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3.2.2. 1-Deoxy-1,1-bis(30-indolyl)-D-glucitol (5). By the
foregoing procedure, indole was reacted with D-glucose
to give 5 as a colorless powder: mp 108–110 ꢀC. Rf 0.12
moiety): 3.26 (1H, dd, J 10.5 and 6.5 Hz, H-3a), 3.35
(1H, dd, J 10.5 and 4.5 Hz, H-3b), 4.28 (1H, dd, J 6.0
and 4.5 Hz, H-2); 13C NMR (CDCl3): d (indolyl moi-
ety): 136.3, 136.1 (C-70a), 128.1, 127.1 (C-30a), 123.5,
123.1 (C-20), 120.7, 120.5 (C-50), 119.4, 119.1 (C-40*),
118.1, 117.9 (C-60*), 117.5, 115.4 (C-70), 111.4, 111.2
(C-30); (propanediol moiety): 74.4 (C-2), 64.9 (C-3),
20
(5:1 CHCl3–MeOH); ½aꢀD +53.3 (c1.035, MeOH); IR
(KBr) m 3400, 3059, 2924, 1456, 1419, 1338, 1246, 1219,
1
1093, 1039, 1012, 744 cmꢁ1; H NMR (DMSO-d6): d
(indolyl moiety): 6.86–7.58 (8H, m, ArH), 7.16 (1H, d,
J 2.1 Hz, H-20), 7.37 (1H, d, J 1.7 Hz, H-200), 10.68
(1H, d, J 2.1 Hz, NH), 10.69 (1H, d, J 1.7 Hz, NH); (glu-
cose moiety): 3.30 (1H, dd, J 6.0 and 10.8 Hz, H-6a), 3.45
(1H, m, H-5), 3.50 (2H, m, H-4 and -6b), 3.62 (1H, dd, J
4.2 and 6.8 Hz, H-3), 4.46 (1H, dd, J 4.2 and 7.3 Hz, H-
2), 4.71 (1H, d, J 7.3 Hz, H-1), 4.39, 4.05, and 4.60 (each
1H, s, OH · 3), 4.29 (2H, s, OH · 2); 13C NMR (DMSO-
d6): d 136.3, 136.2 (C-70a), 127.9, 127.1 (C-30a), 123.5,
123.1 (C-20), 120.7, 120.4 (C-50), 119.6, 119.3 (C-40),
118.1, 117.9 (C-60), 117.4, 115.9 (C-70), 111.3, 111.2 (C-
30); (glucose moiety): 75.4, 73.8, 71.7, 69.4, 63.6 (C-6),
36.2 (C-1); FABMS (m/z) 397 (M+H)+. Anal. Calcd
for C22H24N2O5Æ 0.2H2O: C, 66.05; H, 6.15; N, 7.00.
Found: C, 66.04; H, 6.18; N, 6.92.
36.1 (C-1), : may be interchangeable; FABMS (m/z)
*
307 (M+H)+.
3.3. Methyl 2,2-bis(30-indolyl)ethanoate (2b)1d
To a solution of 2a (100 mg, 0.34 mmol) in EtOAc, a
solution of diazomethane in Et2O was added dropwise
until 2a disappeared on silica gel TLC (1:1 n-hexane–
EtOAc). The reaction mixture was evaporated in vacuo
to give 2b (105 mg, 100%) as a white powder: mp 75–
78 ꢀC (lit.8 45–50 ꢀC). IR (KBr) m 3410, 3128, 3055,
2950, 1728, 1618, 1458, 1431, 1338, 1199, 1170, 1095,
742 cmꢁ1 1H NMR (CDCl3): d 3.74 (3H, s, OMe),
;
5.51 (1H, s, >CH–), 7.03–7.64 (10H, m, ArH), 8.00
(2H, br s, NH · 2); 13C NMR (CDCl3): d 174.1
(C@O), 136.3 (·2), 126.5 (·2), 123.4 (·2), 122.1 (·2),
119.6 (·2), 119.1 (·2), 113.3 (·2), 111.7 (·2), 52.3
(OCH3), 40.4 (>CH–); FABMS (m/z) 305 (M+H)+.
3.2.3. 1,1-Bis(30-indolyl)phenylmethane (1). By the
general procedure in Section 3.2.1, benzaldehyde was
reacted with indole to give 1 as colorless prisms (from
Et2O): mp 151–153 ꢀC (lit.: 150–152 ꢀC,7 88–90 ꢀC.1h)
IR (KBr) m 3398, 3051, 3022, 2923, 2854, 1612, 1599,
3.4. 2,2-Bis(30-indolyl)ethanol (2c)1d
1493, 1456, 1419, 1336, 1091, 1008, 746 cmꢁ1 1H
;
NMR (DMSO-d6): d 5.87 (1H, s, >CH–), 6.60 (1H, d,
J 1.2 Hz, H-2), 6.61 (1H, d, J 0.8 Hz, H-20), 6.87–7.41
(13H, m, ArH), 7.82 (2H, br s, NH · 2); 13C NMR
(CDCl3): d 144.0, 136.5, 128.6, 128.2, 127.0, 126.1,
121.8, 119.8, 119.5, 119.1, 111.0, 40.9 (>CH–); FABMS
(m/z) 323 (M+H)+.
LiAlH4 (134 mg, 3.54 mmol) was added in portions to a
cooled solution of 2b (430 mg, 1.41 mmol) in dry ether
(4 mL) under stirring. The reaction mixture was stirred
for 1 day at room temperature. Satd aq Na2SO4 was
added to the reaction mixture, and the resulting solution
was extracted with AcOEt (3·). The combined organic
layer was washed with brine and dried over anhydrous
Na2SO4, and then evaporated in vacuo. The residue
was purified by flash-column chromatography on silica
gel (1:1 n-hexane–AcOEt) to give 2c (264 mg, 68%) as
a white powder: mp 68–70 ꢀC [lit.1d 50 ꢀC (60–80 ꢀC,
petroleum ether–toluene)]. IR (KBr) m 3537, 3400,
3055, 2929, 2877, 1689, 1618, 1456, 1419, 1338, 1217,
3.2.4. 2,2-Bis(30-indolyl)ethanoic acid (2a).1c,d By the
general procedure in Section 3.2.1, glyoxylic acid methyl
ester was reacted with indole to give 2a as reddish yellow
prisms (from AcOEt): mp 174–175 ꢀC. IR (KBr) m 3408,
3057 2924, 2854, 1705, 1618, 1458, 1338, 1010,
1
744 cmꢁ1; H NMR (DMSO-d6): d 5.34 (1H, s, >CH–),
6.90–7.70 (10H, m, ArH), 10.91 (2H, s, NH · 2), 12.31
(1H, br s, C–OOH); 13C NMR (DMSO-d6) d 174.5
(C@O), 136.5 (·2), 126.7 (·2), 123.8 (·2), 12.1 (·2),
119.2 (·2), 118.6 (·2), 113.0 (·2), 111.7 (·2), 40.5
(>CH–); FABMS (m/z) 291 (M+H)+.
1095, 1010, 742 cmꢁ1 1H NMR (DMSO-d6): d 4.06
;
(2H, d, J 6.8 Hz, CH2), 4.53 (1H, t, J 6.8 Hz, >CH–),
4.62 (1H, br s, OH), 6.87 (2H, dt, J 6.7 and 1.1 Hz,
ArH), 7.00 (2H, dt, J 7.8 and 1.1 Hz, ArH), 7.18 (1H,
d, J 2.2 Hz, ArH), 7.30 (2H, d, J 7.1 Hz, ArH), 7.47
(2H, d, J 7.7 Hz, ArH), 10.76 (2H, s, NH · 2); 13C
NMR (DMSO-d6): d 136.5 (C-70a), 127.2 (C-30a),
122.7 (C-20), 120.7 (C-50), 119.2 (C-40), 118.1 (C-60),
116.6 (C-70), 111.4 (C-30), 65.3 (CH2OH), 37.2 (C-2);
FABMS (m/z) 277 (M+H)+.
3.2.5. 3,3-Bis(30-indolyl)propane-1,2-diol (3). By the
general procedure in Section 3.2.1, indole was reacted
with D,L-glyceraldehyde to give 3 as a white powder:
mp 92–96 ꢀC (lit.9 90–91 ꢀC). IR (KBr) m 3529, 3398,
3051, 2923, 2871, 1456, 1419, 1338, 1246, 1219, 1095,
1
1010, 744 cmꢁ1. H NMR (DMSO-d6): d (indolyl moi-
3.5. 2,2-Bis(30-indolyl)ethyl acetate (2d, streptindole)1d,g,5
ety): 6.84–7.54 (8H, m, ArH), 7.23 (1H, d, J 1.5 Hz,
H-20), 7.32 (1H, d, J 2.0 Hz, H-200), 10.72 (1H, d, J
1.5 Hz, NH), 10.74 (1H, d, J 2.0 Hz, NH); (propanediol
Product 2c was acetylated to give 2d as a white powder:
mp 56–58 ꢀC. 1H NMR (CDCl3): d (2-acetoxyethyl moi-