The Journal of Organic Chemistry
Article
6.6 Hz), 7.53 (d, 2H, J = 8.4 Hz), 7.48 (d, 2H, J = 8.4 Hz), 7.43 (d, 1H, J
= 9.0 Hz), 7.36 (d, 2H, J = 8.4 Hz), 7.13 (d, 2H, J = 8.4 Hz), 7.02−7.05
(m, 1H), 6.80 (td, 1H, J = 6.6, 1.2 Hz), 6.46 (s, 1H), 2.32 (s, 3H).
13C{1H} NMR (CDCl3, 150 MHz): δ 143.7, 139.7, 136.6, 136.5, 133.4,
132.2, 130.7, 129.6, 126.1, 126.0, 122.8, 122.3, 118.9, 115.2, 113.3,
104.2, 21.5. IR (neat): 3157, 3058, 2929, 1502, 1463, 1313, 1276, 1189,
1082, 997, 834, 766, 670 cm−1. HRMS (ESI): m/z calcd for
C21H17BrNO2S [M + H]+ 426.0158; Found 426.0151.
using 1a (0.4 mmol) and 4j (0.2 mmol). 57 mg (75%), greenish solid,
mp 108.6−109.5 °C. 1H NMR (CDCl3, 600 MHz): δ 9.11 (d, 1H, J =
7.2 Hz), 7.50 (d, 2H, J = 7.8 Hz), 7.43 (d, 1H, J = 9.0 Hz), 7.31 (t, 1H, J
= 7.8 Hz), 7.11 (d, 2H, J = 8.4 Hz), 7.01−7.06 (m, 3H), 6.95 (dd, 1H, J
= 8.4, 2.4 Hz), 6.79 (td, 1H, J = 7.2, 1.2 Hz), 6.49 (s, 1H), 3.84 (s, 3H),
2.31 (s, 3H). 13C{1H} NMR (CDCl3, 150 MHz): δ 158.7, 143.5, 139.9,
137.8, 136.4, 135.7, 129.5, 128.4, 126.3, 126.1, 123.1, 122.5, 118.9,
116.2, 115.3, 113.8, 113.0, 104.3, 55.3, 21.5. IR (neat): 3162, 2965,
2836, 1593, 1502, 1474, 1379, 1317, 1246, 1086, 792, 738, 663 cm−1.
HRMS (ESI): m/z calcd for C22H20NO3S [M + H]+ 378.1158; Found
378.1154.
2-(2-Fluorophenyl)-3-tosylindolizine (5k). (eluent: 10:1 hexanes/
ethyl acetate). The product was synthesized by the general procedure B
using 1a (0.4 mmol) and 4k (0.2 mmol). 56 mg (76%), greenish solid,
mp 117.0−117.6 °C. 1H NMR (CDCl3, 600 MHz): δ 8.92 (d, 1H, J =
6.6 Hz), 7.60 (d, 2H, J = 8.4 H z), 7.38−7.46 (m, 3H), 7.21 (t, 1H, J =
7.8 Hz), 7.17 (d, 2H, J = 8.4 Hz), 7.14 (t, 1H, J = 8.4 Hz), 7.00−7.03
(m, 1H), 6.78 (td, 1H, J = 6.6, 1.2 Hz), 6.53 (s, 1H), 2.33 (s, 3H).
13C{1H} NMR (CDCl3, 150 MHz): δ 160.1 (d, J = 245.5 Hz), 143.7,
139.4, 136.4, 132.9, 130.5, 129.9 (d, J = 8.7 Hz), 129.6, 126.4, 125.6,
123.3 (d, J = 4.4 Hz), 122.4, 122.3, 119.1, 115.9, 115.2 (d, J = 21.6 Hz),
113.2, 104.5, 21.5. 19F NMR (564 MHz, CDCl3): δ −113.0. IR (neat):
3149, 2927, 1507, 1468, 1317, 11,44, 1082, 793, 743 cm−1. HRMS
(ESI): m/z calcd for C21H17FNO2S [M + H]+ 366.0959; Found
366.0950.
2-(4-Methoxyphenyl)-3-tosylindolizine (5e). (eluent: 10:1 hex-
anes/ethyl acetate). The product was synthesized by the general
procedure B using 1a (0.4 mmol) and 4e (0.2 mmol). 45 mg (60%),
1
greenish solid, mp 116.9−118.0 °C. H NMR (CDCl3, 600 MHz): δ
9.08 (d, 1H, J = 6.6 Hz), 7.47 (d, 2H, J = 7.8 Hz), 7.40−7.44 (m, 3H),
7.11 (d, 2H, J = 7.8 Hz), 7.00−7.02 (m, 1H), 6.94−6.96 (m, 2H), 6.76
(td, 1H, J = 6.6, 1.2 Hz), 6.45 (s, 1H), 3.87 (s, 3H), 2.30 (s, 3H).
13C{1H} NMR (CDCl3, 150 MHz): δ 159.5, 143.4, 140.0, 138.0, 136.5,
131.8, 129.5, 126.6, 126.1(8), 126.1(6), 122.6, 118.8, 115.0, 113.0,
112.9, 104.3, 55.3, 21.5. IR (neat): 2961, 2844, 1602, 1509, 1466, 1317,
1244, 1149, 1036, 801, 741 cm−1. HRMS (ESI): m/z calcd for
C22H20NO3S [M + H]+ 378.1158; Found 378.1155.
4-(3-Tosylindolizin-2-yl)benzonitrile (5f). (eluent: 10:1 hexanes/
ethyl acetate). The product was synthesized by the general procedure B
using 1a (0.4 mmol) and 4f (0.2 mmol). 35 mg (47%), greenish solid,
mp 120.2−121.1 °C. 1H NMR (CDCl3, 600 MHz): δ 9.04 (d, 1H, J =
7.2 Hz), 7.69 (d, 2H, J = 8.4 Hz), 7.60 (d, 2H, J = 8.4 Hz), 7.46−7.48
(m, 3H), 7.15 (d, 2H, J = 8.4 Hz), 7.06−7.09 (m, 1H), 6.84 (td, 1H, J =
7.2, 1.2 Hz), 6.49 (s, 1H), 2.33 (s, 3H). 13C{1H} NMR (CDCl3, 150
MHz): δ 144.0, 139.5, 139.4, 136.6, 135.7, 131.4. 131.3, 129.7, 126.1,
125.9, 123.0, 119.1, 119.0, 115.3, 113.7, 111.6, 104.2, 21.5. IR (neat):
3125, 2929, 2232, 1612, 1502, 1317, 1274, 1149, 1084, 836, 812, 747
cm−1. HRMS (ESI): m/z calcd for C22H17N2O2S [M + H]+ 373.1005;
Found 373.1006.
2-(4-Nitrophenyl)-3-tosylindolizine (5g). (eluent: 10:1 hexanes/
ethyl acetate). The product was synthesized by the general procedure B
using 1a (0.4 mmol) and 4g (0.2 mmol). 12 mg (15%), yellow solid, mp
167.6−168.1 °C. 1H NMR (CDCl3, 600 MHz): δ 9.04 (d, 1H, J = 6.6
Hz), 8.26−8.28 (m, 2H), 7.67 (d, 2H, J = 7.8 Hz), 7.47−7.49 (m, 3H),
7.16 (d, 2H, J = 8.4 Hz), 7.07−7.10 (m, 1H), 6.85 (td, 1H, J = 6.6, 1.2
Hz), 6.52 (s, 1H), 2.33 (s, 3H). 13C{1H} NMR (CDCl3, 150 MHz): δ
147.5, 144.1, 141.4, 139.4, 136.6, 135.3, 131.5, 129.7, 126.1, 124.9,
123.1, 122.7, 119.1, 115.5, 113.8, 104.2, 21.5. IR (neat): 3127, 2929,
2857, 1606, 1515, 1347, 1315, 1284, 1146, 1084, 857, 805, 743 cm−1.
HRMS (ESI): m/z calcd for C21H17N2O4S [M + H]+ 393.0903; Found
393.0902.
2-(3-Chlorophenyl)-3-tosylindolizine (5h). (eluent: 10:1 hexanes/
ethyl acetate). The product was synthesized by the general procedure B
using 1a (0.6 mmol) and 4h (0.2 mmol). 60 mg (79%), greenish solid,
mp 113.0−113.7 °C. 1H NMR (CDCl3, 600 MHz): δ 9.08 (d, 1H, J =
6.6 Hz), 7.50 (d, 2H, J = 9.0 Hz), 7.45 (d, 1H, J = 9.0 Hz), 7.39−7.41
(m, 1H), 7.30−7.37 (m, 3H), 7.14 (d, 2H, J = 8.4 Hz), 7.03−7.06 (m,
1H), 6.81 (td, 1H, J = 6.6, 1.2 Hz), 6.47 (s, 1H), 2.33 (s, 3H). 13C{1H}
NMR (CDCl3, 150 MHz): δ 143.8, 139.7, 136.4, 133.3, 130.3, 129.6,
129.0, 128.7(2C), 127.9, 126.2(2C), 126.0, 122.7, 119.0, 115.4, 113.3,
104.2, 21.5. IR (neat): 2931, 1600, 1563, 1502, 1317, 1285, 1149, 1082,
795, 739, 674 cm−1. HRMS (ESI): m/z calcd for C21H17ClNO2S [M +
H]+ 382.0663; Found 382.0661.
2-(3-Bromophenyl)-3-tosylindolizine (5i). (eluent: 10:1 hexanes/
ethyl acetate). The product was synthesized by the general procedure B
using 1a (0.4 mmol) and 4i (0.2 mmol). 72 mg (84%), greenish solid,
mp 131.6−132.4 °C. 1H NMR (CDCl3, 600 MHz): δ 9.10 (d, 1H, J =
6.6 Hz), 7.49−7.53 (m, 4H), 7.43−7.46 (m, 2H), 7.27 (t, 1H, J = 8.4
Hz), 7.15 (d, 2H, J = 8.4 Hz), 7.04 (dd, 1H, J = 9.0, 7.8 Hz), 6.81 (td,
1H, J = 6.6, 1.2 Hz), 6.46 (s, 1H), 2.33 (s, 3H). 13C{1H} NMR (CDCl3,
150 MHz): δ 143.8, 139.7, 136.5, 136.4, 136.0, 133.1, 130.8, 129.6,
129.5, 129.0, 126.2, 126.0, 122.7, 121.5, 119.0, 115.5, 113.3. 104.2, 21.5.
IR (neat): 2967, 1373, 1328, 1280, 1153, 1082, 1004, 870, 762, 738
cm−1. HRMS (ESI): m/z calcd for C21H17BrNO2S [M + H]+ 426.0158;
Found 426.0153.
2-(3,4-Dichlorophenyl)-3-tosylindolizine (5l). (eluent: 10:1 hex-
anes/ethyl acetate). The product was synthesized by the general
procedure B using 1a (0.6 mmol) and 4l (0.2 mmol). 61 mg (73%),
1
greenish solid, mp 132.3−133.4 °C. H NMR (CDCl3, 600 MHz): δ
9.05 (d, 1H, J = 6.6 Hz), 7.43−7.49 (m, 5H), 7.35 (dd, 1H, J = 7.8, 1.2
Hz), 7.15 (d, 2H, J = 7.8 Hz), 7.03−7.05 (m, 1H), 6.81 (td, 1H, J = 6.6,
1.2 Hz), 6.45 (s, 1H), 2.32 (s, 3H). 13C{1H} NMR (CDCl3, 150 MHz):
δ 143.9, 139.6, 136.4, 135.1, 134.4, 132.1(7), 132.1(1), 131.6, 130.1,
129.7, 129.5, 126.2, 125.9, 122.9, 119.0, 115.4, 113.5, 104.1, 21.5. IR
(neat): 3155, 3058, 2927, 1502, 1449, 1381, 1280, 1254, 1151, 1041,
795, 747 cm−1. HRMS (ESI): m/z calcd for C21H16Cl2NO2S [M + H]+
416.0273; Found 416.0267.
2-([1,1′-Biphenyl]-4-yl)-3-tosylindolizine (5m). (eluent: 10:1 hex-
anes/ethyl acetate). The product was synthesized by the general
procedure B using 1a (0.4 mmol) and 4m (0.2 mmol). 17 mg (20%),
light green solid, mp 109.4−110.2 °C. 1H NMR (CDCl3, 600 MHz): δ
9.10 (d, 1H, J = 7.8 Hz), 7.68 (d, 2H, J = 6.6 Hz), 7.65 (d, 2H, J = 8.4
Hz), 7.57 (d, 2H, J = 8.4 Hz), 7.51 (d, 2H, J = 8.4 Hz), 7.44−7.49 (m,
3H), 7.37 (t, 1H, J = 7.8 Hz), 7.12 (d, 2H, J = 8.4 Hz), 7.02−7.05 (m,
1H), 6.80 (td, 1H, J = 7.8, 1.2 Hz), 6.53 (s, 1H), 2.31 (s, 3H). 13C{1H}
NMR (CDCl3, 150 MHz): δ 143.5, 140.9, 140.6, 140.0, 137.7, 136.6,
133.4, 131.0, 130.4, 129.5, 128.8, 127.4, 127.2, 126.2(9), 126.2(4),
122.6, 118.9, 115.3, 113.0, 104.4, 21.4. IR (neat): 2922, 1599, 1507,
1468, 1317, 1149, 184, 844, 766 cm−1. HRMS (ESI): m/z calcd for
C27H22NO2S [M + H]+ 424.1366; Found 424.1361.
2-(Naphthalen-2-yl)-3-tosylindolizine (5n). (eluent: 10:1 hexanes/
ethyl acetate). The product was synthesized by the general procedure B
using 1a (0.4 mmol) and 4n (0.2 mmol). 63 mg (79%), greenish solid,
mp 147.1−148.3 °C. 1H NMR (CDCl3, 600 MHz): δ 9.13 (d, 1H, J =
7.2 Hz), 7.87−7.90 (m, 4H), 7.66 (d, 1H, J = 7.8 Hz), 7.51−7.53 (m,
2H), 7.48 (d, 2H, J = 8.4 Hz), 7.46 (d, 1H, J = 9.0 Hz), 7.07 (d, 2H, J =
8.4 Hz), 7.03−7.06 (m, 1H), 6.81 (t, 1H, J = 7.2 Hz), 6.57 (s, 1H), 2.29
(s, 3H). 13C{1H} NMR (CDCl3, 150 MHz): δ 143.6, 139.9, 137.9,
136.5, 132.9, 132.8, 132.0, 129.5, 129.3, 129.0, 128.2, 127.8, 126.8,
126.2(9), 126.2(3), 126.1(7), 126.1(1), 122.6, 118.9, 115.5, 113.1,
104.6, 21.5. IR (neat): 3166, 3028, 1505, 1382, 1315, 1276, 1146, 1079,
792, 758 cm−1. HRMS (ESI): m/z calcd for C25H20NO2S [M + H]+
398.1209; Found 398.1205.
2-(Benzo[d][1,3]dioxol-5-yl)-3-tosylindolizine (5o). (eluent: 10:1
hexanes/ethyl acetate). The product was synthesized by the general
procedure B using 1a (0.4 mmol) and 4o (0.2 mmol). 51 mg (65%),
1
greenish solid, mp 125.4−126.3 °C. H NMR (CDCl3, 600 MHz): δ
9.06 (d, 1H, J = 6.6 Hz), 7.51 (d, 2H, J = 8.4 Hz), 7.41 (d, 1H, J = 9.0
Hz), 7.13 (d, 2H, J = 7.8 Hz), 7.00−7.02 (m, 1H), 6.97−6.98 (m, 1H),
6.92−6.94 (m, 1H), 6.85 (d, 1H, J = 7.2 Hz), 6.77 (dd, 1H, J = 6.6, 1.2
2-(3-Methoxyphenyl)-3-tosylindolizine (5j). (eluent: 10:1 hexanes/
ethyl acetate). The product was synthesized by the general procedure B
N
J. Org. Chem. XXXX, XXX, XXX−XXX