ben zyl-1-d eoxy-3,4:6,7-d i-O-isop r op yl-
id en e-1-(2-fu r yl)-1-(h yd r oxya m in o)-D-er yth r o-L-m a n n o-
h ep titol (33a ). From the nitrone 31 (1.89 g, 5 mmol) by
method A. Isolated by column chromatography (60:40 hex-
ane-diethyl ether): 1.45 g, 65%; sticky oil; [R]D ) +2.1 (c 3.2,
1
CHCl3); H NMR δ 1.18 (s, 3 H), 1.34 (s, 3 H), 1.38 (s, 3 H),
1.45 (s, 3 H), 3.55 (dd, 1 H, J ) 7.7, 3.7 Hz), 3.74 (ABq, 2 H,
J ) 13.4 Hz, ∆δ ) 0.05), 4.11 (dd, 1 H, J ) 8.8, 6.1 Hz), 4.16
(dd, 1 H, J ) 10.1, 3.4 Hz), 4.20 (dd, 1 H, J ) 8.8, 4.3 Hz),
4.32 (d, 1 H, J ) 10.1 Hz), 4.41 (dd, 1 H, J ) 6.1, 3.4 Hz), 4.42
(ddd, 1 H, J ) 7.7, 6.1, 4.3 Hz), 4.67 (dd, 1 H, J ) 6.1, 3.7 Hz),
6.18 (bs, 1 H, ex D2O), 6.34 (dd, 1 H, J )3.2, 0.8 Hz), 6.40 (dd,
1 H, J ) 3.2, 1.9 Hz), 7.21-7.34 (m, 5 H), 7.43 (dd, 1 H, J )
1.9, 0.8 Hz); 13C NMR δ 24.7, 25.3, 25.7, 27.1, 61.0, 61.8, 66.9,
73.1, 80.2, 80.5, 81.2, 82.0, 109.1, 110.0, 110.2, 112.4, 127.1,
128.1, 129.5, 137.6, 142.1, 149.8. Anal. Calcd for C24 H31
-
NO7: C, 64.70; H, 7.01; N, 3.14. Found: C, 64.94; H, 6.93; N,
3.09.
2,5-An h yd r o-N-ben zyl-1-d eoxy-3,4:6,7-d i-O-isop r op yl-
iden e-1-(2-fu r yl)-1-(h ydr oxyam in o)-D-er yth r o-L-glu co-h ep-
titol (33b). From the nitrone 31 (1.89 g, 5 mmol) by method
B. Isolated by column chromatography (60:40 hexane-diethyl
1
ether): 1.47 g, 66%; oil; [R]D ) +5.1 (c 1.04, CHCl3); H NMR
δ 1.32 (s, 6 H), 1.33 (s, 3 H), 1.34 (s, 3 H), 3.45 (dd, 1 H, J )
7.5, 3.5 Hz), 3.65 (d, 1 H, J )13.1 Hz), 3.83 (d, 1 H, J ) 13.1
Hz), 3.86 (dd, 1 H, J ) 8.7, 6.4 Hz), 3.92 (dd, 1 H, J ) 8.7, 4.5
Hz), 4.09 (dd, 1 H, J ) 9.3, 3.3 Hz), 4.29 (ddd, 1 H, J ) 7.5,
6.4, 4.5 Hz), 4.34 (d, 1 H, J ) 9.3 Hz), 4.70 (dd, 1 H, J )5.8,
3.5 Hz), 4.88 (dd, 1 H, J ) 5.8, 3.3 Hz), 5.66 (bs (1 H, ex D2O),
6.33 (dd, 1 H, J )3.2, 0.9 Hz), 6.38 (dd, 1 H, J ) 3.2, 1.8 Hz),
7.22-7.35 (m, 5 H), 7.43 (dd, 1 H, J ) 1.8, 0.9 Hz); 13C NMR
δ 24.7, 25.4, 25.6, 26.8, 61.2, 62.2, 66.7, 73.0, 80.2, 80.6, 81.0,
81.6, 109.0, 110.1, 110.5, 112.1, 127.3, 128.1, 129.5, 137.3,
142.1, 150.2. Anal. Calcd for C24 H31NO7: C, 64.70; H, 7.01;
N, 3.14. Found: C, 64.84; H, 6.80; N, 3.41.
2,6-An h yd r o-N-ben zyl-1-d eoxy-1-(2-fu r yl)-1-(h yd r oxy-
am in o)-3,4,5,7-tetr a-O-ben zyl-D-th r eo-L-ta lo-h eptitol (34b).
From the nitrone 32 (3.29 g, 5 mmol) by method B. Isolated
by column chromatography (60:40 hexane-diethyl ether): 2.58
g, 71%; oil; [R]D ) +11.8 (c 1.40, CHCl3); 1H NMR δ 3.53-3.62
(m, 3 H), 3.64, (dd, 1 H, J ) 9.3, 2.6 Hz), 3.70 (d, 1 H, J ) 12.9
Hz), 3.76 (t, 1 H, J ) 9.4 Hz), 3.89 (d, 1 H, J ) 12.9 Hz), 3.96
(dd, 1 H, J ) 2.6, 0.5 Hz), 4.0 (dd, 1 H, J ) 9.4, 3.9 Hz), 4.35
(d, 1 H, J ) 11.8 Hz), 4.39 (d, 1 H, J ) 11.9 Hz), 4.41 (d, 1 H,
J ) 3.9 Hz), 4.42 (d, 1 H, J ) 11.9 Hz), 4.57 (d, 1 H, J ) 11.8
Hz), 4.66 (d, 1 H, J ) 11.7 Hz), 4.73 (d, 1 H, J ) 11.7 Hz), 4.75
(d, 1 H, J ) 11.8 Hz), 4.91 (d, 1 H, J ) 11.8 Hz), 5.70 (bs, 1 H,
N -Be n zyl-6-d e oxy-1,2:3,4-d i-O-isop r op ylid e n e -6-(2-
fu r yl)-6-(h yd r oxya m in o)-â-L-glycer o-D-ga la cto-1,5-h ex-
op yr a n ose (10a ). From the nitrone 6 (1.82 g, 5 mmol) by