Organic & Biomolecular Chemistry
Paper
+
1
13.40 (minor). HRMS: calcd For C18
H
10ClNO
2
[M] 307.0403; (d, J = 8.7 Hz, 2H), 8.05 (d, J = 8.6 Hz, 2H), 7.90 (d, J = 7.8 Hz,
1H), 7.65 (d, J = 8.2 Hz, 1H), 7.50–7.44 (m, 2H)) including the
found 307.0400.
1
3
olefinic -H, 7.36 (t, J = 7.6 Hz, 1H). C NMR (151 MHz, DMSO)
δ 192.81, 176.83, 156.77, 147.54, 141.24, 140.83, 130.31,
3
-(4-(Benzyloxy)benzylidene)cyclopenta[b]indole-1,2-(3H,4H)-
dione (18)
1
27.41, 126.46, 125.28, 124.68, 124.48, 124.14, 123.48, 121.26,
+
Isomeric ratio: 94 : 06. M.P.: decomposes at >247 °C. Major 120.68, 114.28. HRMS: calcd For C18
H
10
N
2
O
4
[M] 318.0645;
1
isomer: H NMR (600 MHz, DMSO) δ 12.25 (s, 1H), 7.85 (d, J = found 318.0641.
7
7
7
8
.8 Hz, 1H), 7.79 (d, J = 8.6 Hz, 2H), 7.66 (d, J = 8.2 Hz, 1H),
.50 (d, J = 7.3 Hz, 2H), 7.45–7.42 (m, 2H), 7.44–7.40 (m, 1H),
.38–7.35 (m, 1H), 7.34 (s, 1H), 7.33–7.32 (m, 1H), 7.22 (d, J =
3
-(4-(4-(Trifluoromethoxy)phenoxy)benzylidene)cyclo-penta[b]-
indole-1,2(3H,4H)-dione (23)
1
3
1
.6 Hz, 2H), 5.23 (s, 2H). Major isomer: C NMR (151 MHz,
Isomeric ratio: 95 : 05. M.P.: 350–355 °C. Major isomer:
H
DMSO) δ 193.24, 177.01, 160.09, 158.16, 140.73, 136.66,
NMR (600 MHz, DMSO) δ 12.27 (s, 1H), 7.92 (d, J = 8.6 Hz, 2H),
.86 (d, J = 7.8 Hz, 1H), 7.65 (d, J = 8.2 Hz, 1H), 7.53 (d, J = 8.3
Hz, 2H), 7.44 (t, J = 7.7 Hz, 1H), 7.38 (s, 1H), 7.34 (t, J = 7.5 Hz,
1
1
31.47, 128.53, 128.14, 128.03, 127.81, 126.60, 126.32, 124.15,
7
23.98, 120.84, 120.80, 120.43, 115.80, 114.16, 69.51. HRMS:
+
1
3
calcd For C25
H
17NO
3
[M] 379.1203; found 379.1208.
1
1
1
H). C NMR (151 MHz, DMSO) δ 193.00, 176.86, 157.19,
49.12, 140.91, 133.00, 131.37, 127.05, 126.01, 125.52, 124.06,
23.11, 121.69, 121.09, 120.70, 120.08 (q, J = 257.31 Hz),
3
-(4-Methoxybenzylidene)cyclopenta[b]indole-1,2(3H,4H)-
dione (19)
+
+
1
14.19. HRMS (EI ): calcd For C H F NO [M] 357.0617;
19 10 3 3
Isomeric ratio: 94 : 06. M.P.: decomposes with melt at
found 357.0613.
1
2
(
90–294 °C. Major isomer: H NMR (600 MHz, DMSO) δ 12.22
s, 1H), 7.84 (d, J = 7.8 Hz, 1H), 7.79 (d, J = 8.6 Hz, 2H), 7.66 (d, 3-(4-(Trifluoromethoxy)benzylidene)cyclopenta[b]indole-
J = 8.2 Hz, 1H), 7.44–7.39 (m, 1H), 7.34–7.31 (m, 2H) including 1,2(3H,4H)-dione (24)
13
the olefinic -H, 7.14 (d, J = 8.8 Hz, 2H), 3.88 (s, 3H). C NMR
151 MHz, DMSO) δ 193.27, 176.99, 160.97, 158.24, 140.80,
Isomeric ratio: 90 : 10. M.P.: decomposes with melt at
(
1
305–310 °C. Major isomer: H NMR (700 MHz, DMSO) δ 12.21
1
1
3
31.44, 128.17, 126.56, 126.13, 124.12, 123.94, 120.81, 120.41,
(
s, 1H), 7.87–7.83 (m, 3H), 7.65 (d, J = 8.2 Hz, 1H), 7.48 (d, J =
+
15.01, 114.17, 55.47. HRMS: calcd For C H NO [M]
1
9
13
3
8
7
.6 Hz, 2H), 7.44–7.41 (m, 1H), 7.36 (s, 1H), 7.35–7.31 (m, 1H),
.28 (d, J = 9.0 Hz, 2H), 7.18 (d, J = 8.6 Hz, 2H). C NMR
03.0907; found 303.0895.
13
(
176 MHz, DMSO) δ 193.17, 176.92, 158.12, 157.75, 154.41,
44.40, 140.84, 131.65, 129.04, 127.24, 126.78, 124.77, 124.00,
3
-(4-Methylbenzylidene)cyclopenta[b]indole-1,2(3H,4H)-dione
1
1
1
4
(20)
23.20, 121.61, 121.10, 120.94, 120.76, 120.11(q, J = 256 Hz),
Isomeric ratio: 88 : 12. M.P.: decomposes with melt
+
+
18.87, 114.19. HRMS (EI ): calcd For C H F NO [M]
2
5
14
3
4
1
>
1
7
2
308–310 °C. Major isomer: H NMR (600 MHz, DMSO) δ
2.20 (s, 1H), 7.85 (d, J = 7.8 Hz, 1H), 7.70 (d, J = 8.0 Hz, 2H),
.67 (d, J = 8.2 Hz, 1H), 7.45–7.41 (m, 1H), 7.39 (d, J = 7.9 Hz,
H), 7.36–7.32 (m, 2H) including the olefinic -H, 3.33 (s, 1H).
C NMR (151 MHz, DMSO) δ 193.19, 176.95, 157.78, 140.78,
40.21, 130.94, 130.10, 129.35, 128.07, 126.74, 124.69, 123.98,
49.0850; found 449.0875.
Acknowledgements
1
3
1
1
We thank NSERC (JMcN, KK) and the Stanley Medical
Research Institute (CB, RY, LJB, JMcN) for financial support of
this work.
21.63, 120.91, 120.73, 114.24, 21.18. HRMS: calcd For
+
C
19
H
13NO
2
[M] 287.0946; found 287.0946.
3
1
-(Benzo[d][1,3]dioxol-5-ylmethylene)cyclopenta[b]indole-
,2(3H,4H)-dione (21)
Notes and references
Isomeric ratio: 95 : 05. M.P.: decomposes with melt >320 °C.
Major isomer: H NMR (600 MHz, DMSO) δ 12.25 (s, 1H), 7.84
1
1 A. M. Burja, B. Banaigs, E. Abou-Mansour, J. G. Burgess
and P. C. Wright, Tetrahedron, 2001, 57, 9347.
(d, J = 7.8 Hz, 1H), 7.66 (d, J = 8.2 Hz, 1H), 7.42 (t, J = 7.7 Hz,
1
7
H), 7.38–7.35 (m, 2H), 7.33 (t, J = 7.5 Hz, 1H), 7.30 (s, 1H),
.11 (d, J = 7.9 Hz, 1H), 6.16 (s, 2H). C NMR (151 MHz,
2 A. Kobayashi, S. Kajiyama, K. Inawaka, H. Kanzaki and
K. Kawazu, Z. Naturforsch., C: Biosci., 1994, 49, 464.
3 S. S. Hee, G. Chlipala and J. Orjala, J. Microbiol. Biotechnol.,
2008, 18, 1655.
4 (a) A. Ploutno and S. Carmeli, J. Nat. Prod., 2001, 64, 544;
(b) E. P. Balskus and C. T. Walsh, J. Am. Chem. Soc., 2009,
1
3
DMSO) δ 193.21, 176.94, 158.09, 149.21, 148.06, 140.82,
1
1
28.18, 127.78, 126.64, 124.96, 124.35, 123.95, 120.97, 120.87,
20.81, 114.15, 109.31, 108.92, 101.80. HRMS: calcd For
+
C
19
H
11NO
4
[M] 317.0685; found 317.0688.
1
31, 14648.
3
-(4-Nitrobenzylidene)cyclopenta[b]indole-1,2(3H,4H)-
5
P. J. Proteau, W. H. Gerwick, F. Garcia-Pichel and
R. Castenholz, Experientia, 1993, 49, 825.
dione (22)
Isomeric ratio: >98 : 02. M.P.: decomposes with melt >300 °C.
Major isomer: H NMR (600 MHz, DMSO) δ 12.21 (s, 1H), 8.39
6 (a) J. C. Badenock, J. J. Jordan and G. W. Gribble, Tetra-
hedron Lett., 2013, 54, 2759; (b) A. Ekebergh, A. Börje and
1
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