Intramolecular Pd-catalyzed C-H functionalization: Construction of fused tetracyclic bis-indole alkaloid analogues

Article abstract of DOI:10.1016/j.tet.2013.11.079

An efficient Pd-catalyzed intramolecular indole-C2-arylation protocol for the synthesis of pharmaceutically active bis-indole alkaloid analogues from simple and readily available and 3,3′-Bis(1H-indol-3-yl)methanes derivatives has been developed. The corresponding products could be obtained in moderate to excellent yields, which permits selective modification on either one of the two indole moieties independently.

Full text of DOI:10.1016/j.tet.2013.11.079

Accepted Manuscript
Intramolecular Pd-Catalyzed C–H Functionalization: Construction of Fused Tetracyclic
Bis-indole Alkaloid Analogues
Xue-Qiang Chu, You Zi, Xin-Mou Lu, Shun-Yi Wang, Shun-Jun Ji
PII:
S0040-4020(13)01781-X
10.1016/j.tet.2013.11.079
TET 25056
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 14 October 2013
Revised Date: 15 November 2013
Accepted Date: 22 November 2013
Please cite this article as: Chu X-Q, Zi Y, Lu X-M, Wang S-Y, Ji S-J, Intramolecular Pd-Catalyzed C–H
Functionalization: Construction of Fused Tetracyclic Bis-indole Alkaloid Analogues, Tetrahedron (2013),
doi: 10.1016/j.tet.2013.11.079.
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Intramolecular Pd-Catalyzed C–H
Functionalization: Construction of Fused
Tetracyclic Bis-indole Alkaloid Analogue
Xue-Qiang Chu, You Zi, Xin-Mou Lu, Shun-Yi Wang,* Shun-Jun Ji*
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123,
P.R.China

ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Intramolecular Pd-Catalyzed C–H Functionalization: Construction of Fused
Tetracyclic Bis-indole Alkaloid Analogues
Xue-Qiang Chu, You Zi, Xin-Mou Lu, Shun-Yi Wang,* Shun-Jun Ji*
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry , Chemical Engineering and Materials Science, Soochow University, Suzhou
215123, China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
An efficient Pd-catalyzed intramolecular indole-C2-arylation protocol for the
synthesis of pharmaceutically active bis-indole alkaloid analogues from simple and
readily available symmetrical and unsymmetrical 3,3'-Bis(1H-indol-3-yl)methanes
derivatives has been developed. The corresponding products could be obtained in
moderate to excellent yields, which permits selective modification on either one of the
two indole moieties independently.
Available online
Keywords:
Fused Tetracyclic Bis-indole Derivatives,
Indole-C2-Arylation,
© 2013 Elsevier Ltd. All rights reserved.
C-H Bond Functionalization
indole moiety, show high anticancer4 and effective antioxidant
activities, as well as radical scavenging activities.5 Meanwhile,
Yuehchukene (Fig. 1, IV), a polycyclic bis-indole natural
alkaloid, exhibits anti-implantation activity and is a potential
fertility-regulating agent.6 Although, much attention has been
paid to the synthesis and modification of above the C/D rings of
tetracyclic indole derivatives.7 Their traditional strategies involve
the using of phenyl hydrazine and 1-indanone, which are well
known as “Fisher indole synthesis” with the limitation of further
functionalization.8 Other strategies require stoichiometric
amounts of organometallic reagents, which are lengthy or
suffered from multiple-step preparations, the lack of readily
available starting materials, or harsh reaction conditions.9 Taking
these facts into account, the development of a more convenient
1. Introduction
protocol for assembly of these important heterocyclic cores
become highly desirable. Notably, transition-metal-catalyzed
direct C-H bond activation of heteroaromatic compounds has
represented a powerful approach to synthesize polycyclic
derivatives in the past few years.10 As a continuation of our
studies on the construction of diverse heterocycles,11 we herein
report a Pd-catalyzed intramolecular Heck type reaction12 of the
symmetrical and unsymmetrical 3,3'-Bis(1H-indol-3-yl)methanes
(BIMs) derivatives which would provide facile access to the
fused tetracyclic bis-indole alkaloid analogues efficiently.
Figure 1. Representative structures of tetracyclic indole derivatives.
The indole unit exists in numerous privileged pharmaceuticals
and natural alkaloids.1 Particularly, the indeno[1,2-b]indole
scaffold, have received an unprecedented explosion of interest in
the realms of biological and pharmacologically active agents in
the past decades.2 For example, 5, 10-dihydroindeno[1,2-
b]indole (Fig. 1, I), is an important intermediate for the
preparation of the BARAC-Fluor reagent (reagent for in vivo
imaging).3 Compounds II and III (Fig. 1), containing a fused
____________
[a] Corresding auother. Tel: +86-512-65880307; Fax: (+) 86-512-65880307;
E-mail: shunyi@suda.edu.cn; shunjun@suda.edu.cn (S. Ji.)
© 2013 Elsevier Ltd. All rights reserved.
1

ACCEPTED MANUSCRIPT
Table 2. Synthesis of fused tetracyclic bis-indole alkaloid analogues
via Pd-catalyzed intramolecular cyclizationa
Scheme 1. Pd-catalyzed intramolecular indole-C2-arylation of bis-
indole derivatives.
Entry substrates
R
R1
R2
products Time Yeild
(h)
(%)b
94
2. Results and discussion
1
2
3
4
5
6
7
8
9
1a
1b
1c
1d
1e
1f
1g
1h
1i
Me
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
2a
2b
2c
2d
2e
2f
--
2h
2i
5
5
93
86
89
91
Our studies initiated with the preparation of 3,3-bisindolyl
derivative 1a, which could be easily obtained by the reaction of
1-Methyl-1H-indole and 2-Bromobenzaldehyde according to our
previous methods (Scheme 1, A).13 With the 3,3-bisindolyl
derivative 1a in hand, we studied the Pd-catalyzed
intramolecular indole-C2-arylation of 1a. It was found that
corresponding polycyclic fused compound 2a could be
successfully obtained in the presence of 5 mol% Pd(OAc)2 and
10 mol% Ph3P in DMA under basic conditions (Scheme 1, B).
After screening of various bases (e.g., KOAc, NaOAc, CsOAc,
Cs2CO3, K2CO3, t-BuOLi, K3PO4 and Et3N) and solvents (Table
1, entries 1-10), it was found that CsOAc was the best base
additive and the desired product 2a could be obtained in 94%
yield using DMA as solvent (Table 1, entry 3). Moreover, the
feasibility of the palladium catalysts was also investigated and
no better results were observed in these cases (Table 1, entries
5-CH3
6-CH3
7-CH3
5-OMe
2-Me
5-NO2
4-
COOCH3
4-CN
H
12
18
12
12
24
24
12
90
NRc
75
83
10
11
12
1j
1k
1l
H
Me
Me
H
4-CH3
4-F
2j
2k
2l
24
9
12
71
96
81
H
a Reaction conditions: substrates 1 (0.5 mmol), Pd(OAc)2 (5 mol%),
Ph3P (10 mol%) and CsOAc (2 equive) in DMA (2 mL) at 110 oC
under N2 atmosphere.
b Isolated yield.
c NR = No reaction.
Table 3. Synthesis of fused N-heterocycles via Pd-catalyzed
intramolecular cyclization of unsymmetrical 3,3'-Bis(1H-indol-3-
yl)methanesa
12-13). It should be noted that
a control experiment
demonstrated the palladium catalyst was necessary to promote
this reaction (Table 1, entry 11).
Entry
substrates
products
Time Yield(%)b
(h)
HN
Ph
Table 1. Optimization of reaction conditionsa
12
12
24
24
24
92
92
88
87
84
1
Entry Palladium source
(5 mol%)
Base
(2 equiv.)
KOAc
Solvent Yield(%)b
HN
Br
1m
1n
2m
2n
1
2
3
4
5
6
7
8
9
10
11
12
13
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
--
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMF
NRc
<10
94
NaOAc
CsOAc
Cs2CO3
K2CO3
t-BuOLi
K3PO4
2
3
4
5
67
NRc
40
38
Et3Nd
NRc
93
1o
2o
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
Toluene
DMA
DMA
DMA
NRc
NRc
<10
45
PdCl2
1p
2p
Pd(TFA)2
a Reaction conditions: 1a (0.5 mmol), Palladium source (5 mol%),
Ph3P (10 mol%) and base (2 equive) in 2 mL of solvent at 110 oC for
5h under N2.
1q
2q
b Isolated yield.
c NR = No reaction.
d Et3N = Triethylamine.
2ra
95(1:1 c)
With the optimized reaction conditions in hand, the scope of
this intramolecular arylation reaction was evaluated (Table 2).
Gratifyingly, the unprotected bis-indole 1b proceeded well to
furnish the polycyclic compound 2b in satisfactory yield (Table
2, entry 2). Subsequently, the substituent effects on the indole
ring part of the substrates have been examined. As illustrated in
Table 2, indole derivatives with electron-donating groups, such
as methyl and methoxyl, moderate to excellent yields of the
fused heterocycles could be formed (Table 2, entries 3-6).
Noteworthy, the position of substituents on the indole phenyl
ring has no detrimental effect on these reactions (Table 2, entries
24
6
and
1r
2rb
a Reaction conditions: substrates 1 (0.5 mmol), Pd(OAc)2 (5 mol%),
Ph3P (10 mol%) and CsOAc (2 equive) in DMA (2 mL) at 110 oC
under N2 atmosphere.
b Isolated yield.
c The ratios were determined by 1H NMR analysis.
1

ACCEPTED MANUSCRIPT
3-5). Out of our expectation, the presence of methyl group at 2-
results were listed in Table 3. Firstly, we evaluated C2-
substituted heteroaromatic compounds 1m-1q which were
synthesised from (2-Bromophenyl)(1H-indol-3-yl)methanols and
C2-substituted indoles using our previous published methods
with minor modification.14 It was found that variation of
substituents on the phenyl ring of the C2-unsubstituted indole
part with either an electron-donating (Me) or strong withdrawing
groups (NO2, COOCH3) could be successfully employed to
afford the desired fused five-membered indoles in 84-92% yields
(Table 3, entries 1-5). Interestingly, new C-C bonds only
generated at the C2-unsubstituted position of the substrates.
Employment of 1r led to formation of tetracycle 2ra
accompanied by a comparable amount of its chemoisomer 2rb
(1H NMR analysis characterized as a mixture) and no obvious
chemoselectivity was observed (Table 3, entry 6).
position of 1a was inactive in this catalytic process (Table 2,
entry 7). Meanwhile, substrates bearing strong electron-
withdrawing groups (5-NO2, 4-COCH3, 4-CN) also worked
smoothly to give the corresponding tetracyclic products in 75%,
83% and 71% yields, respectively, which needed longer reaction
time under the optimal conditions (Table 2, entries 8–10). As
expected, when bis-indole derivatives 1k and 1l were subjected
to the reaction, bearing Methyl group and F on benzene
ring, the reactions worked well to afford the desired products
2k and 2l in good yields, respectively (Table 2, entries 11-12).
Table 4. Synthesis of polycyclic fused six-membered bis-indole
alkaloid analoguesa
Inspired by the above results, we were eager to know whether
the present protocol was still general enough to generate the
fused six-membered frameworks. Fortunately, the corresponding
product 4a could be obtained in 71% yield when 2,2-Bisindolyl-
1-arylethanone 3a15 was subjected to the reaction instead of 3,3'-
Bis(1H-indol-3-yl)methane derivatives under the identical
conditions (Table 4, entry 1). And such benzo-annulated
carbazoles containing an indole structural unit have been
discovered to display important pharmacological and biological
properties.16 Further exploration of this protocol to other 2,2-
Bisindolyl-1-arylethanones derivatives was also satisfactory, and
the target products were obtained in 62-89% yields (Table 4,
entry 2–6).
It is believed that this palladium-catalyzed intramolecular
alkylation likely proceeds through the Heck type reaction
mechanism12 and is illustrated in Scheme 2. It starts with the
oxidative addition of the Pd(0) species to 3,3'-Bis(1H-indol-3-
yl)methanes derivatives 1 or 3 generating the arylpalladium
complex A (Ar-PdBr). Next, in the presence of CsOAc, complex
A may undergo a direct intramolecular cyclization at the C-2
position via a palladacycle B10 to afford the desired products 2 or
4, and the Pd(0) species back to the catalytic system for the next
cycle.
Entry
1
substrates
products
Time Yeild
(h)
(%)b
N
O
Br
12
71
N
4a
4b
3a
3b
3c
3d
2
3
4
12
13
10
78
70
82
4c
4d
5
6
15
12
62
89
4e
3e
4f
3f
a
Reaction conditions: substrates 3 (0.25 mmol), Pd(OAc)2 (5
mol%), Ph3P (10 mol%) and CsOAc (2 equive) in DMA (2 mL) at
Scheme 2. Proposed mechanism for the synthesis of annulated
indoles.
110 oC under N2 atmosphere.
b Isolated yield.
Considering the 3,3'-Bis(1H-indol-3-yl)methanes derivatives
have the additional advantage of permitting selective
modification on either one of the two indole moieties
independently. Therefore, further expansion of this protocol with
unsymmetrical BIMs derivatives was explored to construct the
bis-indole alkaloid analogues with wider structural diversity, the
3. Conclusion
In summary, we developed an efficient Pd-catalyzed
intramolecular indole-C2-arylation protocol for the synthesis of
pharmaceutically active bis-indole alkaloid analogues from
simple and readily available symmetrical and unsymmetrical
1

ACCEPTED MANUSCRIPT
3,3'-Bis(1H-indol-3-yl)methanes derivatives. The corresponding
staring indole derivative was fully consumed (5–24 h). Upon
completion of the reaction, the resulting solution was diluted
with water (2 mL) and extracted with EtOAc (3×5 mL). The
combined organic extracts were dried with sodium sulfate and
concentrated under reduced pressure. The pure product was
obtained after purification of the residue by column
chromatography (silica gel, ethyl acetate/petroleum ether).
products could be obtained in moderate to excellent yields,
which permits selective modification on either one of the two
indole moieties independently. Moreover, our strategy provided
a practical and efficient way to construct fused tetracyclic indole
derivatives for photophysical and biological activity studies.
4. Experimental Section
4.1 General
General Procedure for the Palladium-Catalyzed Intramolecular
Cyclization
Derivatives.
Reaction
of
2,2-Bisindolyl-1-arylethanones
Unless otherwise stated, all reagents were purchased from
commercial suppliers and used without further purification. All
reactions were carried out in air and using undistilled solvent,
without any precautions to exclude air and moisture unless
otherwise noted. Melting points were recorded on an
Electrothermal digital melting point apparatus. IR spectra were
recorded on a FT-IR spectrophotometer using KBr optics. 1H and
13C NMR spectra were recorded in CDCl3 or D6-DMSO on 300
MHz or 400 MHz spectometers. Tetramethylsilane (TMS) served
2,2-Bisindolyl-1-arylethanones derivatives 3a-3f16 (0.5 mmol),
Pd(OAc)2 (5 mol%), PPh3 (10 mol%), CsOAc (2 equiv.) and 2 ml
DMA (N,N-dimethylacetamide) were added into a flask under N2
atmosphere. The reaction mixture was stirred at 110 °C until the
staring indole derivative was fully consumed (10-15 h). The resulting
solution was diluted with water (2 mL) and extracted with EtOAc
(3×5 mL). The combined organic extracts were dried with sodium
sulfate and concentrated under reduced pressure. The pure product
was obtained after purification of the residue by column
chromatography (silica gel, ethyl acetate/petroleum ether).
1
as internal standard for H NMR and CDCl3 or D6-DMSO was
used as internal standard for 13C NMR. High resolution mass
spectra were obtained using a commercial apparatus (ESI
Source).
4.2
5-Methyl-10-(1-methyl-1H-indol-3-yl)-5,10-dihydro-
indeno[1,2-b]indole (2a): 164 mg, yield 94%. White solid; m.p.
169.7–170.8 °C; IR (KBr): ν = 3445, 3053, 2930, 1613, 1527,
General Procedure for the Preparation of the 3,3'-Bis(1H-
indol-3-yl)methanes Derivatives 1a-1l.13
1460, 1374, 1330, 1155, 1119, 1012, 731, 594 cm-1; H NMR
1
(400 MHz, DMSO-d6): δ = 7.85 (d, J = 7.4 Hz, 1H), 7.53 (d, J =
8.2 Hz, 1H), 7.34 (t, J = 7.0 Hz, 3H), 7.22 (d, J = 7.8 Hz, 1H),
7.16–7.04 (m, 5H), 6.93 (t, J = 7.4 Hz, 1H), 6.85 (t, J = 7.4 Hz,
1H), 5.28 (s, 1H), 4.12 (s, 3H), 3.69 (s, 3H) ppm; 13C NMR (75
MHz, CDCl3): δ = 153.7, 144.1, 142.2, 137.5, 134.5, 128.1,
126.9, 126.4, 125.7, 125.4, 124.2, 124.0, 121.7, 121.3, 119.7,
119.6, 119.0, 117.8, 113.5, 109.9, 109.5 ,39.6, 32.8, 31.4 ppm;
HRMS (ESI): Calcd. for C25H20N2Na: [M+Na]+ 371.1524, found:
371.1518.
A mixture of benzaldehyde (1 mmol), indole (2 mmol) and I2
(0.2 mmol) were ground together in a mortar with a pestle at
room temperature for several minutes. After completion of the
reaction as monitored by TLC, the mixture was filtered. The
precipitate was washed with 10% Na2S2O3 solution (3×3 mL)
and ethanol (5 mL) to afford the pure 3,3'-Bis(1H-indol-3-
yl)methane derivative as a solid (yields: 80-95%).
General Procedure for the Preparation of the Unsymmetrical
4.3 10-(1H-Indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole (2b):
149 mg, yield 93%. Brown solid; m.p. 38.8–39.8 °C; IR (KBr): ν
= 3396, 3054, 2848, 1615, 1497, 1454, 1349, 1245, 1135, 1095,
3,3'-Bis(1H-indol-3-yl)methanes Derivatives 1m-1r.14
1
1009, 876, 801, 753, 597, 510, 481 cm-1; H NMR (400 MHz,
A mixture of (1H-indol-3-yl)(phenyl)methanol derivative (0.5
mmol), indole (0.5 mmol), CAN (Ceric ammonium nitrate) or I2
(0.05 mmol) and anhydrous EtOH (2 mL) was irradiated under
ultrasound in an open vessel at room temperature until the
disappearance of the starting material (2.5 h, checked by TLC).
After standing for 2 h, the reaction mixture was poured into
water and the precipitated solid was collected, washed with
DMSO-d6): δ = 11.65 (s, 1H), 10.86 (s, 1H), 7.63 (d, J = 7.4 Hz,
1H), 7.46 (d, J = 8.1 Hz, 1H), 7.37–7.30 (m, 3H), 7.21 (d, J = 5.8
Hz, 2H), 7.11 (t, J = 7.4 Hz, 1H), 7.07 – 6.95 (m, 3H), 6.89 (t, J
= 7.4 Hz, 1H), 6.77 (t, J = 7.4 Hz, 1H), 5.31 (s, 1H) ppm; 13C
NMR (75 MHz, CDCl3): δ = 153.1, 142.8, 141.0, 136.8, 134.1,
127.5, 127.0, 125.7, 125.6, 125.5, 124.7, 122.2, 121.9, 121.9,
120.4, 119.6, 119.6, 119.5, 117.6, 115.0, 112.3, 111.4, 40.3 ppm;
HRMS (ESI): Calcd. for C23H15N2: [M-H]+ 319.1235, found:
319.1248.
o
warm water (about 80 C, 2×10 mL). The crude mixture was
purified by flash column chromatography to afford the pure
product (yields: 58-90%).
4.4
8-Methyl-10-(5-methyl-1H-indol-3-yl)-5,10-dihydro-
indeno[1,2-b]indole (2c): 149 mg, yield 86%. White solid; m.p.
145.5–147.8 °C; IR (KBr): ν = 3541, 3444, 3386, 2916, 2856,
1709, 1621, 1507, 1441, 1301, 1217, 1092, 1044, 871, 799, 758,
General Procedure for Intramolecular Pd-Catalyzed C–H
Functionalization: Facile Access to Fused Tetracyclic Bis-
indole Alkaloid Analogues.
1
726, 589, 522 cm-1; H NMR (400 MHz, DMSO-d6): δ = 11.48
(s, 1H), 10.70 (s, 1H), 7.60 (d, J = 7.3 Hz, 1H), 7.36–7.28 (m,
3H), 7.21 (d, J = 8.2 Hz, 1H), 7.12–7.06 (m, 2H), 7.00 (s, 1H),
6.90–6.81 (m, 3H), 5.22 (s, 1H), 2.26 (s, 3H), 2.20 (s, 3H) ppm;
13C NMR (75 MHz, CDCl3): δ = 156.6, 153.2, 143.0, 139.3,
135.1, 134.1, 129.6, 128.8, 127.9, 126.9, 125.4, 125.2, 124.9,
123.8, 123.4, 122.0, 119.3, 119.2, 117.5, 114.5, 111.8, 111.1,
40.0, 21.9, 21.7 ppm; HRMS (ESI): Calcd. for C25H19N2: [M-H]+
347.1548, found: 347.1545.
General
Procedure
for
the
Palladium-Catalyzed
Intramolecular Cyclization Reaction of 3,3'-Bis(1H-indol-3-
yl)methanes Derivatives.
3,3'-Bis(1H-indol-3-yl)methane 1a-1r (0.5 mmol), Pd(OAc)2 (5
mol%), PPh3 (10 mol%), CsOAc (2 equiv.), and 2 ml DMA
(N,N-dimethylacetamide) were added into a flask under an inert
atmosphere. The reaction mixture was stirred at 110 °C until the
4.5
7-Methyl-10-(6-methyl-1H-indol-3-yl)-5,10-dihydro-
indeno[1,2-b]indole (2d): 155 mg, yield 89%. White solid; m.p.
1

ACCEPTED MANUSCRIPT
220.0–221.1 °C; IR (KBr): ν = 3410, 2920, 2853, 1713, 1611,
4.10
10-(4-Cyano-1H-indol-3-yl)-5,10-dihydroindeno[1,2-
1443, 1381, 1339, 1214, 1149, 1088, 930, 857, 809, 757, 719,
b]indole-9-carbonitrile (2j): 131 mg, yield 71%. White solid;
m.p. 286.4–287.9 °C; IR (KBr): ν = 3266, 2922, 2852, 2221,
1
595, 497, 433 cm-1; H NMR (300 MHz, DMSO-d6): δ = 11.51
1
(s, 1H), 10.72 (s, 1H), 7.63 (d, J = 6.3 Hz, 1H), 7.39–7.27 (m,
3H), 7.16–7.08 (m, 4H), 6.93 (d, J = 6.9 Hz, 1H), 6.77 (d, J = 6.9
Hz, 1H), 6.64 (d, J = 6.9 Hz, 1H), 5.26 (s, 1H), 2.41 (s, 3H), 2.35
(s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ = 155.2, 144.5,
143.7, 139.6, 136.6, 134.2, 134.0, 129.2, 128.0, 127.7, 127.7,
127.5, 124.8, 124.3, 123.6, 123.5, 121.5, 121.4, 119.6, 117.2,
114.6, 113.7, 42.4, 24.3, 24.2 ppm; HRMS (ESI): Calcd. for
C25H19N2: [M-H]+ 347.1548, found: 347.1548.
1609, 1510, 1343, 1322, 1142, 1050, 787, 738, 605 cm-1; H
NMR (400 MHz, DMSO-d6) δ = 12.43 (s, 1H), 11.45 (s, 1H),
7.87 (d, J = 8.1 Hz, 1H), 7.76 (d, J = 8.2 Hz, 1H), 7.73-7.66 (m,
2H), 7.45 (d, J = 7.4 Hz, 2H), 7.37 (t, J = 7.4 Hz, 1H), 7.30 (t, J
= 7.8 Hz, 1H), 7.27–7.19 (m, 2H), 6.76 (s, 1H), 5.92 (s, 1H).
ppm; 13C NMR (100 MHz, CDCl3): δ = 154.0, 146.6, 140.9,
136.8, 132.2, 127.2, 126.8, 126.1, 125.9, 125.3, 125.2, 125.0,
124.0, 121.4, 121.0, 120.9, 119.9, 119.1, 118.8, 117.7,117.4,
113.4, 100.3, 99.8, 37.8 ppm; HRMS (ESI): Calcd. for C25H13N4:
[M-H]+ 369.1140, found: 369.1131.
4.6
6-Methyl-10-(7-methyl-1H-indol-3-yl)-5,10-dihydro-
indeno[1,2-b]indole (2e): 158 mg, yield 91%. Brown solid; m.p.
98.0–99.3 °C; IR (KBr): ν = 3444, 3051, 2921, 2851, 1720,
1605, 1444, 1303, 1227, 890, 857, 767, 672, 591, 511, 463 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 8.30 (s, 1H), 7.84 (s, 1H),
7.52 (d, J = 7.6 Hz, 2H), 7.47 (d, J = 7.3 Hz, 1H), 7.34–7.26 (m,
2H), 7.11 (t, J = 7.6 Hz, 1H), 7.04–6.94 (m, 4H), 6.91 (d, J = 1.4
Hz, 1H), 5.34 (s, 1H), 2.58 (s, 3H), 2.47 (s, 3H) ppm; 13C NMR
(100 MHz, CDCl3): δ = 153.1, 142.5, 140.4, 136.4, 134.2, 127.1,
126.9, 126.2, 125.4, 125.4, 124.2, 122.6, 122.6, 121.7, 121.3,
120.6, 120.4, 119.7, 117.6, 117.3, 117.2, 115.4, 40.2, 17.1, 16.8
ppm; HRMS (ESI): Calcd. for C25H19N2: [M-H]+ 347.1548,
found: 347.1545.
4.11
3,5-Dimethyl-10-(1-methyl-1H-indol-3-yl)-5,10-
dihydroindeno[1,2-b]indole (2k): 181 mg, yield 96%. Pink
solid; m.p. 158.5–159.7 °C; IR (KBr): ν = 3382, 2921, 2072,
1638, 1529, 1372, 1226, 1193, 1153, 1011, 918, 798, 729, 421
cm-1; H NMR (400 MHz, DMSO-d6): δ = 7.69 (s, 1H), 7.52 (d,
1
J = 8.3 Hz, 1H), 7.35 (d, J = 8.2 Hz, 1H), 7.21 (t, J = 8.5 Hz,
2H), 7.13–7.03 (m, 4H), 6.93 (dd, J = 16.4, 8.3 Hz, 2H), 6.84 (t,
J = 7.4 Hz, 1H), 5.24 (s, 1H), 4.13 (s, 3H), 3.70 (s, 3H), 2.40 (s,
3H) ppm; 13C NMR (75 MHz, DMSO-d6): δ = 150.0, 143.2,
141.6, 137.0, 136.0, 134.2, 127.1, 126.7, 125.8, 124.8, 124.0,
123.3, 121.0, 120.9, 119.3, 119.0, 118.9, 118.5, 118.3, 112.5,
110.5, 109.7, 32.3, 31.1, 21.2 ppm; HRMS (ESI): Calcd. for
C26H21N2: [M-H]+ 361.1705, found: 361.1701.
4.7 8-Methoxy-10-(5-methoxy-1H-indol-3-yl)-5,10-dihydro-
indeno[1,2-b]indole (2f): 171 mg, yield 90%. White solid; m.p.
185.0–186.8 °C; IR (KBr): ν = 3417, 3316, 2937, 2832, 1626,
1570, 1490, 1442, 1300, 1209, 1095, 1051, 924, 784, 639, 478,
4.12
3-Fluoro-5-methyl-10-(1-methyl-1H-indol-3-yl)-5,10-
dihydroindeno[1,2-b]indole (2l): 149 mg, yield 81%. White
solid; m.p. 208.5–209.7 °C; IR (KBr): ν = 3387, 3290, 2900,
1670, 1489, 1226, 1007, 934, 778, 727 cm-1; 1H NMR (400
MHz, DMSO-d6): δ = 7.89–7.84 (m, 1H), 7.54 (d, J = 8.3 Hz,
1H), 7.37 (d, J = 8.2 Hz, 1H), 7.20 (d, J = 7.7 Hz, 2H), 7.17–7.06
(m, 5H), 6.93 (t, J = 7.5 Hz, 1H), 6.86 (t, J = 7.5 Hz, 1H), 5.32
(s, 1H), 4.11 (s, 3H), 3.72 (s, 3H) ppm; 13C NMR (75 MHz,
DMSO-d6): δ = 155.7, 142.3, 141.5, 137.0, 130.5, 127.3, 126.6,
123.5, 123.2, 121.1, 120.9, 119.4, 118.8, 118.5, 113.6, 113.3,
113.1, 112.7, 111.6, 110.6, 109.8, 32.3, 31.0 ppm; HRMS (ESI):
Calcd. for C25H19FN2Na: [M+Na]+ 389.1430, found: 389.1433.
1
426 cm-1; H NMR (400 MHz, DMSO-d6): δ = 11.48 (s, 1H),
10.68 (s, 1H), 7.60 (d, J = 7.4 Hz, 1H), 7.43–7.29 (m, 3H), 7.22
(d, J = 8.6 Hz, 1H), 7.12 (t, J = 7.4 Hz, 1H), 7.06 (s, 1H), 6.73–
6.65 (m, 4H), 5.28 (s, 1H), 3.62 (s, 3H), 3.59 (s, 3H) ppm; 13C
NMR (75 MHz, DMSO-d6): δ = 153.5, 152.8, 152.7, 143.5,
136.0, 134.4, 132.0, 127.0, 125.2, 125.1, 124.3, 124.0, 123.5,
117.8, 113.2, 112.8, 112.3, 110.7, 101.3, 100.7, 55.3, 55.2, 39.7
ppm; HRMS (ESI): Calcd. for C25H19N2O2: [M-H]+ 379.1447,
found: 379.1456.
4.8
8-Nitro-10-(5-nitro-1H-indol-3-yl)-5,10-
dihydroindeno[1,2-b]indole (2h): 154 mg, yield 75%. White
solid; m.p. 319.1–320.5 °C; IR (KBr): ν = 3446, 3295, 3102,
2419, 1765, 1623, 1575, 1551, 1519, 1474, 1420, 1375, 1342,
4.13
10-(2-Phenyl-1H-indol-3-yl)-5,10-dihydroindeno[1,2-
b]indole (2m): 182 mg, yield 92%. Brown solid; m.p. 275.8–
277.0 °C; IR (KBr): ν = 3400, 3053, 2923, 2851, 1702, 1607,
1122, 1047, 888, 742, 664, 637, 573, 420 cm-1; H NMR (400
1455, 1243,1007, 844, 772, 735, 701, 608, 489 cm-1; H NMR
1
1
MHz, DMSO-d6): δ = 12.67 (s, 1H), 11.81 (s, 1H), 8.17 (d, J =
1.9 Hz, 1H), 8.03 (dd, J = 9.0, 2.3 Hz, 1H), 7.95 (dd, J = 8.9, 2.2
Hz, 1H), 7.84 (d, J = 7.2 Hz, 2H), 7.74 (d, J = 9.0 Hz, 2H), 7.57
(d, J = 8.9 Hz, 1H), 7.50 (t, J = 7.4 Hz, 1H), 7.44 (d, J = 7.8 Hz,
1H), 7.30 (td, J = 7.6, 0.7 Hz, 1H), 5.64 (s, 1H) ppm; 13C NMR
(75 MHz, DMSO-d6): δ = 152.3, 146.5, 143.9, 140.8, 140.1,
139.9, 133.2, 127.6, 127.5, 126.6, 125.5, 125.3, 122.7, 118.9,
116.5, 116.3, 115.5, 115.3, 115.2, 114.4, 113.0, 112.2, 42.8 ppm;
HRMS (ESI): Calcd. for C23H13N4O4: [M-H]+ 409.0937, found:
409.0940.
(400 MHz, DMSO-d6) δ = 11.71 (s, 1H), 11.34 (s, 1H), 7.99 (d, J
= 7.3 Hz, 2H), 7.70–7.61 (m, 3H), 7.52–7.42 (m, 2H), 7.36 (t, J
= 7.5 Hz, 1H), 7.27 (d, J = 8.1 Hz, 1H), 7.21 (d, J = 7.3 Hz, 1H),
7.13–7.05 (m, 2H), 7.01 (t, J = 8.2 Hz, 1H), 6.89–6.82 (m, 2H),
6.44 (t, J = 7.6 Hz, 1H), 6.05 (d, J = 7.8 Hz, 1H), 5.39 (s, 1H)
ppm; 13C NMR (75 MHz, DMSO-d6): δ = 152.6, 142.6, 140.8,
136.6, 136.2, 134.6, 133.0, 129.1, 128.8, 127.8, 127.1, 126.5,
125.2, 125.0, 124.6, 123.7, 121.2, 121.0, 119.3, 119.0, 118.3,
118.0, 118.0, 112.6, 111.2, 109.1 ppm; HRMS (ESI): Calcd. for
C29H20N2Na: [M+Na]+ 419.1524, found: 419.1530.
4.9 Methyl 10-(4-(Methoxycarbonyl)-1H-indol-3-yl)-5,10-
dihydroindeno[1,2-b]indole-9-carboxylate (2i): 181 mg, yield
83%. Yellow solid; m.p. 262.1–263.2 °C; IR (KBr): ν = 3402,
3290, 2950, 2358, 1693, 1506, 1434, 1348, 1263, 1139, 923,
4.14
6-Methyl-10-(2-phenyl-1H-indol-3-yl)-5,10-
dihydroindeno[1,2-b]indole (2n): 189 mg, yield 92%. Pale
yellow solid; m.p. 85.6–87.8 °C; IR (KBr): ν = 3409, 3051,
2928, 2851, 1605, 1455, 1444, 1301, 761, 738, 699 cm-1; H
1
1
800, 739, 473 cm-1; H NMR (400 MHz, DMSO-d6): δ = 12.14
NMR (400 MHz, DMSO-d6) δ = 11.52 (s, 1H), 11.30 (s, 1H),
7.99 (d, J = 7.2 Hz, 2H), 7.76 (d, J = 7.2 Hz, 1H), 7.63 (t, J = 6.5
Hz, 2H), 7.48 (t, J = 7.3 Hz, 1H), 7.37 (t, J = 7.2 Hz, 1H), 7.27
(d, J = 7.8 Hz, 1H), 7.20 (d, J = 7.0 Hz, 1H), 7.09 (t, J = 6.7 Hz,
1H), 6.92–6.80 (m, 3H), 6.74 (t, J = 7.5 Hz, 1H), 6.44 (t, J = 7.2
Hz, 1H), 6.08 (d, J = 7.7 Hz, 1H), 5.38 (s, 1H), 2.53 (s, 3H) ppm;
13C NMR (75 MHz, DMSO-d6): δ = 152.5, 142.3, 140.2, 136.5,
136.2, 134.8, 133.0, 129.0, 128.7, 127.8, 127.0, 126.5, 125.1,
125.0, 124.9, 123.3, 121.6, 121.5, 121.1, 119.3, 119.0, 118.2,
118.0, 115.7, 111.1, 109.1, 28.5, 17.0 ppm; HRMS (ESI): Calcd.
for C30H22N2Na: [M+Na]+ 433.1681, found: 433.1673.
(s, 1H), 11.08 (s, 1H), 7.79 (d, J = 7.9 Hz, 1H), 7.74 (d, J = 7.2
Hz, 1H), 7.66–7.57 (m, 3H), 7.29–7.14 (m, 4H), 7.08 (t, J = 7.2
Hz, 1H), 6.39 (s, 1H), 6.24 (s, 1H). ppm; 13C NMR (70 MHz,
DMSO-d6): δ = 168.9, 168.3, 154.5, 145.6, 141.9, 138.0, 132.5,
126.5, 125.9, 124.3, 124.0, 123.5, 123.4, 123.1, 122.8, 122.4,
122.3, 121.2, 120.3, 119.9, 118.6, 117.1, 116.6, 115.8, 52.2,
51.1, 42.4 ppm; HRMS (ESI): Calcd. for C27H19N2O4: [M-H]+
435.1345, found: 435.1344.
1

ACCEPTED MANUSCRIPT
4.15
Methyl
10-(2-phenyl-1H-indol-3-yl)-5,10-
1592, 1474, 1398, 1325, 1223,1205, 1076, 984, 891, 770, 744
1
dihydroindeno[1,2-b]indole-7-carboxylate (2o): 200 mg, yield
88%. Pink solid; m.p. 287.5–290.0 °C; IR (KBr): ν = 3139,
2924, 2787, 1724, 1614, 1415, 1299, 1274, 1236, 1126, 810,
cm-1; H NMR (400 MHz, DMSO-d6): δ = 8.86 (d, J = 7.8 Hz,
1H), 8.44 (d, J = 6.9 Hz, 1H), 8.12 (s, 1H), 7.66 (d, J = 6.8 Hz,
2H), 7.61 (d, J = 6.6 Hz, 2H), 7.55 (s, 1H), 7.30–7.18 (m, 2H),
7.03–6.88 (m, 2H), 6.68–6.78 (m, 2H), 4.41 (s, 3H), 3.98 (s, 3H)
ppm; 13C NMR (75 MHz, DMSO-d6): δ = 144.2, 140.7, 137.1,
129.8, 129.5, 128.2, 125.4, 125.2, 124.2, 123.9, 123.7, 122.3,
122.3, 122.1, 121.3, 119.7, 119.0, 118.4, 118.1, 110.0, 109.2,
108.1, 34.0, 32.8 ppm; HRMS (ESI): Calcd. for C26H20N2NaO:
[M+Na]+ 399.1473, found: 399.1479.
792, 764 cm-1; H NMR (400 MHz, DMSO-d6): δ = 12.18 (s,
1
1H), 11.37 (s, 1H), 8.09 (s, 1H), 7.98 (d, J = 7.8 Hz, 2H), 7.77
(d, J = 7.6 Hz, 1H), 7.64 (t, J = 7.6 Hz, 2H), 7.49 (t, J = 8.3 Hz,
2H), 7.41 (t, J = 7.2 Hz, 1H), 7.26 (dd, J = 13.1, 7.8 Hz, 2H),
7.18 (t, J = 7.4 Hz, 1H), 7.11 (d, J = 8.3 Hz, 1H), 6.86 (t, J = 7.6
Hz, 1H), 6.43 (t, J = 7.5 Hz, 1H), 6.01 (d, J = 8.0 Hz, 1H), 5.45
(s, 1H), 3.81 (s, 3H) ppm; 13C NMR (75 MHz, DMSO-d6): δ =
167.1, 153.1, 146.4, 140.0, 136.7, 136.2, 133.7, 132.9, 129.1,
128.8, 127.9, 127.3, 126.9, 126.4, 126.3, 125.2, 124.7, 121.5,
121.2, 120.3, 118.9, 118.7, 118.4, 117.6, 114.3, 111.2, 108.5,
104.8, 51.8 ppm; HRMS (ESI): Calcd. for C31H22N2NaO2:
[M+Na]+ 477.1579, found: 477.1584.
4.20
11-phenyl-6-(1-phenyl-1H-indol-3-yl)-11H-
benzo[a]carbazol-5-ol (4b): 94.0 mg, yield 78%. Pale yellow
solid; m.p. 78.9–80.6°C; IR (KBr): ν = 3053, 3052, 2957, 2922,
2851, 1720, 1454, 1282, 1209, 1125, 1038, 741, 694, 593 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 8.54 (s, 1H), 8.43 (d, J =
9.1 Hz, 1H), 7.95 (s, 1H), 7.83–7.78 (m, 3H), 7.73–7.64 (m, 5H),
7.55–7.43 (m, 4H), 7.37 (d, J = 9.1 Hz, 1H), 7.32–7.28 (m, 2H),
7.23–7.18 (m, 2H), 7.07 (t, J = 7.3 Hz, 1H), 7.02 (d, J = 7.8 Hz,
1H), 6.92 (d, J = 8.6 Hz, 1H), 6.82 (t, J = 7.3 Hz, 1H) ppm; 13C
NMR (100MHz, DMSO-d6): δ = 145.2, 142.0, 139.8, 139.3,
135.7, 131.7, 131.5, 130.4, 129.9, 129.5, 129.4, 129.0, 128.8,
128.6, 126.4, 125.4, 125.2, 124.5, 124.4, 124.1, 124.0, 123.0,
122.7, 121.5, 121.4, 121.2, 120.3, 120.3, 119.3, 119.2, 111.3,
110.7, 109.8, 109.3 ppm; HRMS (ESI): Calcd. for C36H23N2O:
[M-H]+ 499.1810, found: 499.1805.
4.16
10-(2-Methyl-1H-indol-3-yl)-7-nitro-5,10-
dihydroindeno[1,2-b]indole (2p): 165 mg, yield 87%. Yellow
solid; m.p. 286.6–287.2 °C; IR (KBr): ν = 3452, 3294, 1503,
1459, 1326, 1304, 1133, 1097, 763, 739 cm-1; H NMR (400
1
MHz, DMSO-d6) δ = 12.53 (s, 1H), 10.95 (s, 1H), 7.99–7.91 (m,
2H), 7.74 (d, J = 4.7 Hz, 1H), 7.65 (d, J = 8.2 Hz, 1H), 7.40 (s,
1H), 7.26– 7.14 (m, 3H), 6.74 (t, J = 6.3 Hz, 1H), 6.35 (t, J = 6.5
Hz,1H), 5.85 (d, J = 6.7 Hz, 1H), 5.35 (s, 1H), 2.82 (s, 3H) ppm;
13C NMR (75 MHz, DMSO-d6): δ = 153.1, 146.4, 143.9, 140.6,
135.5, 133.6, 133.5, 127.1, 126.3, 126.2, 126.1, 125.3, 122.9,
119.8, 118.6, 117.8, 117.5, 116.1, 114.2, 112.8, 110.5, 107.0,
38.3, 11.7 ppm; HRMS (ESI): Calcd. for C24H17N3NaO2:
[M+Na]+ 402.1218, found: 402.1221.
4.21
11-benzyl-6-(1-benzyl-1H-indol-3-yl)-11H-
benzo[a]carbazol-5-ol (4c): 94 mg, yield 71%. Pale green solid;
m.p. 89.1–91.6°C; IR (KBr): ν = 3481, 3052, 3028, 2921, 2850,
1717, 1674, 1566, 1464, 1355, 1141, 1073, 935, 767, 739, 667
1
4.17
Methyl
10-(2-methyl-1H-indol-3-yl)-5,10-
cm-1; H NMR (400 MHz, DMSO-d6): δ = 8.85 (d, J = 8.5 Hz,
dihydroindeno[1,2-b]indole-7-carboxylate (2q): 165 mg, yield
84%. Gray solid; m.p. 242.7–244.8 °C; IR (KBr): ν =3387, 3310,
3056, 2945, 1694, 1616, 1460, 1434, 1347, 1272, 1217, 1089,
758, 729, 613 cm-1; 1H NMR (400 MHz, DMSO-d6) δ = 12.08 (s,
1H), 10.88 (s, 1H), 8.09 (s, 1H), 7.75 (d, J = 6.6 Hz, 1H), 7.51
(d, J = 7.7 Hz, 1H), 7.40 (t, J = 6.6 Hz, 1H), 7.27–7.09 (m, 4H),
6.74 (t, J = 6.2 Hz, 1H), 6.35 (t, J = 6.5 Hz, 1H), 5.84 (d, J = 6.8
Hz, 1H), 5.29 (s, 1H), 3.82 (s, 3H), 2.79 (s, 3H) ppm; 13C NMR
(75 MHz, DMSO-d6): δ = 167.1, 153.4, 146.3, 140.0, 135.4,
133.8, 133.4, 127.2, 127.0, 126.2, 126.1, 125.4, 125.1, 124.9,
121.4, 120.2, 119.7, 118.7, 117.7, 114.2, 110.3, 107.4, 51.8, 11.7
ppm; HRMS (ESI): Calcd. for C26H20N2NaO2: [M+Na]+
415.1422, found: 415.1423.
1H), 8.58 (d, J = 4.9 Hz, 2H), 8.38 (d, J = 8.3 Hz, 1H), 7.77 (t, J
= 7.5 Hz, 1H), 7.51 (t, J = 7.6 Hz, 1H), 7.45 (d, J = 8.3 Hz, 1H),
7.39–7.35 (m, 2H), 7.29–7.18 (m, 5H), 7.15–7.06 (m, 7H), 6.95
(t, J = 7.4 Hz, 1H), 6.63–6.58 (m, 2H), 5.40 (d, J = 15.9 Hz, 1H),
5.28 (d, J = 15.6 Hz, 1H), 5.17 (d, J = 17.0 Hz, 1H), 4.95 (d, J =
16.9 Hz, 1H) ppm; 13C NMR (100MHz, DMSO-d6): δ = 151.3,
139.7, 138.5, 138.4, 137.8, 136.1, 131.5, 130.2, 129.5, 129.3,
128.4, 128.1, 127.5, 127.2, 127.0, 126.6, 125.4, 123.8, 123.4,
122.7, 122.6, 122.3, 121.7, 121.3, 120.6, 120.2, 119.6, 119.1,
110.5, 110.2, 108.5, 105.4, 102.5, 49.5, 46.0 ppm; HRMS (ESI):
Calcd. for: C38H27N2O: [M-H]+ 527.2123, found: 527.2118.
4.22
6-(1,7-dimethyl-1H-indol-3-yl)-10,11-dimethyl-11H-
benzo[a]carbazol-5-ol (4d): 99 mg, yield 82%. Pale yellow
solid; m.p. 204.6–206.2°C; IR (KBr): ν = 3486, 2958, 2922,
2851, 1732, 1600, 1449, 1374, 1261, 1105, 755, 745, 736 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 8.62 (d, J = 8.4 Hz, 1H),
8.39 (d, J = 8.3 Hz, 1H), 8.00 (s, 1H), 7.66 (t, J = 7.1 Hz, 1H),
7.58 (t, J = 7.5 Hz, 1H), 7.40 (s, 1H), 7.01–6.96 (m, 1H), 6.88 (d,
J = 6.3 Hz, 1H), 6.79–6.70 (m, 2H), 6.65–6.58 (m, 2H), 4.39 (s,
3H), 4.21 (s, 3H), 2.86 (s, 3H), 2.81 (s, 3H) ppm; 13C NMR
(100MHz, DMSO-d6): δ = 144.8, 142.3, 135.6, 132.2, 131.2,
129.3, 127.1, 125.2, 124.3, 124.1, 123.8, 123.7, 122.7, 121.8,
121.3, 120.9, 119.3, 119.1, 118.9, 117.8, 109.7, 107.6, 37.9,
36.5, 20.3, 19.3 ppm; HRMS (ESI): Calcd. for C28H23N2O: [M-
H]+ 403.1810, found: 403.1805.
4.18
b]indole
10-(5-Nitro-1H-indol-3-yl)-5,10-dihydroindeno[1,2-
(2ra) and 10-(1H-indol-3-yl)-8-nitro-5,10-
dihydroindeno[1,2-b]indole (2rb): 174 mg, yield 95%. Yellow
solid; m.p. 210.2–212.3 °C; IR (KBr): ν = 3407, 3292, 3049,
2921, 1618, 1508, 1455, 1328, 1102, 813, 761, 738 cm-1;
Characterized as a 1.1:1 mixture. 1H NMR (400 MHz, DMSO-
d6): δ = 12.55 (s, 1H), 11.77 (s, 1H), 8.10 (s, 1H), 7.97 (d, J = 9.1
Hz, 1H), 7.89 (d, J = 9.1 Hz, 1H), 7.52–7.45 (m, 2H), 7.44–7.37
(m, 3H), 7.25-7.18 (m, 2H), 7.14 (t, J = 7.4 Hz, 1H), 6.99 (t, J =
1
7.4 Hz, 1H), 5.45 (s, 1H). Isomer H NMR (400 MHz, DMSO-
d6): 11.70 (s, 1H), 10.97 (s, 1H), 7.80 (s, 1H), 7.73 (d, J = 7.3
Hz, 1H), 7.70–7.64(m, 2H), 7.62 (m, 1H), 7.37–7.30 (m, 3H),
7.06 (t, J = 7.5 Hz, 1H), 6.93–6.86 (m, 2H), 6.76 (t, J = 7.5 Hz,
1H), 5.43 (s, 1H); 13C NMR (75 MHz, DMSO-d6): mixture of
2qa and 2qb δ = 153.0, 152.1, 146.4, 143.9, 142.7, 140.8, 140.7,
140.0, 139.9, 136.7, 134.3, 133.3, 127.3, 127.2, 127.2, 126.3,
126.1, 126.1, 125.3, 125.3 ,125.0, 123.8, 123.7, 123.4, 122.9,
121.1, 121.0, 119.4, 118.7, 118.5, 118.4, 118.2, 118.1, 116.4,
116.2, 116.1, 115.8, 114.5, 112.8, 112.6, 112.1, 112.0, 111.7
ppm; HRMS (ESI): Calcd. for C23H14N3O2: [M-H]+ 364.1086,
found: 364.1099.
4.23
8-methoxy-6-(5-methoxy-1-phenyl-1H-indol-3-yl)-11-
phenyl-11H-benzo[a]carbazol-5-ol (4e): 100 mg, yield 62%.
Pale red solid; m.p. 242.0–243.8°C; IR (KBr): ν = 3478, 2957,
1928, 2845, 1709, 1586, 1449, 1260, 1245, 1055, 1016, 759,
749, 708 cm-1; 1H NMR (400 MHz, DMSO-d6): δ = 8.58 (s, 1H),
8.42 (d, J = 8.3 Hz, 1H), 7.90 (s, 1H), 7.77–7.62 (m, 9H), 7.52–
7.40 (m, 3H), 7.37 (d, J = 8.5 Hz, 1H), 7.29 (t, J = 8.3 Hz, 1H),
6.99–6.90 (m, 2H), 6.83 (d, J = 8.9 Hz, 1H), 6.67 (s, 1H), 6.33
(s, 1H), 3.57 (s, 3H), 3.20 (s, 3H) ppm; 13C NMR (100MHz,
DMSO-d6): δ = 154.4, 153.0, 144.9, 140.1, 139.4, 137.3, 131.5,
130.7, 130.4, 130.2, 130.1, 129.9, 129.2, 128.7, 128.6, 126.2,
125.5, 125.2, 124.3, 123.9, 123.5, 123.2, 121.6, 121.5, 119.1,
4.19
11-Methyl-6-(1-methyl-1H-indol-3-yl)-11H-
benzo[a]carbazol-5-ol (4a): 134 mg, yield 71%. Pale yellow
solid; m.p. 258.6–260.4 °C; IR (KBr): ν = 3500, 3050, 2939,
1

ACCEPTED MANUSCRIPT
Planta Med. 1985, 50, 304–307; (c) Wenkert, E.; Moeller, P. D. R.;
113.9, 112.4, 111.5, 111.1, 110.5, 109.2, 103.5, 102.2, 55.4, 54.4
ppm; HRMS (ESI): Calcd. for C38H27N2O3: [M-H]+ 559.2022,
found: 559.2016.
Piettre, S. R. J. Org. Chem. 1988, 53, 3170–3178; (d) Bergman, J.;
Venemalm, L. Tetrahedron Lett. 1988, 29, 2993–2994; (e) Chan, W.-L.;
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6479–6480; (b) Campo, M. A.; Larock, R. C. J. Org. Chem. 2002, 67,
5616–5620; (c) Zeni, G.; Larock, R. C. Chem. Rev. 2004, 104, 2285–
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H.; You, J. S.; Song, F. J. Chem.–Eur. J. 2013, 19, 1189–1193; (g)
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4.24
8-methyl-6-(5-methyl-1-phenyl-1H-indol-3-yl)-11-
phenyl-11H-benzo[a]carbazol-5-ol (4f): 136 mg, yield 89%.
White solid; m.p. 235.7–237.1°C; IR (KBr): ν = 3467, 3066,
2958, 2918, 2852, 1727, 1593, 1476, 1397, 1285, 1212, 1076,
789, 704 cm-1; 1H NMR (400 MHz, DMSO-d6): δ = 8.48 (s, 1H),
8.41 (d, J = 8.5 Hz, 1H), 7.87 (s, 1H), 7.78–7.64 (m, 9H), 7.53–
7.42 (m, 3H), 7.35 (d, J = 8.3 Hz, 1H), 7.30–7.25 (m, 1H), 7.13
(d, J = 8.6 Hz, 1H), 7.03 (d, J = 4.8 Hz, 2H), 6.91 (d, J = 8.4 Hz,
1H), 6.74 (s, 1H), 2.29 (s, 3H), 2.07 (s, 3H) ppm; 13C NMR
(100MHz, DMSO-d6): δ = 145.1, 140.5, 140.0, 139.5, 134.1,
131.7, 130.4, 129.9, 129.7, 129.6, 129.0, 128.8, 128.7, 128.6,
128.6, 127.6, 126.2, 125.8, 125.3, 125.1, 124.2, 124.2, 123.8,
123.7, 123.2, 121.5, 121.4, 121.0, 119.8, 119.1, 111.2, 110.4,
109.6, 109.6, 21.2, 20.9 ppm; HRMS (ESI): Calcd. for
C38H27N2O: [M-H]+ 527.2123, found: 527.2118.
8. Okaoto, T. A.; Kobayashi, S. M.; Yamamoto, H. N.; German Pat.
DE1952019, 1970.
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14, 4894–4897; (c) Cai, Z.-J.; Wang, S.-Y.; Ji, S.-J. Org. Lett., 2012, 14,
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Acknowledgements
We gratefully acknowledge the Natural Science Foundation of
China (No. 21172162, 21372174), the Young National Natural
Science Foundation of China (No. 21202111), the Young
Natural Science Foundation of Jiangsu Province (BK2012174),
Key Laboratory of Organic Synthesis of Jiangsu Province
(KJS1211), PAPD, and Soochow University for financial
support.
References
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Kenda, B.; Quesnel, Y.; Ates, A.; Michel, P.; Turet, L.; Mercier, J.
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G. R.; Kuethe, J. T. Chem. Rev. 2006, 106, 2875–2911.
2. (a) Lewis, S. E. Tetrahedron 2006, 62, 8655–8681; (b) Higuchi, T.;
Kawasaki, T. Nat. Prod. Rep. 2007, 24, 843–868; (c) Lounasmaa, M.;
Tolvanen, A. Nat. Prod. Rep. 2000, 17, 175–191.
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4303–4427.
1

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Supporting Information
Intramolecular Pd-Catalyzed C–H Functionalization:
Construction of Fused Tetracyclic Bis-indole Alkaloid
Analogues
Xue-Qiang Chu, You Zi, Xin-Mou Lu, Shun-Yi Wang,* Shun-Jun Ji*
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,
Chemical Engineering and Materials Science, Dushu Lake Campus, Soochow
University, Suzhou, 215123, People’s Republic of China.
Fax : (+86)-512-65880307; phone: (+86)- 512-65880307; E-mail: shunyi@suda.edu.cn;
shunjun@suda.edu.cn
Table of Contents
General Information
page S2
General procedure for intramolecular Pd-catalyzed C–H functionalization: facile
access to fused tetracyclic bis-indole alkaloid analogues
Analytical and spectral data for compounds
page S2
page S5
The 1H and 13C NMR spectra of compounds
page S14
S1

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General Information
Melting points were recorded on an Electrothermal digital melting point apparatus. IR spectra
were recorded on a Varian FT-1000 spectrophotome-ter using KBr optics. 1H NMR spectra
were recorded on a Varian INOVA 400 and and 13C NMR were recorded on a Varian INOVA
75 or 100 MHz spectrometer using CDCl3 as solvent and TMS as internal standard. High
resolution mass spectra were obtained using Microma GCT-TOF instrument.
General Procedure for the preparation of the 3,3'-Bis(1H-indol-3-yl)methanes
derivatives 1a-1l[1]
A mixture of benzaldehyde (1 mmol), indole (2 mmol) and I2 (0.2 mmol) were ground
together in a mortar with a pestle at room temperature for several minutes. After completion
of the reaction as monitored by TLC, the mixture was filtered. The precipitate was washed
with 10% Na2S2O3 solution (3 ×3 mL) and ethanol (5 mL) to afford the pure
3,3'-Bis(1H-indol-3-yl)methane derivative as a solid (yields: 80-95%).
General
Procedure
for
the
preparation
of
the
unsymmetrical
3,3'-Bis(1H-indol-3-yl)methanes derivatives 1m-1r[2]
R3
Br
NH
R2
OH
CAN or I2
U.S. EtOH
Br
R2
R1
R3
N
H
N
HN
H
R1
A mixture of (1H-indol-3-yl)(phenyl)methanol derivative (0.5 mmol), indole (0.5 mmol),
CAN(Ceric ammonium nitrate) or I2 (0.05 mmol) and anhydrous EtOH (2 mL) was irradiated
under ultrasound in an open vessel at room temperature until the disappearance of the starting
material (2.5 h, checked by TLC). After standing for 2 h, the reaction mixture was poured into
o
water and the precipitated solid was collected, washed with warm water (about 80 C, 2×10
mL). The crude mixture was purified by flash column chromatography to afford the pure
product (yields: 58-90%).
S2

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General procedure for intramolecular Pd-catalyzed C–H functionalization: facile
access to fused tetracyclic bis-indole alkaloid analogues
General Procedure for the Palladium-Catalyzed Intramolecular cyclization Reaction of
3,3'-Bis(1H-indol-3-yl)methanes derivatives
3,3'-Bis(1H-indol-3-yl)methane 1a-1r (0.5 mmol), Pd(OAc)2 (5 mol%), PPh3 (10 mol%),
CsOAc (2 equiv.), and 2 ml DMA (N,N-dimethylacetamide) were added into a flask under an
inert atmosphere. The reaction mixture was stirred at 110 °C until the staring indole derivative
was fully consumed (5–24 h). Upon completion of the reaction, the resulting solution was
diluted with water (10 mL) and extracted with EtOAc (3×5 mL). The combined organic
extracts were dried with sodium sulfate and concentrated under reduced pressure. The pure
product was obtained after purification of the residue by column chromatography (silica gel,
ethyl acetate/petroleum ether).
General Procedure for the Palladium-Catalyzed Intramolecular cyclization Reaction of
2,2-Bisindolyl-1-arylethanones derivatives
2,2-Bisindolyl-1-arylethanones derivative 3a-3f[3] (0.25 mmol), Pd(OAc)2 (5 mol%), PPh3 (10
mol%), CsOAc (2 equiv.), and 2 ml DMA (N,N-dimethylacetamide) were added into a flask
under an inert atmosphere. The reaction mixture was stirred at 110 °C for 10-15 h. The
resulting solution was diluted with water (10 mL) and extracted with EtOAc (3×5 mL). The
combined organic extracts were dried with sodium sulfate and concentrated under reduced
pressure. The pure product was obtained after purification of the residue by column
chromatography (silica gel, ethyl acetate/petroleum ether).
References
[1] a) Ji, S.-J.; Wang, S.-Y.; Zhang, Y.; Loh, T.-P. Tetrahedron 2004, 60, 2051–2055; b) Wang, S.-Y.; Ji,
S.-J. Tetrahedron 2006, 62, 1527-1535.
[2] a) Zeng, X.-F.; Wang, S.-Y.; Ji, S.-J. Tetrahedron 2005, 61, 10235–10241; b) Guo, Q.-X.; Peng,
Y.-G.; Zhang, J.-W.; Song, L.; Feng, Z.; L.-Z. Gong Org. Lett. 2009, 11, 4620–4623; c) Lin, H.; Zang,
Y.; Sun, X.-W.; Lin, G.-Q, Chin. J. Chem. 2012, 30, 2309–2314; d) Elayaraja, R.; Karunakaran, R. J.
Tetrahedron Lett. 2012, 53, 6901-6904.
[3] Zhu, Y.-P.; Liu, M.-C.; Jia, F.-C.; Yuan, J.-J.; Gao, Q.-H.; Lian, M.; Wu, A.-X. Org. Lett. 2012, 14,
3392–3395.
S3

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Analytical and spectral data for compounds
5-Methyl-10-(1-methyl-1H-indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole(2a)
White solid; m.p. 169.7–170.8 °C;
IR (KBr): ν = 3445, 3053, 2930, 1613, 1527, 1460, 1374, 1330, 1155, 1119, 1012, 731, 594
cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 7.85 (d, J = 7.4 Hz, 1H), 7.53 (d, J = 8.2 Hz, 1H), 7.34 (t,
J = 7.0 Hz, 3H), 7.22 (d, J = 7.8 Hz, 1H), 7.16–7.04 (m, 5H), 6.93 (t, J = 7.4 Hz, 1H), 6.85 (t,
J = 7.4 Hz, 1H), 5.28 (s, 1H), 4.12 (s, 3H), 3.69 (s, 3H) ppm;
13C NMR (75 MHz, CDCl3): δ = 153.7, 144.1, 142.2, 137.5, 134.5, 128.1, 126.9, 126.4, 125.7,
125.4, 124.2, 124.0, 121.7, 121.3, 119.7, 119.6, 119.0, 117.8, 113.5, 109.9, 109.5 ,39.6, 32.8,
31.4 ppm;
HRMS (ESI): Calcd. for C25H20N2Na: [M+Na]+ 371.1524, found: 371.1518.
10-(1H-Indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole (2b)
Brown solid; m.p. 38.8–39.8 °C;
IR (KBr): ν = 3396, 3054, 2848, 1615, 1497, 1454, 1349, 1245, 1135, 1095, 1009, 876, 801,
753, 597, 510, 481 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 11.65 (s, 1H), 10.86 (s, 1H), 7.63 (d, J = 7.4 Hz, 1H),
7.46 (d, J = 8.1 Hz, 1H), 7.37–7.30 (m, 3H), 7.21 (d, J = 5.8 Hz, 2H), 7.11 (t, J = 7.4 Hz, 1H),
7.07–6.95 (m, 3H), 6.89 (t, J = 7.4 Hz, 1H), 6.77 (t, J = 7.4 Hz, 1H), 5.31 (s, 1H) ppm;
13C NMR (75 MHz, CDCl3): δ = 153.1, 142.8, 141.0, 136.8, 134.1, 127.5, 127.0, 125.7, 125.6,
125.5, 124.7, 122.2, 121.9, 121.9, 120.4, 119.6, 119.6, 119.5, 117.6, 115.0, 112.3, 111.4, 40.3
ppm;
HRMS (ESI): Calcd. for C23H15N2: [M-H]+ 319.1235, found: 319.1248.
8-Methyl-10-(5-methyl-1H-indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole(2c)
White solid; m.p. 145.5–147.8 °C;
IR (KBr): ν = 3541, 3444, 3386, 2916, 2856, 1709, 1621, 1507, 1441, 1301, 1217, 1092, 1044,
871, 799, 758, 726, 589, 522 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 11.48 (s, 1H), 10.70 (s, 1H), 7.60 (d, J = 7.3 Hz, 1H),
7.36–7.28 (m, 3H), 7.21 (d, J = 8.2 Hz, 1H), 7.12–7.06 (m, 2H), 7.00 (s, 1H), 6.90–6.81 (m,
3H), 5.22 (s, 1H), 2.26 (s, 3H), 2.20 (s, 3H) ppm;
13C NMR (75 MHz, CDCl3): δ = 156.6, 153.2, 143.0, 139.3, 135.1, 134.1, 129.6, 128.8, 127.9,
126.9, 125.4, 125.2, 124.9, 123.8, 123.4, 122.0, 119.3, 119.2, 117.5, 114.5, 111.8, 111.1, 40.0,
21.9, 21.7 ppm;
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HRMS (ESI): Calcd. for C25H19N2: [M-H]+ 347.1548, found: 347.1545.
7-Methyl-10-(6-methyl-1H-indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole(2d)
White solid; m.p. 220.0–221.1 °C;
IR (KBr): ν = 3410, 2920, 2853, 1713, 1611, 1443, 1381, 1339, 1214, 1149, 1088, 930, 857,
809, 757, 719, 595, 497, 433 cm-1;
1H NMR (300 MHz, DMSO-d6): δ = 11.51 (s, 1H), 10.72 (s, 1H), 7.63 (d, J = 6.3 Hz, 1H),
7.39–7.27 (m, 3H), 7.16–7.08 (m, 4H), 6.93 (d, J = 6.9 Hz, 1H), 6.77 (d, J = 6.9 Hz, 1H), 6.64
(d, J = 6.9 Hz, 1H), 5.26 (s, 1H), 2.41 (s, 3H), 2.35 (s, 3H) ppm;
13C NMR (100 MHz, CDCl3): δ = 155.2, 144.5, 143.7, 139.6, 136.6, 134.2, 134.0, 129.2,
128.0, 127.7, 127.7, 127.5, 124.8, 124.3, 123.6, 123.5, 121.5, 121.4, 119.6, 117.2, 114.6,
113.7, 42.4, 24.3, 24.2 ppm;
HRMS (ESI): Calcd. for C25H19N2: [M-H]+ 347.1548, found: 347.1548.
6-Methyl-10-(7-methyl-1H-indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole(2e)
Brown solid; m.p. 98.0–99.3 °C;
IR (KBr): ν = 3444, 3051, 2921, 2851, 1720, 1605, 1444, 1303, 1227, 890, 857, 767, 672, 591,
511, 463 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 8.30 (s, 1H), 7.84 (s, 1H), 7.52 (d, J = 7.6 Hz, 2H), 7.47
(d, J = 7.3 Hz, 1H), 7.34–7.26 (m, 2H), 7.11 (t, J = 7.6 Hz, 1H), 7.04–6.94 (m, 4H), 6.91 (d, J
= 1.4 Hz, 1H), 5.34 (s, 1H), 2.58 (s, 3H), 2.47 (s, 3H) ppm;
13C NMR (100 MHz, CDCl3): δ = 153.1, 142.5, 140.4, 136.4, 134.2, 127.1, 126.9, 126.2,
125.4, 125.4, 124.2, 122.6, 122.6, 121.7, 121.3, 120.6, 120.4, 119.7, 117.6, 117.3, 117.2,
115.4, 40.2, 17.1, 16.8 ppm;
HRMS (ESI): Calcd. for C25H19N2: [M-H]+ 347.1548, found: 347.1545.
8-Methoxy-10-(5-methoxy-1H-indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole(2f)
White solid; m.p. 185.0–186.8 °C;
IR (KBr): ν = 3417, 3316, 2937, 2832, 1626, 1570, 1490, 1442, 1300, 1209, 1095, 1051, 924,
784, 639, 478, 426 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 11.48 (s, 1H), 10.68 (s, 1H), 7.60 (d, J = 7.4 Hz, 1H),
7.43–7.29 (m, 3H), 7.22 (d, J = 8.6 Hz, 1H), 7.12 (t, J = 7.4 Hz, 1H), 7.06 (s, 1H), 6.73–6.65
(m, 4H), 5.28 (s, 1H), 3.62 (s, 3H), 3.59 (s, 3H) ppm;
13C NMR (75 MHz, DMSO-d6): δ = 153.5, 152.8, 152.7, 143.5, 136.0, 134.4, 132.0, 127.0,
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125.2, 125.1, 124.3, 124.0, 123.5, 117.8, 113.2, 112.8, 112.3, 110.7, 101.3, 100.7, 55.3, 55.2,
39.7 ppm;
HRMS (ESI): Calcd. for C25H19N2O2: [M-H]+ 379.1447, found: 379.1456.
8-Nitro-10-(5-nitro-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole(2h)
White solid; m.p. 319.1–320.5 °C;
IR (KBr): ν = 3446, 3295, 3102, 2419, 1765, 1623, 1575, 1551, 1519, 1474, 1420, 1375, 1342,
1122, 1047, 888, 742, 664, 637, 573, 420 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 12.67 (s, 1H), 11.81 (s, 1H), 8.17 (d, J = 1.9 Hz, 1H),
8.03 (dd, J = 9.0, 2.3 Hz, 1H), 7.95 (dd, J = 8.9, 2.2 Hz, 1H), 7.84 (d, J = 7.2 Hz, 2H), 7.74 (d,
J = 9.0 Hz, 2H), 7.57 (d, J = 8.9 Hz, 1H), 7.50 (t, J = 7.4 Hz, 1H), 7.44 (d, J = 7.8 Hz, 1H),
7.30 (td, J = 7.6, 0.7 Hz, 1H), 5.64 (s, 1H) ppm;
13C NMR (75 MHz, DMSO-d6): δ = 152.3, 146.5, 143.9, 140.8, 140.1, 139.9, 133.2, 127.6,
127.5, 126.6, 125.5, 125.3, 122.7, 118.9, 116.5, 116.3, 115.5, 115.3, 115.2, 114.4, 113.0, 112.2,
42.8 ppm;
HRMS (ESI): Calcd. for C23H13N4O4: [M-H]+ 409.0937, found: 409.0940.
Methyl
10-(4-(Methoxycarbonyl)-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole-9-carboxylate(
2i)
Yellow solid; m.p. 262.1–263.2 °C;
IR (KBr): ν = 3402, 3290, 2950, 2358, 1693, 1506, 1434, 1348, 1263, 1139, 923, 800, 739,
473 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 12.14 (s, 1H), 11.08 (s, 1H), 7.79 (d, J = 7.9 Hz, 1H),
7.74 (d, J = 7.2 Hz, 1H), 7.66–7.57 (m, 3H), 7.29–7.14 (m, 4H), 7.08 (t, J = 7.2 Hz, 1H), 6.39
(s, 1H), 6.24 (s, 1H) ppm;
13C NMR (70 MHz, DMSO-d6): δ = 168.9, 168.3, 154.5, 145.6, 141.9, 138.0, 132.5, 126.5,
125.9, 124.3, 124.0, 123.5, 123.4, 123.1, 122.8, 122.4, 122.3, 121.2, 120.3, 119.9, 118.6,
117.1, 116.6, 115.8, 52.2, 51.1, 42.4 ppm;
HRMS (ESI): Calcd. for C27H19N2O4: [M-H]+ 435.1345, found: 435.1344.
10-(4-Cyano-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole-9-carbonitrile(2j)
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ACCEPTED MANUSCRIPT
white solid; m.p. 286.4–287.9 °C;
IR (KBr): ν = 3266, 2922, 2852, 2221, 1609, 1510, 1343, 1322, 1142, 1050, 787, 738, 605
cm-1;
1H NMR (400 MHz, DMSO-d6) δ = 12.43 (s, 1H), 11.45 (s, 1H), 7.87 (d, J = 8.1 Hz, 1H),
7.76 (d, J = 8.2 Hz, 1H), 7.73–7.66 (m, 2H), 7.45 (d, J = 7.4 Hz, 2H), 7.37 (t, J = 7.4 Hz, 1H),
7.30 (t, J = 7.8 Hz, 1H), 7.27–7.19 (m, 2H), 6.76 (s, 1H), 5.92 (s, 1H). ppm;
13C NMR (100 MHz, CDCl3): δ = 154.0, 146.6, 140.9, 136.8, 132.2, 127.2, 126.8, 126.1,
125.9, 125.3, 125.2, 125.0, 124.0, 121.4, 121.0, 120.9, 119.9, 119.1, 118.8, 117.7,117.4, 113.4,
100.3, 99.8, 37.8 ppm;
HRMS (ESI): Calcd. for C25H13N4: [M-H]+ 369.1140, found: 369.1131.
3,5-Dimethyl-10-(1-methyl-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole(2k)
Pink solid; m.p. 158.5–159.7 °C;
IR (KBr): ν = 3382, 2921, 2072, 1638, 1529, 1372, 1226, 1193, 1153, 1011, 918, 798, 729,
421 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 7.69 (s, 1H), 7.52 (d, J = 8.3 Hz, 1H), 7.35 (d, J = 8.2 Hz,
1H), 7.21 (t, J = 8.5 Hz, 2H), 7.13–7.03 (m, 4H), 6.93 (dd, J = 16.4, 8.3 Hz, 2H), 6.84 (t, J =
7.4 Hz, 1H), 5.24 (s, 1H), 4.13 (s, 3H), 3.70 (s, 3H), 2.40 (s, 3H) ppm;
13C NMR (75MHz, DMSO-d6): δ = 150.0, 143.2, 141.6, 137.0, 136.0, 134.2, 127.1, 126.7,
125.8, 124.8, 124.0, 123.3, 121.0, 120.9, 119.3, 119.0, 118.9, 118.5, 118.3, 112.5, 110.5, 109.7,
32.3, 31.1, 21.2 ppm;
HRMS (ESI): Calcd. for C26H21N2: [M-H]+ 361.1705, found: 361.1701.
3-Fluoro-5-methyl-10-(1-methyl-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole(2l)
white solid; m.p. 208.5–209.7 °C;
IR (KBr): ν = 3387, 3290, 2900, 1670, 1489, 1226, 1007, 934, 778, 727 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 7.89-7.84 (m, 1H), 7.54 (d, J = 8.3 Hz, 1H), 7.37 (d, J =
8.2 Hz, 1H), 7.20 (d, J = 7.7 Hz, 2H), 7.17-7.06 (m, 5H), 6.93 (t, J = 7.5 Hz, 1H), 6.86 (t, J =
7.5 Hz, 1H), 5.32 (s, 1H), 4.11 (s, 3H), 3.72 (s, 3H). ppm;
13C NMR (75MHz, DMSO-d6): δ = 155.7, 142.3, 141.5, 137.0, 130.5, 127.3, 126.6, 123.5,
123.2, 121.1, 120.9, 119.4, 118.8, 118.5, 113.6, 113.3, 113.1, 112.7, 111.6, 110.6, 109.8, 32.3,
31.0 ppm;
HRMS (ESI): Calcd. for C25H19FN2Na: [M+Na]+ 389.1430, found: 389.1433.
10-(2-Phenyl-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole(2m)
Brown solid; m.p. 275.8–277.0 °C.
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ACCEPTED MANUSCRIPT
IR (KBr): ν = 3400, 3053, 2923, 2851, 1702, 1607, 1455, 1243,1007, 844, 772, 735, 701, 608,
489 cm-1;
1H NMR (400 MHz, DMSO-d6) δ = 11.71 (s, 1H), 11.34 (s, 1H), 7.99 (d, J = 7.3 Hz, 2H),
7.70–7.61 (m, 3H), 7.52–7.42 (m, 2H), 7.36 (t, J = 7.5 Hz, 1H), 7.27 (d, J = 8.1 Hz, 1H), 7.21
(d, J = 7.3 Hz, 1H), 7.13–7.05 (m, 2H), 7.01 (t, J = 8.2 Hz, 1H), 6.89–6.82 (m, 2H), 6.44 (t, J
= 7.6 Hz, 1H), 6.05 (d, J = 7.8 Hz, 1H), 5.39 (s, 1H) ppm;
13C NMR (75MHz, DMSO-d6): δ = 152.6, 142.6, 140.8, 136.6, 136.2, 134.6, 133.0, 129.1,
128.8, 127.8, 127.1, 126.5, 125.2, 125.0, 124.6, 123.7, 121.2, 121.0, 119.3, 119.0, 118.3,
118.0, 118.0, 112.6, 111.2, 109.1 ppm;
HRMS (ESI): Calcd. for C29H20N2Na: [M+Na]+ 419.1524, found: 419.1530.
6-Methyl-10-(2-phenyl-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole(2n)
Pale yellow solid; m.p. 85.6–87.8 °C.
IR (KBr): ν = 3409, 3051, 2928, 2851, 1605, 1455, 1444, 1301, 761, 738, 699 cm-1;
1H NMR (400 MHz, DMSO-d6) δ = 11.52 (s, 1H), 11.30 (s, 1H), 7.99 (d, J = 7.2 Hz, 2H),
7.76 (d, J = 7.2 Hz, 1H), 7.63 (t, J = 6.5 Hz, 2H), 7.48 (t, J = 7.3 Hz, 1H), 7.37 (t, J = 7.2 Hz,
1H), 7.27 (d, J = 7.8 Hz, 1H), 7.20 (d, J = 7.0 Hz, 1H), 7.09 (t, J = 6.7 Hz, 1H), 6.92–6.80 (m,
3H), 6.74 (t, J = 7.5 Hz, 1H), 6.44 (t, J = 7.2 Hz, 1H), 6.08 (d, J = 7.7 Hz, 1H), 5.38 (s, 1H),
2.53 (s, 3H) ppm;
13C NMR (75MHz, DMSO-d6): δ = 152.5, 142.3, 140.2, 136.5, 136.2, 134.8, 133.0, 129.0,
128.7, 127.8, 127.0, 126.5, 125.1, 125.0, 124.9, 123.3, 121.6, 121.5, 121.1, 119.3, 119.0,
118.2, 118.0, 115.7, 111.1, 109.1, 28.5, 17.0 ppm;
HRMS (ESI): Calcd. for C30H22N2Na: [M+Na]+ 433.1681, found: 433.1673.
HN
Ph
H3COOC
N
H
Methyl 10-(2-phenyl-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole-7-carboxylate(2o)
Pink solid; m.p. 287.5–290.0 °C.
IR (KBr): ν = 3139, 2924, 2787, 1724, 1614, 1415, 1299, 1274, 1236, 1126, 810, 792, 764
cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 12.18 (s, 1H), 11.37 (s, 1H), 8.09 (s, 1H), 7.98 (d, J =
7.8 Hz, 2H), 7.77 (d, J = 7.6 Hz, 1H), 7.64 (t, J = 7.6 Hz, 2H), 7.49 (t, J = 8.3 Hz, 2H), 7.41 (t,
J = 7.2 Hz, 1H), 7.26 (dd, J = 13.1, 7.8 Hz, 2H), 7.18 (t, J = 7.4 Hz, 1H), 7.11 (d, J = 8.3 Hz,
1H), 6.86 (t, J = 7.6 Hz, 1H), 6.43 (t, J = 7.5 Hz, 1H), 6.01 (d, J = 8.0 Hz, 1H), 5.45 (s, 1H),
3.81 (s, 3H) ppm;
13C NMR (75MHz, DMSO-d6): δ = 167.1, 153.1, 146.4, 140.0, 136.7, 136.2, 133.7, 132.9,
129.1, 128.8, 127.9, 127.3, 126.9, 126.4, 126.3, 125.2, 124.7, 121.5, 121.2, 120.3, 118.9,
118.7, 118.4, 117.6, 114.3, 111.2, 108.5, 104.8, 51.8 ppm;
HRMS (ESI): Calcd. for C31H22N2NaO2: [M+Na]+ 477.1579, found: 477.1584.
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ACCEPTED MANUSCRIPT
10-(2-Methyl-1H-indol-3-yl)-7-nitro-5,10-dihydroindeno[1,2-b]indole(2p)
Yellow solid; m.p. 286.6–287.2 °C.
IR (KBr): ν = 3452, 3294, 1503, 1459, 1326, 1304, 1133, 1097, 763, 739 cm-1;
1H NMR (400 MHz, DMSO-d6) δ = 12.53 (s, 1H), 10.95 (s, 1H), 7.99-7.91 (m, 2H), 7.74 (d, J
= 4.7 Hz, 1H), 7.65 (d, J = 8.2 Hz, 1H), 7.40 (s, 1H), 7.26–7.14 (m, 3H), 6.74 (t, J = 6.3 Hz,
1H), 6.35 (t, J = 6.5 Hz,1H), 5.85 (d, J = 6.7 Hz, 1H), 5.35 (s, 1H), 2.82 (s, 3H).
13C NMR (75MHz, DMSO-d6): δ = 153.1, 146.4, 143.9, 140.6, 135.5, 133.6, 133.5, 127.1,
126.3, 126.2, 126.1, 125.3, 122.9, 119.8, 118.6, 117.8, 117.5, 116.1, 114.2, 112.8, 110.5, 107.0,
38.3, 11.7 ppm;
HRMS (ESI): Calcd. for C24H17N3NaO2: [M+Na]+ 402.1218, found: 402.1221.
Methyl 10-(2-methyl-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole-7-carboxylate(2q)
Gray solid; m.p. 242.7–244.8 °C.
IR (KBr): ν = 3387, 3310, 3056, 2945, 1694, 1616, 1460, 1434, 1347, 1272, 1217, 1089, 758,
729, 613 cm-1;
1H NMR (400 MHz, DMSO-d6) δ = 12.08 (s, 1H), 10.88 (s, 1H), 8.09 (s, 1H), 7.75 (d, J = 6.6
Hz, 1H), 7.51 (d, J = 7.7 Hz, 1H), 7.40 (t, J = 6.6 Hz, 1H), 7.27–7.09 (m, 4H), 6.74 (t, J = 6.2
Hz, 1H), 6.35 (t, J = 6.5 Hz, 1H), 5.84 (d, J = 6.8 Hz, 1H), 5.29 (s, 1H), 3.82 (s, 3H), 2.79 (s,
3H) ppm;
13C NMR (75MHz, DMSO-d6): δ = 167.1, 153.4, 146.3, 140.0, 135.4, 133.8, 133.4, 127.2,
127.0, 126.2, 126.1, 125.4, 125.1, 124.9, 121.4, 120.2, 119.7, 118.7, 117.7, 114.2, 110.3,
107.4, 51.8, 11.7 ppm;
HRMS (ESI): Calcd. for C26H20N2NaO2: [M+Na]+ 415.1422, found: 415.1423.
and
10-(5-Nitro-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole (2ra) and 10-(1H-indol-3-yl)
-8-nitro-5,10-dihydroindeno[1,2-b]indole (2rb)
Yellow solid; m.p. 210.2–212.3 °C.
IR (KBr): ν = 3407, 3292, 3049, 2921, 1618, 1508, 1455, 1328, 1102, 813, 761, 738 cm-1;
Characterized as a 1.1:1 mixture. 1H NMR (400 MHz, DMSO-d6): δ = 12.55 (s, 1H), 11.77 (s,
S9

ACCEPTED MANUSCRIPT
1H), 8.10 (s, 1H), 7.97 (d, J = 9.1 Hz, 1H), 7.89 (d, J = 9.1 Hz, 1H), 7.52–7.45 (m, 2H),
7.44–7.37 (m, 3H), 7.25–7.18 (m, 2H), 7.14 (t, J = 7.4 Hz, 1H), 6.99 (t, J = 7.4 Hz, 1H), 5.45
1
(s, 1H). Isomer H NMR (400 MHz, DMSO-d6): 11.70 (s, 1H), 10.97 (s, 1H), 7.80 (s, 1H),
7.73 (d, J = 7.3 Hz, 1H), 7.70–7.64(m, 2H), 7.62 (m, 1H), 7.37–7.30 (m, 3H), 7.06 (t, J = 7.5
Hz, 1H), 6.93–6.86 (m, 2H), 6.76 (t, J = 7.5 Hz, 1H), 5.43 (s, 1H) ppm;
13C NMR (75MHz, DMSO-d6): mixture of 2qa and 2qb δ = 153.0, 152.1, 146.4, 143.9, 142.7,
140.8, 140.7, 140.0, 139.9, 136.7, 134.3, 133.3, 127.3, 127.2, 127.2, 126.3, 126.1, 126.1,
125.3, 125.3 ,125.0, 123.8, 123.7, 123.4, 122.9, 121.1, 121.0, 119.4, 118.7, 118.5, 118.4,
118.2, 118.1, 116.4, 116.2, 116.1, 115.8, 114.5, 112.8, 112.6, 112.1, 112.0, 111.7 ppm;
HRMS (ESI): Calcd. for C23H14N3O2: [M-H]+ 364.1086, found: 364.1099.
11-Methyl-6-(1-methyl-1H-indol-3-yl)-11H-benzo[a]carbazol-5-ol (4a)
Pale yellow solid; m.p.208.5–209.9 °C.
IR (KBr): ν = 3500, 3050, 2939, 1592, 1474, 1398, 1325, 1223, 1205, 1076, 984, 891, 770,
744 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 8.86 (d, J = 7.8 Hz, 1H), 8.44 (d, J = 6.9 Hz, 1H), 8.12 (s,
1H), 7.66 (d, J = 6.8 Hz, 2H), 7.61 (d, J = 6.6 Hz, 2H), 7.55 (s, 1H), 7.30–7.18 (m, 2H),
7.03–6.88 (m, 2H), 6.68–6.78 (m, 2H), 4.41 (s, 3H), 3.98 (s, 3H) ppm;
13C NMR (75MHz, DMSO-d6): δ = 144.2, 140.7, 137.1, 129.8, 129.5, 128.2, 125.4, 125.2,
124.2, 123.9, 123.7, 122.3, 122.3, 122.1, 121.3, 119.7, 119.0, 118.4, 118.1, 110.0, 109.2,
108.1, 34.0, 32.8 ppm;
HRMS (ESI): Calcd. for C26H20N2NaO: [M+Na]+ 399.1473, found: 399.1479.
Ph
N
OH
N
Ph
11-phenyl-6-(1-phenyl-1H-indol-3-yl)-11H-benzo[a]carbazol-5-ol (4b)
Pale yellow solid; m.p. 78.9–80.6°C.
IR (KBr): ν = 3053, 3052, 2957, 2922, 2851, 1720, 1454, 1282, 1209, 1125, 1038, 741, 694,
593 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 8.54 (s, 1H), 8.43 (d, J = 9.1 Hz, 1H), 7.95 (s, 1H),
7.83–7.78 (m, 3H), 7.73–7.64 (m, 5H), 7.55–7.43 (m, 4H), 7.37 (d, J = 9.1 Hz, 1H),
7.32–7.28 (m, 2H), 7.23–7.18 (m, 2H), 7.07 (t, J = 7.3 Hz, 1H), 7.02 (d, J = 7.8 Hz, 1H), 6.92
(d, J = 8.6 Hz, 1H), 6.82 (t, J = 7.3 Hz, 1H) ppm;
13C NMR (100MHz, DMSO-d6): δ = 145.2, 142.0, 139.8, 139.3, 135.7, 131.7, 131.5, 130.4,
129.9, 129.5, 129.4, 129.0, 128.8, 128.6, 126.4, 125.4, 125.2, 124.5, 124.4, 124.1, 124.0,
123.0, 122.7, 121.5, 121.4, 121.2, 120.3, 120.3, 119.3, 119.2, 111.3, 110.7, 109.8, 109.3 ppm;
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ACCEPTED MANUSCRIPT
HRMS (ESI): Calcd. for C36H23N2O: [M-H]+ 499.1810, found: 499.1805.
11-benzyl-6-(1-benzyl-1H-indol-3-yl)-11H-benzo[a]carbazol-5-ol (4c)
Pale green solid; m.p. 89.1–91.6°C.
IR (KBr): ν = 3481, 3052, 3028, 2921, 2850, 1717, 1674, 1566, 1464, 1355, 1141, 1073, 935,
767, 739, 667 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 8.85 (d, J = 8.5 Hz, 1H), 8.58 (d, J = 4.9 Hz, 2H), 8.38
(d, J = 8.3 Hz, 1H), 7.77 (t, J = 7.5 Hz, 1H), 7.51 (t, J = 7.6 Hz, 1H), 7.45 (d, J = 8.3 Hz, 1H),
7.39–7.35 (m, 2H), 7.29–7.18 (m, 5H), 7.15–7.06 (m, 7H), 6.95 (t, J = 7.4 Hz, 1H), 6.63–6.58
(m, 2H), 5.40 (d, J = 15.9 Hz, 1H), 5.28 (d, J = 15.6 Hz, 1H), 5.17 (d, J = 17.0 Hz, 1H), 4.95
(d, J = 16.9 Hz, 1H) ppm;
13C NMR (100MHz, DMSO-d6): δ = 151.3, 139.7, 138.5, 138.4, 137.8, 136.1, 131.5, 130.2,
129.5, 129.3, 128.4, 128.1, 127.5, 127.2, 127.0, 126.6, 125.4, 123.8, 123.4, 122.7, 122.6,
122.3, 121.7, 121.3, 120.6, 120.2, 119.6, 119.1, 110.5, 110.2, 108.5, 105.4, 102.5, 49.5, 46.0
ppm;
HRMS (ESI): Calcd. for: C38H27N2O: [M-H]+ 527.2123, found: 527.2118.
6-(1,7-dimethyl-1H-indol-3-yl)-10,11-dimethyl-11H-benzo[a]carbazol-5-ol (4d)
Pale yellow solid; m.p. 204.6–206.2°C.
IR (KBr): ν = 3486, 2958, 2922, 2851, 1732, 1600, 1449, 1374, 1261, 1105, 755, 745, 736
cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 8.62 (d, J = 8.4 Hz, 1H), 8.39 (d, J = 8.3 Hz, 1H), 8.00 (s,
1H), 7.66 (t, J = 7.1 Hz, 1H), 7.58 (t, J = 7.5 Hz, 1H), 7.40 (s, 1H), 7.01–6.96 (m, 1H), 6.88
(d, J = 6.3 Hz, 1H), 6.79–6.70 (m, 2H), 6.65–6.58 (m, 2H), 4.39 (s, 3H), 4.21 (s, 3H), 2.86 (s,
3H), 2.81 (s, 3H) ppm;
13C NMR (100MHz, DMSO-d6): δ = 144.8, 142.3, 135.6, 132.2, 131.2, 129.3, 127.1, 125.2,
124.3, 124.1, 123.8, 123.7, 122.7, 121.8, 121.3, 120.9, 119.3, 119.1, 118.9, 117.8, 109.7,
107.6, 37.9, 36.5, 20.3, 19.3 ppm;
HRMS (ESI): Calcd. for C28H23N2O: [M-H]+ 403.1810, found: 403.1805.
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ACCEPTED MANUSCRIPT
8-methoxy-6-(5-methoxy-1-phenyl-1H-indol-3-yl)-11-phenyl-11H-benzo[a]carbazol-5-ol
(4e)
Pale red solid; m.p. 242.0–243.8°C.
IR (KBr): ν = 3478, 2957, 1928, 2845, 1709, 1586, 1449, 1260, 1245, 1055, 1016, 759, 749,
708 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 8.58 (s, 1H), 8.42 (d, J = 8.3 Hz, 1H), 7.90 (s, 1H),
7.77–7.62 (m, 9H), 7.52–7.40 (m, 3H), 7.37 (d, J = 8.5 Hz, 1H), 7.29 (t, J = 8.3 Hz, 1H),
6.99–6.90 (m, 2H), 6.83 (d, J = 8.9 Hz, 1H), 6.67 (s, 1H), 6.33 (s, 1H), 3.57 (s, 3H), 3.20 (s,
3H) ppm;
13C NMR (100MHz, DMSO-d6): δ = 154.4, 153.0, 144.9, 140.1, 139.4, 137.3, 131.5, 130.7,
130.4, 130.2, 130.1, 129.9, 129.2, 128.7, 128.6, 126.2, 125.5, 125.2, 124.3, 123.9, 123.5,
123.2, 121.6, 121.5, 119.1, 113.9, 112.4, 111.5, 111.1, 110.5, 109.2, 103.5, 102.2, 55.4, 54.4
ppm;
HRMS (ESI): Calcd. for C38H27N2O3: [M-H]+ 559.2022, found: 559.2016.
8-methyl-6-(5-methyl-1-phenyl-1H-indol-3-yl)-11-phenyl-11H-benzo[a]carbazol-5-ol (4f)
White solid; m.p. 235.7–237.1°C.
IR (KBr): ν = 3467, 3066, 2958, 2918, 2852, 1727, 1593, 1476, 1397, 1285, 1212, 1076, 789,
704 cm-1;
1H NMR (400 MHz, DMSO-d6): δ = 8.48 (s, 1H), 8.41 (d, J = 8.5 Hz, 1H), 7.87 (s, 1H),
7.78–7.64 (m, 9H), 7.53–7.42 (m, 3H), 7.35 (d, J = 8.3 Hz, 1H), 7.30–7.25 (m, 1H), 7.13 (d, J
= 8.6 Hz, 1H), 7.03 (d, J = 4.8 Hz, 2H), 6.91 (d, J = 8.4 Hz, 1H), 6.74 (s, 1H), 2.29 (s, 3H),
2.07 (s, 3H) ppm;
13C NMR (100MHz, DMSO-d6): δ = 145.1, 140.5, 140.0, 139.5, 134.1, 131.7, 130.4, 129.9,
129.7, 129.6, 129.0, 128.8, 128.7, 128.6, 128.6, 127.6, 126.2, 125.8, 125.3, 125.1, 124.2,
124.2, 123.8, 123.7, 123.2, 121.5, 121.4, 121.0, 119.8, 119.1, 111.2, 110.4, 109.6, 109.6, 21.2,
20.9 ppm;
HRMS (ESI): Calcd. for C38H27N2O: [M-H]+ 527.2123, found: 527.2118.
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ACCEPTED MANUSCRIPT
The 1H NMR and 13C NMR charts of products
5-Methyl-10-(1-methyl-1H-indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole(2a)
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ACCEPTED MANUSCRIPT
10-(1H-Indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole (2b)
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ACCEPTED MANUSCRIPT
8-Methyl-10-(5-methyl-1H-indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole(2c)
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ACCEPTED MANUSCRIPT
7-Methyl-10-(6-methyl-1H-indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole(2d)
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ACCEPTED MANUSCRIPT
6-Methyl-10-(7-methyl-1H-indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole(2e)
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ACCEPTED MANUSCRIPT
8-Methoxy-10-(5-methoxy-1H-indol-3-yl)-5,10-dihydro-indeno[1,2-b]indole(2f)
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ACCEPTED MANUSCRIPT
8-Nitro-10-(5-nitro-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole(2h)
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ACCEPTED MANUSCRIPT
Methyl 10-(4-(Methoxycarbonyl)-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole-9-carb
-oxylate(2i)
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ACCEPTED MANUSCRIPT
10-(4-Cyano-1H-indol-3-yl)-5,10-dihydroindeno[1,2-b]indole-9-carbonitrile(2j)
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