C. Ferna´ndez et al. / Carbohydrate Research 327 (2000) 353–365
361
filtered, and concentrated to give a residue,
which was purified by flash chromatography
(2:11:1 hexane–EtOAc), affording com-
pound 16 as a solid (2.11 g, 70%); mp 125–
7.04–7.38 (m, 30 H, aromatics), 6.81 (d, 1 H,
J 8.2 Hz, H-5 Ar), 6.76 (d, 1 H, J 2.1 Hz,
H-2 Ar), 6.61 (dd, 1 H, J 2.1 Hz and 8.2 Hz,
H-6 Ar), 5.53 (d, 1 H, J 7.9 Hz, H-1), 5.38
(m, 1 H, NH), 5.07 and 5.06 (2s, 4 H, 2
CH2ꢀPh), 4.83–4.36 (m, 8 H, 4 CH2ꢀPh),
3.69–3.45 (m, 6 H, H-2,-3,-4,-6,-6%), 3.34 (m,
2 H, CH2NH), 2.62–2.55 (m, 4 H, CH2 succ.
and CH2ꢀAr), 2.24 (m, 2 H, CH2 succ.); 13C
NMR (50 MHz, CDCl3): l 171.4 (COO),
170.7 (CONH), 147.8 and 149.1 (C-3 and
C-4 Ar), 137.3–138.4 (C ipso Bn), 132.3 (C-1
Ar), 121.6 (C-6 Ar), 115.6, 115.9 (C-5, C-2
Ar), 94.3 (C-1), 84.8, 80.9, 77.2, 75.6 (C-2,-
3,-4,-5), 75.6–71.3 (CH2Ph); 68.1 (C-6), 40.7
(CH2NH), 35.1 (CH2Ar), 30.8 and 29.7 (2
CH2 succ.); Anal. Calcd for C60H58NO10: C,
75.61; H, 6.13; N, 1.47. Found: C, 75.31; H,
6.09; N, 1.52.
127 °C;
Rf
0.35
(2:1:0.15
hexane–
EtOAc–AcOH); 1H NMR (200 MHz,
CHCl3): l 6.67 (d, 1 H, J 8.1 Hz, H-5 Ar),
6.65 (d, 1 H, J 3.0 Hz, H-2 Ar), 6.53 (m, 1
H, H-6 Ar), 5.06 (s, 2 H, CH2Ph), 3.27 (t, 2
H, J 7.5 Hz, CH2NH), 2.62 (t, 2 H, J 7.7
Hz, CH2Ar); 13C NMR (50 MHz, CD3OD):
159.1 (CO), 146.5 (C-3 Ar), 145.0 (C-4 Ar),
138.7 (C ipso), 132.3 (C-1 Ar), 129.7–129.0
(4 C, aromatics), 121.4 (C-6 Ar), 117.2 and
116.6 (C-2 and C-5 Ar), 67.5 (CH2ꢀPh), 44.0
(CH2ꢀNH), 36.8 (CH2ꢀAr); Anal. Calcd for
C16H17NO3: C, 70.83; H, 6.32; N, 5.16.
Found: C, 70.71; H, 6.39; N, 5.02.
N-Benzyloxycarbonyl-3,4-dihydroxy-3-O-(2,
3,4,6 - tetra - O - acetyl - i -
D
- glucopyranosyl)-
1 - O - [N - (3,4 - Dihydroxyphenylethyl) - succ-
phenylethylamine (18) and N-benzyloxycar-
inamyl]-i- -glucopyranose (3).—A solution
D
bonyl - 3,4 - dihydroxy - 4 - O - (2,3,4,6 - tetra - O-
of 15 (146 mg, 0.153 mmol) was hy-
drogenolyzed in 3:2 MeOH–EtOAc, in the
presence of Pd/C (175 mg). After 3 h, work-
up was carried out as described for 1, giving
3 as a solid (63 mg, 99%); Rf 0.32 (4:1:1
EtOAc–AcOH–water); [h]2D0 −4° (c 1,
acetyl - i -
(19).—To a solution of 16 (1.5 g, 5.22
mmol) and b- -glucose pentaacetate (17, 3.06
D
- glucopyranosyl)phenylethylamine
D
g, 7.83 mmol) in dry CH2Cl2 (53 mL) was
added BF3·OEt2 dropwise (3.2 mL, 26.10
mmol), stirring under argon for 4 h. Then,
the mixture was diluted with CH2Cl2 and
washed with satd NaHCO3, water and dried
(NaSO4). Evaporation of the solvent, fol-
lowed by purification by silica gel chro-
1
MeOH); H NMR (300 MHz, CD3OD): l
6.87 (d, 1 H, J 8.1 Hz, H-5 Ar), 6.83 (d, 1
H, J 2.0 Hz, H-2 Ar), 6.72 (dd, J 8.1 and 2.0
Hz, H-6 Ar), 5.67 (d, 1 H, J 8.1 Hz, H-1),
2.68 (t, 2 H, J 6.7 Hz, CH2CON); 13C NMR
(50 MHz, CD3OD): l 174.0 and 173.1 (2
CO), 146.2 and 144.7 (C-3 and C-4 Ar),
132.0 (C-1 Ar), 121.3 (C-6 Ar), 116.8 and
116.3 (C-2 and C-5 Ar), 95.8 (C-1), 78.8–
71.0 (4 C, C-2,-3,-4,-5), 62.3 (C-6), 42.4
(CH2NH), 35.9 (CH2ꢀAr), 31.2 and 30.4 (2
CH2 succ.); Anal. Calcd for C18H25NO10: C,
52.04; H, 6.07; N, 3.37. Found: C, 52.27; H,
5.93; N, 3.15.
N-Benzyloxycarbonyl-3,4-dihydroxyphenyl-
ethylamine (16).—To a solution of dopamine
hydrochloride (2 g, 10.5 mmol) in MeOH (33
mL) and Et3N (4.4 mL, 31.6 mmol), was
added benzylchloroformate dropwise (1.9
mL) at 0 °C. Then, the stirred solution was
allowed to attain rt and the stirring was con-
tinued for 2 h. The reaction mixture was
neutralised with amberlite IR 150 (H+)
matography
(2:11:1
hexane–EtOAc)
afforded compounds 18 (0.58 g, 18%) and 19
(1.74 g, 54%) as solids; 18: mp 42–45 °C; Rf
0.40, (1:1 hexane–EtOAc); [h]2D0 −13.2° (c 1,
1
CHCl3), H NMR (400 MHz, CDCl3): l 7.32
(m, 5 H, aromatics), 6.85 (m, 2 H, H-5 and
H-6 Ar), 6.80 (s, 1 H, H-2 Ar), 5.94 (s, 1 H,
OH), 4.93 (d, 1 H, J 7.3 Hz, H-1), 4.81 (s, 1
H, NH), 4.26 (dd, 1 H, J5,6 5.1 Hz, J6,6% 12.4
Hz, H-6), 4.18 (dd, 1 H, J5,6% 2.4 Hz, J6,6%
12.4 Hz, H-6%), 3.82 (m, 1 H, H-5), 3.41 (m,
2 H, CH2ꢀNH), 2.72 (t, 2 H, J 6.59 Hz,
CH2ꢀAr), 2.05 (m, 12 H, 4 CH3, Ac); 13C
NMR (50 MHz, CDCl3). l 177.1 (CO),
170.6–169.3 (4 C, CO, Ac), 156.2 (C-3 Ar),
145.9 (C-4 Ar), 144.0 (C ipso Bn), 136.4 (C-1
Ar), 130.7–128.5 (5 C, aromatics), 125.4 (C-6
Ar), 118.0 (C-2 Ar), 116.3 (C-5 Ar), 101.4