9
NMR [125 MHz]: δ 19.9 (C1''''), 20.2 (C1''''')A, 4C6.0C(ECP3''T), E54D.5 MAmNetUhySlbCutR-2IP-eTn-1-yl)-[2,3'-biindolinylidene] -2',3-
(C3'''), 108.8 (C7'), 111.0 (C3'), 112.3 (C1''), 112.5 (C7), 114.9
(C1'''), 121.5 (C3'a), 121.9 (C5'), 122.3 (C3a), 122.5 (C5), 125.1
(C4), 125.6 (C4'), 129.8 (C6'), 136.6 (C6), 139.1 (C2'''), 139.7
(C2''), 142.0 (C2), 142.3 (C7'a), 154.5 (C7a), 167.0 (C2'), 188.6
(
dione (17).
Following the general procedure A, a suspension of indirubin
209 mg, 798 μmol) in DMF (20 mL) was heated with caesium
carbonate (624 mg, 1.91 mmol) and 3,3-dimethylallyl bromide
267 μL, 2.31 mmol) for 16 h to obtain (Z)-1'-(3-methylbut-2-en-
-yl)-[2,3'-biindolinylidene]-2',3-dione (12) as a red solid (76.4
mg, 29%). Mp 184-186 °C. UV/Vis: λ (ε) 535 (10777) nm. IR
1
2
3
4
5
6
7
8
(
+
C3). MS (EI): m/z 370 (M , 100%). HRMS (EI): calculated for
(
1
C H N O : 370.1681, found 370.1686.
2
4
22
2
2
Further elution of the SiO2 flash column provided 1-(2-
methylallyl)indoline-2,3-dione (5) (8.0 mg, 3%) as an orange
max
-
1
[
(
cm ]: ν 3316 (w), 2920 (w), 1641 (s), 1600 (s), 1464 (s), 1350
s), 1318 (s), 1166 (s), 1068 (s), 1036 (s), 742 (s). H NMR [300
3
b
1
1
solid. Mp 87-88 ºC (Lit. Mp 87-88 °C). H NMR [500 MHz]: δ
1.77 (3H, s, H1''), 4.30 (2H, s, H3'), 4.98 (2H, d, J = 19.5 Hz,
H1'), 6.89 (1H, d, J = 8.0 Hz, H7), 7.12 (1H, t, J = 7.5 Hz, H5),
MHz]: δ 1.73 (3H, s, H1''), 1.86 (3H, s, H1'''), 4.41 (2H, d, J = 6.3
Hz, H4''), 5.22 (1H, t, J = 6.6 Hz, H3''), 6.83 (1H, d, J = 8.1 Hz,
H7'), 6.93-7.00 (2H, m, H5, H7), 7.10 (1H, t, J = 7.5 Hz, H5'),
7.47 (1H, t, J = 7.2 Hz, H6), 7.71 (1H, d, J = 7.5 Hz, H4), 8.86
(1H, d, J = 7.5 Hz, H4'), 10.53 (1H, s, NH). C NMR [75 MHz]:
δ 18.5 (C1''), 26.0 (C1'''), 38.2 (C4''), 107.1 (C3'), 108.7 (C7'),
112.2 (C7), 118.8 (C2''), 120.4 (C3a), 121.6 (C3'a), 121.8 (C5),
122.8 (C5'), 125.5 (C4), 125.9 (C4'), 129.4 (C6'), 137.0 (C2''),
137.2 (C6), 139.6 (C2), 141.7 (C7'a), 152.0 (C7a), 170.5 (C2'),
9
1
3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
0 7.56 (1H, t, J = 7.5 Hz, H6), 7.62 (1H, d, J = 7.5 Hz, H4).
C
1 NMR [125 MHz]: δ 20.1 (C1''), 46.3 (C3'), 111.3 (C7), 113.7
1
3
2 (C1'), 117.7 (C3a), 124.0 (C5), 125.5 (C4), 138.3 (C2'), 138.6
+
3 (C6), 151.3 (C7a), 158.3 (C2), 183.4 (C3). MS (EI): m/z 201 (M ,
4 100%).
5
3
.3.1.3. (Z)-1'-(But-2-en-1-yl)-[2,3'-
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
biindolinylidene] -2',3-dione (11); (Z)-1,1'-di(but-2-
en-1-yl)-[2,3'-biindolinylidene] -2',3-dione (16).
+
+
188.6 (C3). MS (EI): m/z 330 (M , 80), 262 (M -C
HRMS (ESI): calculated for C21 : 331.1447, found
331.1425.
H , 100%).
5
8
H N O
19 2 2
Following the general procedure A, a suspension of indirubin
(
201 mg, 767 μmol) in DMF (20 mL) was heated with caesium
carbonate (600 mg, 1.84 mmol) and crotyl bromide (229 μL, 2.22
mmol) for 16 to obtain (Z)-1'-(but-2-en-1-yl)-[2,3'-
Further elution of the SiO flash column provided (Z)-1,1'-
bis(3-methylbut-2-en-1-yl)-[2,3'-biindolinylidene]-2',3-dione (17)
9.53 mg, 3%) as a blue solid. Mp: 92-94 °C. UV/Vis: λ (ε)
2
h
(
5
max
biindolinylidene]-2',3-dione (11) with a 2.3:1.0 ratio mixture of
E:Z in the N'-side chain (119 mg, 49 %) as a red solid. Mp 190-
1
-1
78 (5892) nm. IR [cm ]: ν 2958 (w), 2917 (m), 2875 (w), 1673
1
-
1
(s), 1603 (s), 1460 (s), 1325 (s), 1163 (s), 1071 (s), 742 (s). H
NMR [500 MHz]: δ 1.66 (3H, s, H1'''), 1.70 (3H, s, H1'''''), 1.71
(3H, s, H1''), 1.84 (3H, s, H1''''), 4.41 (2H, d, J = 7.0 Hz, H4''),
.82 (2H, d, J = 6.0 Hz, H4'''), 5.18-5.24 (2H, m, H3'', H3'''), 6.90
(1H, d, J = 7.5 Hz, H7'), 7.02-7.06 (3H, m, H5, H5', H7), 7.25
(1H, t, J = 7.5 Hz, H6'), 7.51 (1H, t, J = 7.0 Hz, H6), 7.70 (1H, d,
J = 7.0 Hz, H4), 8.61 (1H, d, J = 7.5 Hz, H4'). C NMR [125
MHz]: δ 18.4 (C1'''), 18.5 (CH '''), 25.8 (C1''), 25.9 (CH ''), 38.3
(C4'''), 48.1 (C4''), 108.5 (C7'), 108.7 (C3'), 112.5 (C7), 119.1
(C3''), 120.2 (C3'''), 121.8 (C5'), 122.0 (C3'a), 122.4 (C5), 122.6
(C3a), 124.9 (C4), 125.6 (C4'), 129.6 (C6'), 136.4 (C2'''), 136.5
92 °C. UV/Vis: λmax (ε) 535 (10711) nm. IR [cm ]: ν 3306 (w),
2
923 (w), 1646 (s), 1601 (s), 1459 (s), 1317 (s), 1165 (s), 1103
1
(s), 1072 (s), 743 (s). H NMR [300 MHz]: δ 1.69 (3H, d, J = 6.0
4
Hz, H1''), 4.39 (2H, d, 5.5 Hz, H4''), 5.40-5.55 (1H, m, H3''),
.69-5.77 (1H, m, H2''), 6.89 (1H, d, J = 7.8 Hz, H7'), 6.96-7.03
2H, m, H5, H7), 7.13 (1H, t, J = 7.5 Hz, H5'), 7.29 (1H, t, J =
.0 Hz, H6'), 7.50 (1H, t, 7.4 Hz, H6), 7.73 (1H, d, J = 7.5 Hz,
5
(
8
13
13
3
3
H4), 8.89 (1H, d, J = 8.1 Hz, H4'), 10.56 (1H, s, NH). C NMR
75 MHz]: δ 17.9 (C1''), 41.8 (C4''), 108.6 (C3), 108.9 (C7'),
[
1
1
1
1
12.2 (C7), 120.4 (C3'a), 121.5 (C3a), 121.9 (C5), 122.9 (C5'),
24.6 (C3''), 125.5 (C4), 125.8 (C4'), 128.7 (C2''), 129.4 (C6'),
37.2 (C6), 139.6 (C5), 141.6 (C3'a), 151.6 (C3a), 170.6 (C2'),
(C6), 136.6 (C2''), 142.1 (C7'a), 142.6 (C2), 154.5 (C7a), 166.6
+
+
+
(C2'), 188.9 (C3). MS (EI): m/z 398 (M , 90), 329 (M+-C
5
H
9
,
88.6 (C3). MS (EI): m/z 316 (M , 100%), 262 (M -C H , 40).
+
4
6
5
7), 262 (M -C H , 100%). HRMS (ESI): calculated for
10 16
HRMS (ESI): calculated for C H N O : 317. 1290, found
3
2
0
17
2
2
C H N O : 399.2073, found 399.2060.
26 27
2
2
17.1303.
3
2
.3.1.5. (Z)-1'-Cinnamyl-[2,3'-biindolinylidene] -
',3-dione (13).
Further elution of the SiO flash column provided (Z)-1,1'-
2
di(but-2-en-1-yl)-[2,3'-biindolinylidene]-2',3-dione (16) with a
.5:1.0 ratio mixture of E:Z in the N-side chain and a 2.0:1.0 ratio
mixture of E:Z in the N'-side chain (25.5 mg, 9%) as a blue solid.
5
Following the general procedure A, a suspension of indirubin
(
204 mg, 779 μmol) in DMF (20 mL) was heated with caesium
carbonate (609 mg, 1.87 mmol) and cinnamyl bromide (450 mg,
2.26 mmol) for 16 to obtain (Z)-1'-cinnamyl-[2,3'-
biindolinylidene]-2',3-dione (13) (61.8 mg, 21%) as a red solid.
Mp 180-182 °C. UV/Vis: λmax (ε) 535 (10159) nm. IR [cm ]: ν
3303 (w), 2920 (w), 2847 (w), 1638 (s), 1600 (s), 1464 (s), 1356
s), 1315 (s), 1169 (s), 1074 (s), 742 (s). H NMR [300 MHz]: δ
.58 (2H, d, J = 5.7 Hz, H3''), 6.22 (1H, dt, J = 15.9 Hz, J = 5.7
Hz, H2''), 6.59 (1H, d, J = 15.9 Hz, H1''), 6.87-6.99 (3H, m, H5,
H7, H7'), 7.09 (1H, t, J = 7.8 Hz, H5'), 7.20-7.32 (6H, m, ArH2,
ArH3, ArH4, ArH5, ArH6, H6'), 7.45 (1H, t, J = 7.5 Hz, H6),
7.69 (1H, d, J = 7.2 Hz, H7'), 8.86 (1H, d, J = 7.5 Hz, H4'), 10.51
1H, s, NH). C NMR [75 MHz]: δ 42.1 (H3''), 106.8 (C3'),
08.9 (C7), 112.2 (C7'), 120.4 (C3a), 121.5 (C3'a), 121.9 (C5),
123.0 (C2''), 123.3 (C5'), 125.6 (C4), 125.9 (C4'), 126.8 (ArC2,
ArC6), 128.2 (C6'), 128.9 (ArC3, ArC5), 129.5 (Ar4), 133.1
-
1
Mp 88-90 °C. IR [cm ]: ν 2952 (w), 2914 (m), 2844 (w), 1705
1
(
s), 1606 (s), 1467 (s), 1356 (m), 1176 (m), 1081 (m), 752 (s). H
NMR [300 MHz]: δ 1.63-1.66 (6H, m, H1'', H1'''), 4.36 (2H, d, J
5.7 Hz, H4''), 4.76 (2H, d, J = 6.0 Hz, H4'''), 5.41-5.74 (4H, m,
H3'', H3''', H2'', H2'''), 6.82 (1H, d, J = 8.7 Hz, H7'), 6.70-7.08
2H, m, H5, H5'), 7.16 (1H, d, J = 8.1 Hz, H7), 7.25 (1H, t, J =
.8 Hz, H6'), 7.52 (1H, t, J = 8.1 Hz, H6), 7.70 (1H, d, J = 7.5
h
-
1
=
1
(
7
(
4
13
Hz, H4), 8.62 (1H, d, J = 7.5 Hz, H4'). C NMR [75 MHz]: δ
1
1
1
1
1
3
7.9 (H1'''), 18.1 (H1''), 41.9 (H4'''), 52.0 (H4''), 108.7 (C7'),
10.9 (C3), 112.7 (C7), 121.8 (C5'), 122.0 (C3a), 122.48 (C5'),
22.53 (C3'a), 124.8 (C4), 125.0 (C3''), 125.7 (H4'), 126.3 (C3'''),
26.4 (C2'''), 129.7 (C6'), 130.4 (C2''), 136.6 (C6), 142.2 (C7'a),
42.5 (C2), 154.6 (C7a), 166.8 (C2'), 188.7 (C3'). MS (EI): m/z
13
(
1
+
70 (M , 100%), 315 (M+-C H , 56). HRMS (ESI): calculated
4
7
for C H N O : 371.1760, found 371.1744.
2
4
23
2
2
(
(
(
C1''), 136.5 (ArC1), 137.2 (C6), 139.7 (C2), 141.4 (C7'a), 151.9
C7a), 170.7 (C2'), 188.5 (C3). MS (EI): m/z 378 (M , 86), 263
3
.3.1.4. (Z)-1'-(3-Methylbut-2-en-1-yl)-[2,3'-
+
biindolinylidene] -2',3-dione (12); (Z)-1,1'-bis(3-
+
M -C H , 100%). HRMS (ESI): calculated for C H N O :
9
7
25 19
2
2
3
79.1447, found 379.1454.