108
F. Saab et al. / Tetrahedron 66 (2010) 102–110
(CHAr), 115.0 (CHAr), 119.3 (C-6), 120.7 (C-7), 120.8 (CHAr), 122.9
(CHAr), 124.9 (CHAr), 126.7 (2ꢂCHAr), 127.1 (Cq), 128.8 (Cq), 129.5
(2ꢂCHAr), 130.1 (C-2), 134.2 (CHAr), 137.7 (Cq), 137.8 (Cq), 139.0 (Cq),
148.1 (Cq),149.9 (Cq),150.1 (Cq); HRMS (TOF ESþ) m/z calculated for
C26H24N3O4S (MHþ) 474.1488; found 474.1473.
chromatography (petroleum ether/EtOAc 8/2) to afford 25 as brown
oil (20 mg, 23%). Rf (petroleum ether/EtOAc 7/3) 0.43; IR (ATR di-
amond,
(250 MHz, CDCl3)
n
, cmꢀ1) 2924, 2856, 1593, 1370, 1168, 1131, 723; 1H NMR
d
0.87 (t, 3H, CH3, J¼7.2 Hz), 1.26–1.38 (m, 12H,
6ꢂCH2), 1.60 (quint, 2H, CH2, J¼7.2 Hz), 3.28 (q, 2H, CH2, J¼7.2 Hz),
4.44 (t, 1H, NH, J¼7.2 Hz), 6.36 (d, 1H, H-6, J6,7¼9.0 Hz), 6.58 (d, 1H,
4.3.14. (1-Benzenesulfonyl-1H-pyrrolo[3,2–b]pyridin-5-yl)-(4-me-
thoxy-phenyl)-amine (22). The reaction was carried out as de-
scribed in general procedure D using the 4-methoxy-phenylamine
(36 mg, 0.295 mmol). The mixture was refluxed for 1 h. The residue
was purified by flash chromatography (petroleum ether/EtOAc 5/5)
to afford 22 as brown oil (91.4 mg, 98%). Rf (petroleum ether/EtOAc
H-3, J3,2¼3.6 Hz), 7.43 (dd, 2H, 2ꢂHAr, J¼J0¼7.5 Hz), 7.53 (dd,1H, HAr
,
,
J¼J0¼7.5 Hz), 7.56 (d, 1H, H-2, J2,3¼3.6 Hz), 7.80 (d, 2H, 2ꢂHAr
J¼7.5 Hz), 8.01 (d, 1H, H-7, J7,6¼9.0 Hz); 13C NMR (100.61 MHz,
CDCl3)
d 14.1 (CH3), 22.6 (CH2), 27.0 (CH2), 29.2 (CH2), 29.4 (CH2),
29.5 (CH2), 29.6 (CH2), 31.8 (CH2), 42.5 (CH2), 104.7 (C-6), 110.0 (C-
3), 122.2 (Cq), 123.3 (C-7), 126.6 (2ꢂCHAr), 128.3 (C-2), 129.2
(2ꢂCHAr), 133.8 (CHAr), 138.1 (Cq), 147.5 (Cq), 157.0 (Cq); HRMS (TOF
ESþ) m/z calculated for C22H30N3O2S (MHþ) 400.2059; found
400.2073.
5/5) 0.45; IR (ATR diamond,
1591, 1509, 1409, 1168, 1120, 723; 1H NMR (250 MHz, CDCl3)
(s, 3H, CH3), 6.57 (d, 1H, H-3, J3,2¼4.0 Hz), 6.62 (d, 1H, H-6,
n
, cmꢀ1) 3179, 3105, 3007, 2933, 2835,
3.78
d
J6,7¼9.0 Hz), 6.87 (d, 2H, 2ꢂHAr, J¼8.8 Hz), 7.26 (d, 2H, 2ꢂHAr
,
J¼8.8 Hz), 7.41 (dd, 2H, 2ꢂHAr, J¼J0¼7.5 Hz), 7.52 (dd, 1H, HAr
,
4.3.18. (1-Benzenesulfonyl-1H-pyrrolo[3,2-b]pyridin-5-yl)-(3-me-
thoxy-benzyl)-amine (26). The reactionwas carried out as described
in general procedure D using the 3-methoxy-benzylamine
J¼J0¼7.5 Hz), 7.59 (d, 1H, H-2, J2,3¼4.0 Hz), 7.80 (d, 2H, 2ꢂHAr
,
J¼7.5 Hz), 8.02 (d, 1H, H-7, J7,6¼9.0 Hz); 13C NMR (100.61 MHz,
CDCl3)
d
55.4 (CH3), 105.3 (C-6), 109.9 (C-3), 114.5 (2ꢂCHAr), 122.9
(0.040 mL, 0.295 mmol). The mixture was refluxed for 7 h. The res-
idue was purified by flash chromatography (petroleum ether/EtOAc
7/3) to afford 26 as brown oil (24 mg, 25%). Rf (petroleum ether/
(Cq), 123.2 (C-7), 123.7 (2ꢂCHAr), 126.6 (2ꢂCHAr), 128.6 (C-2), 129.2
(2ꢂCHAr), 133.5 (Cq), 133.9 (CHAr), 137.9 (Cq), 147.3 (Cq), 155.1 (Cq),
156.1 (Cq); HRMS (TOF ESþ) m/z calculated for C20H18N3O3S
380.1069 (MHþ); found 380.1077.
EtOAc 6/4) 0.39; IR (ATR diamond,
n
, cmꢀ1) 3428, 2954, 1588, 1367,
3.84 (s, 3H, CH3), 4.52 (d,
1167,1130, 723; 1H NMR (250 MHz, CDCl3)
d
2H, CH2, J¼6.0 Hz), 4.97 (t, 1H, NH, J¼6.0 Hz), 6.38 (d, 1H, H-6,
J6,7¼9.0 Hz), 6.60 (d,1H, H-3, J3,2¼3.6 Hz), 6.86–6.90 (m, 2H, 2ꢂHAr),
7.23 (dd, 1H, HAr, J¼9.0 Hz, J0¼1.6 Hz), 7.31 (dd, 1H, HAr, J¼9.0 Hz,
4.3.15. (1-Benzenesulfonyl-1H-pyrrolo[3,2–b]pyridin-5-yl)-(2-
methyl-quinolin-4-yl)-amine (23). The reaction was carried out as
described in general procedure D using the 2-methyl-quinolin-4-
ylamine (47 mg, 0.295 mmol). The mixture was refluxed for 3 h.
The residue was purified by flash chromatography (CH2Cl2/MeOH
95/5) to afford 23 as a light brown solid (93 mg, 91%). Mp 123 ꢁC; Rf
J0¼1.6 Hz), 7.42 (dd, 2H, 2ꢂHAr
,
J¼J0¼7.5 Hz), 7.53 (dd, 1H,
HAr, J¼J0¼7.5 Hz), 7.56 (d, 1H, H-2, J2,3¼3.6 Hz), 7.80 (d, 2H, 2ꢂHAr
,
J¼7.5 Hz), 7.98 (d, 1H, H-7, J7,6¼9.0 Hz); 13C NMR (100.61 MHz,
CDCl3) d 42.0 (CH3), 55.3 (CH2), 105.1 (C-6), 110.0 (CHAr), 110.2 (C-3),
(CH2Cl2/MeOH 9/1) 0.39; IR (ATR diamond,
n
, cmꢀ1) 3166, 1569,
2.65 (s, 3H,
120.5 (CHAr),122.3 (Cq),123.2 (C-7),126.6 (2ꢂCHAr),127.1 (Cq),128.2
(C-2), 128.5 (CHAr), 129.1 (CHAr), 129.2 (2ꢂCHAr), 133.8 (CHAr), 138.1
(Cq), 147.4 (Cq), 156.9 (Cq), 157.5 (Cq); HRMS (TOF ESþ) m/z calcu-
lated for C21H20N3O3S (MHþ) 394.1219; found 394.1225.
1365, 1165, 1136, 754, 722; 1H NMR (250 MHz, CDCl3)
d
CH3), 6.75 (d, 1H, H-3, J3,2¼4.0 Hz), 7.12 (d, 1H, H-6, J6,7¼9.0 Hz),
7.38 (dd, 1H, HAr, J¼J0¼8.0 Hz), 7.46 (dd, 2H, 2ꢂHAr, J¼J0¼7.5 Hz),
7.57 (dd, 1H, HAr, J¼J0¼7.5 Hz), 7.61 (dd, 1H, HAr, J¼J0¼8.0 Hz), 7.74
(d, 1H, H-2, J2,3¼4.0 Hz), 7.83 (s, 1H, HAr), 7.87 (d, 2H, 2ꢂHAr
,
4.3.19. N-(1-Benzenesulfonyl-1H-pyrrolo[3,2-b]pyridin-5-yl)-benza-
mide (27). The reaction was carried out as described in general
procedureDusing thebenzamide(36 mg, 0.295 mmol). Themixture
was refluxed for 3 h. The residue was purified by flash chromato-
graphy (petroleum ether/EtOAc 6/4) to afford 27 as a light brown
solid (87 mg, 94%). Mp 134 ꢁC; Rf (petroleum ether/EtOAc 6/4) 0.39;
J¼7.5 Hz), 7.94 (d, 1H, HAr, J¼8.0 Hz), 7.97 (d, 1H, HAr, J¼8.0 Hz), 8.22
(d, 1H, H-7, J7,6¼9.0 Hz); 13C NMR (100.61 MHz, CDCl3)
d 25.7 (CH3),
106.2 (CHAr), 109.4 (C-6), 109.9 (C-3), 118.9 (Cq), 119.8 (CHAr), 123.3
(C-7), 124.4 (Cq), 125.0 (CHAr), 126.7 (2ꢂCHAr), 129.1 (C-2), 129.4
(CHAr), 129.5 (3ꢂCHAr), 134.2 (CHAr), 137.9 (Cq), 144.4 (Cq), 147.3
(Cq), 148.5 (Cq), 151.6 (Cq), 159.6 (Cq); HRMS (TOF ESþ) m/z calcu-
lated for C23H19N4O2S (MHþ) 415.1229; found 415.1223.
IR (ATR diamond,
n
, cmꢀ1) 3134, 3105, 1661, 1533, 1406, 1349, 1287,
6.61 (d, 1H, H-3,
1168, 1131, 723, 686; 1H NMR (250 MHz, CDCl3)
d
J3,2¼3.6 Hz), 7.42–7.59 (m, 6H, 6ꢂHAr), 7.74 (d, 1H, H-2, J2,3¼3.6 Hz),
7.86–7.92 (m, 4H, 4ꢂHAr), 8.33 (d, 1H, H-7, J7,6¼9.0 Hz), 8.44 (d, 1H,
H-6, J6,7¼9.0 Hz), 8.92 (d, 1H, NH, J¼7.2 Hz); 13C NMR (100.61 MHz,
4.3.16. 1-Benzenesulfonyl-5-morpholin-4-yl-1H-pyrrolo [3,2–b]pyri-
dine (24). The reaction was carried out as described in general
procedure D using the morpholine (0.026 mL, 0.295 mmol). The
mixture was refluxed for 2.5 h. The residue was purified by flash
chromatography (petroleum ether/EtOAc 6/4) to afford 24 as a light
brown solid (68 mg, 80%). Mp 130 ꢁC; Rf (petroleum ether/EtOAc 5/
CDCl3)
d 109.2 (C-3), 110.7 (C-6), 123.2 (C-7), 125.9 (Cq), 126.7
(2ꢂCHAr), 127.2 (2ꢂCHAr), 128.7 (2ꢂCHAr), 129.4 (2ꢂCHAr), 129.9 (C-
2), 132.2 (CHAr), 134.2 (CHAr), 134.2 (Cq), 137.7 (Cq), 146.6 (Cq), 148.9
(Cq), 165.7 (Cq); HRMS (TOF ESþ) m/z calculated for C20H16N3O3S
(MHþ) 378.0912; found 378.0912.
5) 0.43; IR (ATR diamond,
n
, cmꢀ1) 3093, 2856,1574,1362,1247,1168,
3.50 (t, 4H, 2ꢂCH2, J¼4.8 Hz), 3.82
724; 1H NMR (250 MHz, CDCl3)
d
(t, 4H, 2ꢂCH2, J¼4.8 Hz), 6.64 (d,1H, H-3, J3,2¼3.6 Hz), 6.66 (d,1H, H-
4.3.20. N-(1-Benzenesulfonyl-1H-pyrrolo[3,2–b]pyridin-5-yl)-acet-
amide (28). The reaction was carried out as described in general
procedure D using the acetamide (14 mg, 0.295 mmol). The mixture
was refluxed for 1.5 h. The residue was purified by flash chroma-
tography (petroleum ether/EtOAc 4/6) to afford 28 as a colorless oil
6, J6,7¼9.0 Hz), 7.43 (dd, 2H, 2ꢂHAr, J¼J0¼7.6 Hz), 7.53 (dd, 1H, HAr
,
J¼J0¼7.6 Hz), 7.62 (d, 1H, H-2, J2,3¼3.6 Hz), 7.81 (d, 2H, 2ꢂHAr
,
J¼J0¼7.6 Hz), 8.10 (d, 1H, H-7, J7,6¼9.0 Hz); 13C NMR (100.61 MHz,
CDCl3)
d
46.3 (2ꢂCH2), 66.8 (2ꢂCH2), 104.6 (C-6), 110.2 (C-3), 122.7
(Cq), 123.1 (C-7), 126.6 (2ꢂCHAr), 128.8 (C-2), 129.3 (2ꢂCHAr), 133.9
(CHAr), 138.0 (Cq), 147.4 (Cq), 157.8 (Cq); HRMS (TOF ESþ) m/z cal-
culated for C17H18N3O3S (MHþ) 344.1057; found 344.1069.
(78 mg, 99%); Rf (CH2Cl2/MeOH 98/2) 0.3; IR (ATR diamond,
n )
, cmꢀ1
3412, 3277, 3097, 1674, 1532, 1405, 1376, 1129, 726; 1H NMR
(250 MHz, CDCl3)
d
2.14 (s, 3H, CH3), 6.63 (d, 1H, H-3, J3,2¼3.8 Hz),
7.43 (dd, 2H, 2ꢂHAr, J¼J0¼7.5 Hz), 7.54 (dd,1H, HAr, J¼J0¼7.5 Hz), 7.74
(d, 1H, H-2, J2,3¼3.8 Hz), 7.84 (d, 2H, 2ꢂHAr, J¼J0¼7.5 Hz), 8.22–8.28
(m, 2H, H-6, H-7), 8.77 (bs, 1H, NH); 13C NMR (100.61 MHz, CDCl3)
4.3.17. (1-Benzenesulfonyl-1H-pyrrolo[3,2–b]pyridin-5-yl)-nonyl-
amine (25). The reaction was carried out as described in general
procedure D using the nonylamine (0.054 mL, 0.295 mmol). The
mixture was refluxed for 7 h. The residue was purified by flash
d
24.6 (CH3), 108.8 (C-6), 110.6 (C-3), 123.6 (C-7), 125.7 (Cq), 126.7
(2ꢂCHAr), 129.5 (2ꢂCHAr),130.0 (C-2), 134.3 (CHAr), 137.7 (Cq), 145.7