The Journal of Organic Chemistry
Article
(d, J = 8.0 Hz, 1H), 7.34−7.26 (m, 2H), 7.18−7.14 (m, 1H), 6.51 (d, J
= 0.8 Hz, 1H), 6.01 (s, 1H), 3.48 (s, 3H), 2.31 (s, 3H), 2.16 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3): δ 150.1, 142.7, 135.5, 133.6,
126.1, 122.5, 121.1, 120.1, 109.5, 106.0, 98.4, 29.2, 13.6, 11.4. IR (neat,
cm−1): 3053, 2924, 2349, 1563, 1451, 1393, 1345, 1314, 1119, 1030,
783, 730, 656. HRMS (ESI+, m/z): [M + H]+ calcd for C14H16N3,
226.1344; found, 226.1342.
2-(3,5-Dimethyl-1H-pyrazol-1-yl)-3-methyl-1H-indole (4c2). Fol-
lowing the general procedure, the product was isolated as a white solid
in 159.7 mg (71%) by column chromatography (9:1 hexanes/ethyl
acetate). Mp 173.9−174.9 °C. 1H NMR (400 MHz, CDCl3): δ 8.48 (s,
1H), 7.57 (d, J = 7.6 Hz, 1H), 7.30−7.28 (m, 1H), 7.22−7.20 (m,
1H), 7.16−7.12 (m, 1H), 5.97 (s, 1H), 2.26 (s, 3H) 2.18−2.17 (m,
6H). 13C{1H} NMR (100 MHz, CDCl3): δ 150.3, 142.4, 133.7, 129.3,
127.7, 123.0, 119.7, 119.3, 111.0, 106.1, 105.9, 13.6, 11.2, 8.5. IR (neat,
cm−1): 3057, 2917, 2349, 1629, 1452, 1300, 1131, 1037, 778, 735.
HRMS (ESI+, m/z): [M + H]+ calcd for C14H16N3, 226.1344; found,
226.1354.
131.2, 125.6, 123.4, 121.4, 120.8, 109.8, 97.5, 29.9. HRMS (ESI+, m/
z): [M + H]+ calcd for C11H11N4, 199.0978; found, 199.0986.
3-Methyl-2-(1H-1,2,4-triazol-1-yl)-1H-indole (4f2). Following the
general procedure, the product was isolated as a white solid in 169.9
mg (86%) by column chromatography (1:1 hexanes/ethyl acetate).
1
Mp 125.2−125.5 °C. H NMR (400 MHz, CDCl3): δ 8.96 (s, 1H),
8.52 (s, 1H), 8.14 (s, 1H), 7.59 (d, J = 8.0 Hz, 1H), 7.34 (d, J = 8.0
Hz, 1H), 7.28−7.25 (m, 1H), 7.23−7.16 (m, 1H), 2.39 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3): δ 152.1, 142.8, 133.3, 128.0,
127.5, 123.5, 120.4, 119.3, 111.1, 101.6, 8.5. IR (neat, cm−1): 3117,
2916, 1721, 1509, 1334, 1144, 983, 962, 729, 666. HRMS (ESI+, m/
z): [M + H]+ calcd for C11H11N4, 199.0978; found, 199.0988.
2-(1H-1,2,4-Triazol-1-yl)-1H-indole (4f3).10 Following the general
procedure, the product was isolated as a white solid in 119.8 mg (65%)
by column chromatography (1:1 hexanes/ethyl acetate). 1H NMR
(400 MHz, CDCl3): δ 9.29 (s, 1H), 8.61 (s, 1H) 8.12 (s, 1H), 7.61 (d,
J = 8.0 Hz, 1H), 7.38 (dd, J = 8.0, 0.8 Hz, 1H), 7.26−7.22 (m, 1H),
7.19−7.15 (m, 1H), 6.58 (d, J = 1.6 Hz, 1H). 13C{1H} NMR (100
MHz, CDCl3): δ 152.2, 141.4, 133.6, 131.3, 127.2, 123.1, 121.1, 120.9,
111.3, 90.0. HRMS (ESI+, m/z): [M + H]+ calcd for C10H9N4,
185.0822; found, 185.0824.
2-(1H-Imidazol-1-yl)-1-methyl-1H-indole (4d1).10 Following the
general procedure, the product was isolated as a yellow solid in 179.2
mg (91%) by column chromatography (1:4 hexanes/ethyl acetate). 1H
NMR (400 MHz, CDCl3): δ 7.69 (s, 1H), 7.63 (d, J = 8.0 Hz, 1H),
7.35−7.29 (m, 2H), 7.25−7.24 (m, 1H), 7.21−7.17 (m, 1H), 7.14 (s,
1H), 6.53 (s, 1H), 3.52 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ
138.7, 135.6, 132.1, 130.0, 125.9, 123.0, 121.3, 121.1, 120.8, 109.7,
97.8, 29.2. HRMS (ESI+, m/z): [M + H]+ calcd for C12H12N3,
198.1026; found, 198.1031.
1-(1-Methyl-1H-indol-2-yl)-1H-benzo[d]imidazole (4g). Following
the general procedure, the product was isolated as a white solid in
193.4 mg (78%) by column chromatography (1:2 hexanes/ethyl
acetate). Mp 144.4−145.1 °C. 1H NMR (400 MHz, CDCl3): δ 7.98 (s,
1H), 7.87−7.85 (m, 1H), 7.64 (d, J = 8.0 Hz, 1H), 7.36−7.26 (m,
4H), 7.22−7.16 (m, 2H), 6.60 (s, 1H), 3.43 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3): δ 143.6, 143.2, 135.9, 135.4, 130.3, 126.2, 124.3,
123.2, 123.1, 121.2, 120.7, 120.6, 110.5, 109.8, 99.1, 29.4. IR (neat,
cm−1); 3113, 2923, 1581, 1454, 1399, 1220, 751, 733, 659. HRMS
(ESI+, m/z): [M + H]+ calcd for C16H14N3, 248.1188; found,
248.1180.
2-(1H-Imidazol-1-yl)-3-methyl-1H-indole (4d2).8 Following the
general procedure, the product was isolated as a white solid in 191.3
mg (97%) by column chromatography (1:4 hexanes/ethyl acetate). 1H
NMR (400 MHz, CDCl3): δ 11.14 (s, 1H), 7.69 (s, 1H), 7.62 (d, J =
8.0 Hz, 1H), 7.42 (d, J = 8.0 Hz, 1H), 7.30−7.25 (m, 2H), 7.23−7.19
(m, 1H), 7.15 (s, 1H), 2.29 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3): δ 137.3, 133.7, 128.5, 127.8, 127.7, 122.8, 120.7, 119.8, 119.0,
111.2, 103.3, 7.9. HRMS (ESI+, m/z): [M + H]+ calcd for C12H12N3,
198.1026; found, 198.1040.
1-(1-Methyl-1H-indol-2-yl)-1H-benzo[d][1,2,3]triazole (4h1). Fol-
lowing the general procedure, the product was isolated as a pale-yellow
solid in 227.7 mg (92%) by column chromatography (4:1 hexanes/
1
ethyl acetate). Mp 158.0−158.7 °C. H NMR (400 MHz, CDCl3): δ
1-Methyl-2-(1H-1,2,3-triazol-1-yl)-1H-indole (4e1).10 Following
the general procedure, the product was isolated as a yellow solid in
184.3 mg (93%) by column chromatography (2:1 hexanes/ethyl
7.99 (d, J = 8.0 Hz, 1H), 7.53 (d, J = 8.0 Hz, 1H), 7.40−7.36 (m, 2H),
7.30−7.26 (m, 2H), 7.21−7.17 (m, 1H), 7.07−7.03 (m, 1H), 6.58 (s,
1H), 3.46 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 145.4, 136.0,
134.7, 130.2, 128.9, 126.1, 124.7, 123.4, 121.4, 120.8, 120.2, 110.2,
109.9, 98.2, 29.9. IR (neat, cm−1): 3053, 2930, 1561, 1451, 1318, 1286,
1035, 788, 744, 651. HRMS (ESI+, m/z): [M + Na]+ calcd for
C15H12N4Na, 271.0954; found, 271.0963.
1
acetate). H NMR (400 MHz, CDCl3): δ 7.87 (dd, J = 5.2, 0.8 Hz,
2H), 7.65 (d, J = 8.0 Hz, 1H), 7.39−7.32 (m, 2H), 7.22−7.18 (m,
1H), 6.62 (s, 1H), 3.66 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ
135.9, 133.5, 131.4, 126.5, 125.7, 123.4, 121.3, 120.8, 109.9, 97.3, 30.0.
HRMS (ESI+, m/z): [M + H]+ calcd for C11H11N4, 199.0978; found,
199.0984.
1-(3-Methyl-1H-indol-2-yl)-1H-benzo[d][1,2,3]triazole (4h2). Fol-
lowing the general procedure, the product was isolated as a yellow gel,
235.9 mg (95%) by column chromatography (4:1 hexanes/ethyl
acetate). 1H NMR (400 MHz, CDCl3): δ 8.49 (s, 1H), 8.14 (d, J = 8.0
Hz, 1H), 7.68 (d, J = 8.0 Hz, 1H), 7.58−7.54 (m, 1H), 7.51−7.48 (m,
1H), 7.47−7.42 (m, 2H), 7.34 (td, J = 8.0, 1.2 Hz, 1H), 7.26−7.22 (m,
1H), 2.27 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 145.4, 134.3,
133.9, 128.7, 127.9, 125.8, 124.6, 123.9, 120.4, 120.3, 119.7, 111.3,
110.3, 106.8, 8.60. IR (neat, cm−1): 3209, 2919, 1920, 1722, 1452,
1278, 1048, 1004, 782, 739. HRMS (ESI+, m/z): [M + H]+ calcd for
C15H13N4, 249.1135; found, 249.1149.
3-Methyl-2-(1H-1,2,3-triazol-1-yl)-1H-indole (4e2).8 Following the
general procedure, the product was isolated as a white solid in 170.6
mg (86%) by column chromatography (2:1 hexanes/ethyl acetate). 1H
NMR (400 MHz, CDCl3): δ 9.03 (s, 1H), 8.04 (d, J = 1.0 Hz, 1H),
7.88 (d, J = 1.0 Hz, 1H), 7.60 (d, J = 8.0 Hz, 1H), 7.40 (d, J = 8.0 Hz,
1H), 7.30−7.26 (m, 1H), 7.21−7.17 (m, 1H), 2.40 (s, 3H). 13C{1H}
NMR (100 MHz, CDCl3): δ 134.1, 133.4, 127.9, 127.5, 123.7, 123.5,
120.4, 119.4, 111.3, 101.7, 8.5. IR (neat, cm−1): 3170, 2917, 2349,
1626, 1504, 1417, 1231, 1027, 766, 742. HRMS (ESI+, m/z): [M +
H]+ calcd for C11H11N4, 199.0978; found, 199.0992.
1-(1H-Indol-2-yl)-1H-benzo[d][1,2,3]triazole (4h3). Following the
general procedure, the product was isolated as a white solid in 135.3
mg (58%) by column chromatography (4:1 hexanes/ethyl acetate).
2-(1H-1,2,3-Triazol-1-yl)-1H-indole (4e3).10 Following the general
procedure, the product was isolated as a white solid in 96.9 mg (53%)
by column chromatography (2:1 hexanes/ethyl acetate). 1H NMR
(400 MHz, CDCl3): δ 9.35 (s, 1H), 8.06 (s, 1H), 7.85 (s, 1H), 7.62 (d,
J = 8.0 Hz, 1H), 7.44 (d, J = 8.0 Hz, 1H), 7.29−7.25 (m, 1H), 7.19−
7.16 (m, 1H), 6.58−6.57 (m, 1H). 13C{1H} NMR (100 MHz,
CDCl3): δ 134.5, 133.8, 131.4, 127.0, 123.5, 121.7, 121.2, 121.0, 111.4,
90.5. HRMS (ESI+, m/z): [M + Na]+ calcd for C10H8N4Na, 207.0641;
found, 207.0650.
1
Mp 166.1−166.3 °C. H NMR (400 MHz, CDCl3): δ 9.57 (s, 1H),
8.14 (d, J = 8.4 Hz, 1H), 7.89 (d, J = 8.4 Hz, 1H), 7.70−7.68 (m, 1H),
7.64−7.60 (m, 1H), 7.51−7.44 (m, 2H), 7.31−7.26 (m, 1H), 7.22−
7.18 (m, 1H), 6.78 (d, J = 1.6 Hz, 1H). 13C{1H} NMR (100 MHz,
CDCl3): δ 146.2, 133.7, 131.4, 131.2, 129.0, 127.4, 125.0, 123.2, 121.0,
120.9, 120.4, 111.3, 110.8, 91.0. IR (neat, cm−1): 3363, 1561, 1445,
1296, 1061, 766, 748, 738, 648, 548. HRMS (ESI+, m/z): [M + Na]+
calcd for C14H10N4Na, 257.0803; found, 257.0815.
1-Methyl-2-(1H-1,2,4-triazol-1-yl)-1H-indole (4f1).10 Following the
general procedure, the product was isolated as a yellow solid in 124.9
mg (63%) by column chromatography (1:2 hexanes/ethyl acetate). 1H
NMR (400 MHz, CDCl3): δ 8.38 (s, 1H), 8.19 (s, 1H), 7.65 (d, J =
8.0 Hz, 1H), 7.38−7.31 (m, 2H), 7.22−7.18 (m, 1H), 6.61 (s, 1H),
3.66 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 153.2, 145.5, 136.0
(1-(1-Methyl-1H-indol-2-yl)-1H-imidazol-5-yl)methanol (4i). Fol-
lowing the general procedure, the product was isolated as a white solid
in 113.6 mg (50%) by column chromatography (1:9 methanol/ethyl
1
acetate). Mp 156.0−157.2 °C. H NMR (400 MHz, CDCl3): δ 7.63
(d, J = 8.0 Hz, 1H), 7.47 (s, 1H), 7.34−7.28 (m, 2H), 7.18−7.14 (m,
G
J. Org. Chem. XXXX, XXX, XXX−XXX