H. Luo et al. / Carbohydrate Research 344 (2009) 2454–2460
2459
3.4.6. 1-C-(4-O-Acetyl-2,3-di-O-benzyl-5-deoxy-5-p-
nitrobenzylamino- -ribopyranosyl)propan-2-one (8f)
55.8 (C-5), 48.8 (C-1), 45.2 (C-10), 30.1 (COCH3), 21.0 (OCOCH3).
HRESIMS: calcd for C31H35ClNO5 [M+H]+: 536.2198, found:
536.2189.
D
Yield: 50% (over three steps).
(8f–a
) ½a 2D5
ꢀ
45.7 (c 0.3, CHCl3); 1H NMR (CDCl3): d 8.15 (d, 2H,
J = 8.5 Hz, Ar), 7.42 (d, 2H, J = 7.7 Hz, Ar), 7.37–7.28 (m, 10H, Ar),
4.80–4.75 (m, 2H, PhCH2, H-4), 4.70 (d, 1H, J = 11.9 Hz, PhCH2),
4.55 (d, 1H, J = 11.6 Hz, PhCH2), 4.48 (d, 1H, J = 11.6 Hz, PhCH2),
4.15 (br s, 1H, H-3), 3.90 (m, 1H, H-1), 3.87 (d, 1H, J = 13.8 Hz, N-
CH2-Ar), 3.70 (m, 1H, H-2), 3.55 (d, 1H, J = 14.2 Hz, N-CH2-Ar),
3.25 (dd, 1H, J5a,5b = 17.1, J5a,4 = 4.6 Hz, H-5a), 2.79 (dd, 1H,
J = 11.2, 10.3 Hz, H-10a), 2.73 (dd, 1H, J5a,5b = 17.3, J4,5b = 5.0 Hz,
H-5b), 2.41 (d, 1H, J = 7.7 Hz, H-10b), 2.12 (s, 3H, COCH3), 1.96 (s,
3H, OCOCH3); 13C NMR (CDCl3): d 208.7 (C@O), 170.1 (–O–C@O),
147.3 (Ar), 138.7 (Ar), 137.9 (Ar), 128.8 (Ar), 128.4 (Ar), 128.2
(Ar), 128.1 (Ar), 127.7 (Ar), 127.6 (Ar), 127.5 (Ar), 123.6 (Ar), 76.4
(C-2), 76.0 (C-3), 74.8 (C-4), 71.2 (PhCH2), 69.8 (PhCH2), 57.8 (N-
CH2-Ar), 55.5 (C-5), 43.5 (C-1), 37.9 (C-10), 30.9 (COCH3), 20.9
(OCOCH3). HRESIMS: calcd for C31H34N2NaO7 [M+Na]+: 569.2258,
found: 569.2270.
3.4.8. 1-C-(4-O-Acetyl-2,3-di-O-benzyl-5-o-chlorobenzylamino-
5-deoxy-D-ribopyranosyl)propan-2-one (8h)
Yield: 50% (over three steps).
(8h–a
) ½a 2D5
ꢀ
68.2 (c 0.4, CHCl3); 1H NMR (CDCl3): d 7.37–7.26
(m, 12H, Ar), 7.22 (m, 1H, Ar), 7.16 (m, 1H, Ar), 4.78 (d, 1H,
J = 12.0 Hz, PhCH2), 4.76 (m, 1H, H-4), 4.69 (d, 1H, J = 11.9 Hz,
PhCH2), 4.57 (d, 1H, J = 11.7 Hz, PhCH2), 4.48 (d, 1H, J = 11.8 Hz,
PhCH2), 4.16 (br s, 1H, H-3), 3.95 (m, 1H, H-1), 3.77 (d, 1H,
J = 14.5 Hz, N-CH2-Ar), 3.70 (br s, 1H, H-2), 3.66 (d, 1H,
J = 14.5 Hz, N-CH2-Ar), 3.26 (dd, 1H, J5a,5b = 16.5, J4,5a = 5.5 Hz, H-
5a), 2.84 (dd, 1H, J = 11.2, 11.2 Hz, H-10a), 2.74 (dd, 1H,
0
0
J5a,5b = 16.5, J4,5b = 5.9 Hz, H-5b), 2.48 (dd, 1H, JH-1 a,H-1 b = 11.3, JH-
1,H-1 b = 4.7 Hz, H-10b), 2.10 (s, 3H, COCH3), 1.95 (s, 3H, OCOCH3);
0
13C NMR (CDCl3): d 208.9 (C@O), 170.1 (–O–C@O), 138.9 (Ar),
138.1 (Ar), 136.1 (Ar), 134.1 (Ar), 130.1 (Ar), 129.4 (Ar), 128.4
(Ar), 128.2 (Ar), 127.7 (Ar), 127.6 (Ar), 127.5 (Ar), 126.7 (Ar), 76.6
(C-2), 76.2 (C-3), 74.8 (C-4), 71.2 (PhCH2), 69.9 (PhCH2), 55.9 (N-
CH2-Ar), 55.3 (C-5), 43.5 (C-1), 38.1 (C-10), 31.0 (COCH3), 21.0
(OCOCH3). HRESIMS: calcd for C31H34ClNNaO5 [M+Na]+:
558.2018, found: 558.2008.
(8f–b) ½a 2D5
ꢀ
11.5 (c 0.5, CHCl3); 1H NMR (CDCl3): d 8.14 (d, 2H,
J = 8.7 Hz, Ar), 7.43 (d, 2H, J = 8.1 Hz, Ar), 7.37–7.26 (m, 10H, Ph),
4.81 (d, 1H, J = 9.5 Hz, H-4), 4.77 (d, 1H, J = 12.0 Hz, PhCH2), 4.67
(d, 1H, J = 11.9 Hz, PhCH2), 4.63 (d, 1H, J = 11.5 Hz, PhCH2), 4.42
(d, 1H, J = 11.4 Hz, PhCH2), 4.22 (br s, 1H, H-3), 3.86 (d, 1H,
J = 14.8 Hz, N-CH2-Ar), 3.53 (br s, 1H, H-1), 3.46 (d, 1H,
J = 14.8 Hz, N-CH2-Ar), 3.40 (d, 1H, J = 9.1 Hz, H-2), 2.86 (dd, 1H,
J5a,5b = 16.8, J5a,4 = 3.8 Hz, H-5a), 2.77 (dd, 1H, J = 11.2, 10.8 Hz, H-
5b), 2.64–2.59 (m, 2H, H-10), 2.06 (s, 3H, COCH3), 1.95 (s, 3H,
OCOCH3); 13C NMR (CDCl3): d 207.0 (C@O), 170.2 (–O–C@O),
147.2 (Ar), 138.7 (Ar), 137.5 (Ar), 128.8 (Ar), 128.5 (Ar), 128.2
(Ar), 127.9 (Ar), 127.8 (Ar), 127.6 (Ar), 127.5 (Ar), 79.9 (C-2), 74.1
(C-3), 72.8 (C-4), 71.4 (PhCH2), 69.5 (PhCH2), 56.1 (N–CH2–Ph),
55.8 (C-5), 49.1 (C-1), 45.1 (C-10), 30.1 (COCH3), 20.9 (OCOCH3).
HRESIMS: calcd for C31H34N2NaO7 [M+Na]+: 569.2258, found:
569.2256.
(8h–b) ½a 2D5
ꢀ
11.1 (c 0.5, CHCl3); 1H NMR (CDCl3): d 7.35–7.29 (m,
12H, Ar), 7.20 (m, 1H, Ar), 7.15 (m, 1H, Ar), 4.83 (m, 1H, H-4), 4.77
(d, 1H, J = 12.1 Hz, PhCH2), 4.65 (d, 1H, J = 11.5 Hz, PhCH2), 4.63 (d,
1H, J = 11.4 Hz, PhCH2), 4.42 (d, 1H, J = 11.5 Hz, PhCH2), 4.21 (br s,
1H, H-3), 3.84 (d, 1H, J = 14.8 Hz, N-CH2-Ar), 3.55 (m, 1H, H-2),
3.53 (d, 1H, J = 14.5 Hz, N-CH2-Ar), 3.42 (m, 1H, H-1), 2.84 (dd,
1H, J = 10.9, 10.7 Hz, H-10a), 2.77 (dd, 1H, J5b,5a = 16.7,
J4,5a = 4.9 Hz, H-5a), 2.64 (dd, 1H, J5a,5b = 16.6, J4,5b = 5.8 Hz, H-5b),
2.60 (dd, 1H, J1 ,1 = 11.0, J1,1 = 4.5 Hz, H-10b), 2.04 (s, 3H, COCH3),
1.95 (s, 3H, OCOCH3); 13C NMR (CDCl3): d 207.0 (C@O), 170.2 (–
O–C@O), 138.8 (Ar), 137.6 (Ar), 136.4 (Ar), 133.8 (Ar), 130.3 (Ar),
129.4 (Ar), 128.4 (Ar), 128.2 (Ar), 127.8 (Ar), 127.6 (Ar), 127.4
(Ar), 126.7 (Ar), 79.6 (C-2), 74.0 (C-3), 72.9 (C-4), 71.4 (PhCH2),
69.7 (PhCH2), 56.4 (N–CH2–Ph), 53.6 (C-5), 49.2 (C-1), 45.0 (C-10),
30.1(COCH3), 21.0(OCOCH3). HRESIMS: calcd for C31H34ClNNaO5
[M+Na]+: 558.2018, found: 558.2010.
0
0
0
3.4.7. 1-C-(4-O-Acetyl-2,3-di-O-benzyl-5-p-chlorobenzylamino-
5-deoxy-D-ribopyranosyl)propan-2-one (8g)
Yield: 58% (over three steps).
(8g–a
) ½a 2D5
ꢀ
60.3 (c 0.4, CHCl3); 1H NMR (CDCl3): d 7.36–7.26 (m,
12H, Ar), 7.18 (d, 2H, J = 7.8 Hz, Ar), 4.78 (d, 1H, J = 11.8 Hz, PhCH2),
4.73 (m, 1H, H-4), 4.68 (d, 1H, J = 12.0 Hz, PhCH2), 4.55 (d, 1H,
J = 11.8 Hz, PhCH2), 4.47 (d, 1H, J = 11.8 Hz, PhCH2), 4.15 (br s, 1H,
H-3), 3.92 (m, 1H, H-1), 3.74 (d, 1H, J = 13.9 Hz, N-CH2-Ar), 3.67
(d, 1H, J = 2.2 Hz, H-2), 3.41 (d, 1H, J = 13.6 Hz, N-CH2-Ar), 3.22
(dd, 1H, J5a,5b = 16.8, J5a,4 = 4.8 Hz, H-5a), 2.74–2.69 (m, 2H, H-10),
2.42 (dd, 1H, J5a,5b = 10.8, J4,5b = 4.2 Hz, H-5b), 2.09 (s, 3H, COCH3),
1.95 (s, 3H, OCOCH3); 13C NMR (CDCl3): d 209.0 (C@O), 170.1 (–O–
C@O), 138.9 (Ar), 138.0 (Ar), 137.3 (Ar), 132.8 (Ar), 129.7 (Ar),
128.4 (Ar), 128.2 (Ar), 127.7 (Ar), 127.5 (Ar), 127.4 (Ar), 76.6 (C-
2), 76.2 (C-3), 74.8 (C-4), 71.2 (PhCH2), 69.9 (PhCH2), 57.8 (N-
CH2-Ar), 55.7 (C-5), 43.1 (C-1), 38.0 (C-10), 30.9 (COCH3), 21.0
(OCOCH3). HRESIMS: calcd for C31H35ClNO5 [M+H]+: 536.2198,
found: 536.2186.
3.4.9. 1-C-[4-O-Acetyl-2,3-di-O-benzyl-5-deoxy-5-(thiophen-2-
ylmethyl)amino-D-ribopyranosyl]propan-2-one (8i)
Yield: 51% (over three steps).
(8i–a
) ½a 2D5
ꢀ
66.1 (c 0.6, CHCl3); 1H NMR (CDCl3): d 7.36–7.27 (m,
10H, Ar), 7.20 (d, 1H, J = 4.7 Hz, thiophen), 6.91 (s, 1H, thiophen),
6.84 (s, 1H, thiophen), 4.79–4.76 (m, 2H, PhCH2, H-4), 4.67 (d,
1H, J = 11.7 Hz, PhCH2), 4.56 (d, 1H, J = 11.8 Hz, PhCH2), 4.48 (d,
1H, J = 11.7 Hz, PhCH2), 4.14 (br s, 1H, H-3), 3.97 (m, 1H, H-1),
3.94 (d, 1H, J = 14.3 Hz, N-CH2-thiophen), 3.71 (d, 2H, H-2, N-CH2-
thiophen), 3.22 (dd, 1H, J5b,5a = 16.6, J4,5a = 4.9 Hz, H-5a), 2.76 (dd,
1H, J = 10.9, 10.8 Hz, H-10a), 2.67 (dd, 1H, J5a,5b = 16.2,
J4,5b = 5.5 Hz, H-5b). 2.60 (d, 1H, J = 6.8 Hz, H-10b), 2.08 (s, 3H,
COCH3), 1.96 (s, 3H, OCOCH3); 13C NMR (CDCl3): d 208.9 (C@O),
170.1 (–O–C@O), 143.3 (thiophen), 138.9 (Ar), 138.1 (Ar), 128.3
(Ar), 127.7 (Ar), 127.6 (Ar), 127.5 (Ar), 126.4 (Ar), 125.2 (Ar),
124.9 (Ar), 76.2 (C-2, C-3), 74.7 (C-4), 71.3 (PhCH2), 69.9 (PhCH2),
55.5 (N-CH2-thiophen), 53.4 (C-5), 43.3 (C-1), 38.0 (C-10), 30.9
(COCH3), 21.0 (OCOCH3). HRESIMS: calcd for C29H33NNaO5S
[M+Na]+: 530.1972, found: 530.1950.
(8g–b) ½a 2D5
ꢀ
11.4 (c 0.4, CHCl3); 1H NMR (CDCl3): d 7.36–7.24 (m,
12H, Ar), 7.18 (d, 2H, J = 7.2 Hz, Ar), 4.79–4.75 (m, 2H, H-4, PhCH2),
4.65 (d, 1H, J = 11.6 Hz, PhCH2), 4.63 (d, 1H, J = 11.2 Hz, PhCH2),
4.41 (d, 1H, J = 11.5 Hz, PhCH2), 4.20 (br s, 1H, H-3), 3.74 (d, 1H,
J = 13.7 Hz, N-CH2-Ar), 3.48 (m, 1H, H-1), 3.38 (d, 1H, J = 7.7 Hz,
H-2), 3.30 (d, 1H, J = 13.7 Hz, N-CH2-Ar), 2.83 (dd, 1H, J5a,5b = 16.6,
J4,5a = 1.1 Hz, H-5a), 2.70 (dd, 1H, J = 11.2, 11.1 Hz, H-10a), 2.59–
2.52 (m, 2H, H-10b, H-5b), 2.06 (s, 3H, COCH3), 1.94 (s, 3H,
OCOCH3); 13C NMR (CDCl3): d 207.1 (C@O), 170.2 (–O–C@O),
138.8 (Ar), 137.5 (Ar), 132.7 (Ar), 129.7 (Ar), 128.5 (Ar), 128.2
(Ar), 127.9 (Ar), 127.8 (Ar), 127.6 (Ar), 127.5 (Ar), 79.3 (C-2), 74.0
(C-3), 72.8 (C-4), 71.3 (PhCH2), 69.7 (PhCH2), 56.1 (N-CH2-Ar),
(8i–b) ½a 2D5
ꢀ
11.5 (c 0.2, CHCl3); 1H NMR (CDCl3): d 7.38–7.27 (m,
10H, Ar), 7.20 (d, 1H, J = 9.5 Hz, thiophen), 6.90 (m, 1H, thiophen),
6.84 (s, 1H, thiophen), 4.80 (d, 1H, J = 8.6 Hz, H-4), 4.75 (d, 1H,
J = 12.0 Hz, PhCH2), 4.66–4.60 (m, 2H, PhCH2), 4.41 (d, 1H,
J = 11.5 Hz, PhCH2), 4.21 (br s, 1H, H-3), 3.92 (d, 1H, J = 14.4 Hz,
N-CH2-thiophen), 3.69 (d, 1H, J = 14.6 Hz, N-CH2-thiophen), 3.47