3738
P. Merino et al. / Tetrahedron: Asymmetry 14 (2003) 3731–3743
4.2.4.
4-[(3S,5S)-1-Benzyl-3-hydroxy-2-oxo-5-pyrro-
-lyxo-tetro-
OH), 3.85 (ddd, 1H, J=3.6, 7.2, 9.4 Hz, H5), 3.91 (d,
lidinyl]-2,3-O-isopropyliden-1-O-methyl-a-
D
1H, J=3.3 Hz, H3%), 4.08 (dd, 1H, J=3.3, 9.4 Hz, H4%),
4.36 and 5.05 (2d, 2H, J=14.6 Hz, NCH2Ph), 4.39 (d,
1H, J=11.8 Hz, OCH2Ph), 4.42 (t, 1H, J=8.6 Hz, H3),
4.56 (d, 1H, J=3.8 Hz, H2%), 4.63 (d, 1H, J=11.8 Hz,
OCH2Ph), 5.98 (d, 1H, J=3.8 Hz, H1%), 7.16–7.36 (m,
10H, ArH). 13C NMR (CDCl3) l 26.2, 26.7, 31.5, 46.2,
53.4, 68.7, 71.8, 81.1, 82.5, 84.0, 105.6, 111.9, 127.3,
128.0, 128.3, 128.5, 128.5, 128.6, 134.2, 136.1, 174.9.
Anal. calcd for C25H29NO6: C, 68.32; H, 6.65; N, 3.19.
Found: C, 68.56; H, 6.44; N, 3.11.
furanose 7d. (Et2O; Rf=0.32); 0.327 g (90%); white
solid; mp 76–78°C; [h]2D5=+46 (c 0.30, CHCl3); IR
(wCꢀO) 1685 cm−1; H NMR (CDCl3, 55°C) l 1.26 (s,
1
3H, CH3), 1.33 (s, 3H, CH3), 1.72 (td, 1H, J=6.7, 13.4
Hz, H4b), 2.61 (ddd, 1H, J=7.2, 8.3, 13.4 Hz, H4a), 3.14
(s, 3H, OCH3), 3.74 (dt, 1H, J=6.7, 8.3 Hz, H5), 3.95
(dd, 1H, J=3.5, 8.3 Hz, H4%), 4.34 (t, 1H, J=7.1 Hz,
H3), 4.48 (d, 1H, J=5.8 Hz, H2%), 4.49 (d, 1H, J=14.4
Hz, NCH2Ph), 4.71 (dd, 1H, J=3.5, 5.8 Hz, H3%), 4.91
(s, 1H, H1%), 4.98 (d, 1H, J=14.4 Hz, NCH2Ph), 4.60
(bs, 1H, OH), 7.07–7.19 (m, 5H, ArH). 13C NMR
(CDCl3) l 24.9, 26.0, 30.8, 45.9, 54.7, 54.8, 69.3, 80.5,
84.8 (2C), 107.9, 112.7, 127.3, 128.3, 128.4, 137.1, 175.7.
Anal. calcd for C19H25NO6: C, 62.80; H, 6.93; N, 3.85.
Found: C, 62.72; H, 6.95; N, 3.91.
4.2.8.
4-[(3S,5S)-1-Benzyl-3-hydroxy-2-oxo-5-pyrro-
-xylo-tetro-
lidinyl]-3-O-benzyl-1,2-O-isopropyliden-a-
D
furanose 8d. (Et2O; Rf=0.29); 0.365 g (83%); white
solid; mp 197–199°C; [h]2D5=−29 (c 0.81, CHCl3); IR
(wCꢀO) 1700 cm−1; H NMR (CDCl3, 55°C) l 1.29 (s,
1
3H, CH3), 1.34 (s, 3H, CH3), 1.52 (td, 1H, J=7.6, 13.1
Hz, H4b), 2.00 (bs, 1H, OH), 2.42 (td, 1H, J=7.6, 13.1
Hz, H4a), 3.77 (q, 1H, J=8.1 Hz, H5), 3.95 (d, 1H,
J=3.1 Hz, H3%), 4.11 (dd, 1H, J=3.1, 8.3 Hz, H4%), 4.31
(t, 1H, J=7.6 Hz, H3), 4.40 (d, 1H, J=11.4, OCH2Ph),
4.53 (d, 1H, J=14.5 Hz, NCH2Ph), 4.56 (d, 1H, J=3.8
Hz, H2%), 4.63 (d, 1H, J=11.4, OCH2Ph), 4.88 (d, 1H,
J=14.5 Hz, NCH2Ph), 5.99 (d, 1H, J=3.8 Hz, H1%),
7.06–7.43 (m, 10H, ArH). 13C NMR (CDCl3) l 26.3,
26.6, 29.7, 45.5, 54.7, 69.0, 71.9, 80.5, 82.7, 84.0, 105.6,
111.9, 127.2, 128.0, 128.3, 128.5, 128.6, 128.8, 136.6,
137.2, 175.4. Anal. calcd for C25H29NO6: C, 68.32; H,
6.65; N, 3.19. Found: C, 68.21; H, 6.77; N, 3.07.
4.2.5.
4-[(3R,5R)-1-Benzyl-3-hydroxy-2-oxo-5-pyrro-
-xylo-tetro-
lidinyl]-3-O-benzyl-1,2-O-isopropyliden-a-
D
furanose 8a. (Et2O; Rf=0.27); 0.334 g (76%); white
solid; mp 152–154°C; [h]2D5=−22 (c 0.88, CHCl3); IR
(wCꢀO) 1700 cm−1; H NMR (CDCl3, 55°C) l 1.26 (s,
1
3H, CH3), 1.32 (s, 3H, CH3), 2.23 (td, 1H, J=5.6, 14.0
Hz, H4b), 2.42 (td, 1H, J=7.8, 14.0 Hz, H4a), 3.75 (ddd,
1H, J=3.4, 5.6, 7.4 Hz, H5), 3.80 (d, 1H, J=3.4 Hz,
H3%), 4.09 (bs, 1H, OH), 4.19 (d, 1H, J=15.6 Hz,
NCH2Ph), 4.25–4.30 (m, 1H, H3), 4.29 (t, 1H, J=3.4
Hz, H4%), 4.32 (d, 1H, J=11.7 Hz, OCH2Ph), 4.56 (d,
1H, J=3.8 Hz, H2%), 4.58 (d, 1H, J=11.7 Hz,
OCH2Ph), 4.77 (d, 1H, J=15.6 Hz, NCH2Ph), 5.90 (d,
1H, J=3.8 Hz, H1%), 7.06–7.30 (m, 10H, ArH). 13C
NMR (CDCl3) l 26.3, 26.8, 30.8, 45.0, 54.6, 69.4, 71.8,
77.8, 82.1, 82.7, 104.6, 111.9, 127.4, 127.5 (2C), 128.0,
128.4, 128.7, 136.3, 137.0, 175.0. Anal. calcd for
C25H29NO6: C, 68.32; H, 6.65; N, 3.19. Found: C,
68.42; H, 6.72; N, 3.23.
4.2.9.
lidinyl]-1,2:3,4-di-O-isopropyliden-a-
ranose 9a. (Et2O; Rf=0.40); 0.394 g (90%); white solid;
mp 124–126°C; [h]2D5=+47 (c 0.40, CHCl3); IR (wCꢀO
5-[(3R,5R)-1-Benzyl-3-hydroxy-2-oxo-5-pyrro-
D
-galacto-pentopy-
)
1688 cm−1; 1H NMR (CDCl3, 55°C) l 1.29 (s, 3H,
CH3), 1.33 (s, 3H, CH3), 1.43 (s, 3H, CH3), 1.57 (s, 3H,
CH3), 2.25–2.42 (m, 2H, H4b and H4a), 3.27 (bs, 1H,
OH), 3.62–3.67 (m, 1H, H5), 4.00 (d, 1H, J=15.3 Hz,
NCH2Ph), 4.01 (bs, 1H, H5%), 4.10 (dd, 1H, J=1.6, 8.0
Hz, H4%), 4.25 (dd, 1H, J=5.8, 6.9 Hz, H3), 4.31 (dd,
1H, J=2.0, 5.1 Hz, H2%), 4.59 (dd, 1H, J=2.0, 8.0 Hz,
H3%), 5.20 (d, 1H, J=15.3 Hz, NCH2Ph), 5.57 (d, 1H,
J=5.1 Hz, H1%), 7.14–7.35 (m, 5H, ArH). 13C NMR
(CDCl3) l 24.1, 24.7, 25.8, 26.1, 30.2, 44.1, 55.6, 65.0,
70.0, 70.5, 71.2, 71.6, 96.7, 108.6, 109.5, 127.6, 127.8,
128.8, 136.2, 175.1. Anal. calcd for C22H29NO7: C,
62.99; H, 6.97; N, 3.34. Found: C, 62.85; H, 7.15; N,
3.37.
4.2.6.
4-[(3S,5R)-1-Benzyl-3-hydroxy-2-oxo-5-pyrro-
lidinyl]-3-O-benzyl-1,2-O-isopropyliden-a- -xylo-tetro-
D
furanose 8b. (Et2O; Rf=0.35); 0.365 g (83%); oil;
[h]2D5=−86 (c 0.64, CHCl3); IR (wCꢀO) 1695 cm−1; H
1
NMR (CDCl3, 55°C) l 1.29 (s, 3H, CH3), 1.36 (s, 3H,
CH3), 1.79 (td, 1H, J=9.0, 13.0 Hz, H4b), 2.84 (ddd,
1H, J=1.0, 8.3, 13.0 Hz, H4a), 3.64 (bs, 1H, OH), 3.71
(bdd, 1H, J=3.3, 9.0, H5), 3.80 (d, 1H, J=3.3 Hz, H3%),
4.15 (d, 1H, J=15.2 Hz, NCH2Ph), 4.23 (t, 1H, J=3.3
Hz, H4%), 4.38 (d, 1H, J=11.9, OCH2Ph), 4.59 (t, 1H,
J=8.8 Hz, H3), 4.59 (d, 1H, J=3.8 Hz, H2%), 4.63 (d,
1H, J=11.9, OCH2Ph), 4.82 (d, 1H, J=15.2 Hz,
NCH2Ph), 5.91 (d, 1H, J=3.8 Hz, H1%), 7.10–7.35 (m,
10H, ArH). 13C NMR (CDCl3) l 26.2, 26.8, 31.3, 45.3,
54.6, 69.1, 71.8, 78.5, 82.1, 82.8, 104.9, 111.9, 127.4,
127.6, 127.7, 128.1, 128.6, 128.8, 135.9, 137.0, 176.0.
Anal. calcd for C25H29NO6: C, 68.32; H, 6.65; N, 3.19.
Found: C, 68.14; H, 6.73; N, 3.27.
4.2.10.
5-[(3S,5R)-1-Benzyl-3-hydroxy-2-oxo-5-pyrro-
lidinyl]-1,2:3,4-di-O-isopropyliden-a- -galacto-pentopy-
D
ranose 9b. (Et2O; Rf=0.39); 0.381 g (91%); oil;
[h]2D5=−115 (c 0.35, CHCl3); IR (wCꢀO) 1695 cm−1; H
1
NMR (CDCl3, 55°C) l 1.24 (s, 3H, CH3), 1.32 (s, 3H,
CH3), 1.44 (s, 3H, CH3), 1.52 (s, 3H, CH3), 1.85 (td,
1H, J=8.5, 13.1 Hz, H4b), 2.86 (dd, 1H, J=8.8, 13.1
Hz, H4a), 3.00 (bs, 1H, OH), 3.58 (dd, 1H, J=4.3, 8.2
Hz, H5), 3.76 (dd, 1H, J=1.8, 4.3 Hz, H5%), 3.92 (d, 1H,
J=14.9 Hz, NCH2Ph), 4.10 (dd, 1H, J=1.8, 8.0 Hz,
H4%), 4.31 (dd, 1H, J=2.3, 5.1 Hz, H2%), 4.52 (t, 1H,
J=9.0 Hz, H3), 4.59 (dd, 1H, J=2.3, 8.0 Hz, H3%), 5.18
(d, 1H, J=14.9 Hz, NCH2Ph), 5.51 (d, 1H, J=5.1 Hz,
4.2.7.
4-[(3R,5S)-1-Benzyl-3-hydroxy-2-oxo-5-pyrro-
lidinyl]-3-O-benzyl-1,2-O-isopropyliden-a- -xylo-tetro-
D
furanose 8c. (Et2O; Rf=0.25); 0.356 g (81%); oil;
[h]2D5=+24 (c 0.34, CHCl3); IR (wCꢀO) 1686 cm−1; H
1
NMR (CDCl3, 55°C) l 1.32 (s, 3H, CH3), 1.45 (s, 3H,
CH3), 1.86–1.93 (m, 2H, H4a and H4b), 3.70 (bs, 1H,