Palladium-catalyzed cyclocarbonylation of cyclic diaryliodoniums: Synthesis of fluorenones

Article abstract of DOI:10.1002/aoc.3817

An efficient approach to the synthesis of fluorenones via the palladium-catalyzed cyclocarbonylation of cyclic diaryliodoniums was developed. Our route enables facile access to fluorenones with various substituents in modest to high yields.

Full text of DOI:10.1002/aoc.3817

Received: 31 October 2016
DOI: 10.1002/aoc.3817
Revised: 18 January 2017
Accepted: 4 March 2017
F U L L PA P E R
Palladium‐catalyzed cyclocarbonylation of cyclic diaryliodoniums:
Synthesis of fluorenones
2
2
1
1
2
1
Li Liu | Jian Qiang | Shuhua Bai | Yang Li | Chunbao Miao | Jian Li
1
School of Pharmaceutical Engineering &
An efficient approach to the synthesis of fluorenones via the palladium‐catalyzed
cyclocarbonylation of cyclic diaryliodoniums was developed. Our route enables fac-
ile access to fluorenones with various substituents in modest to high yields.
Life Sciences, Changzhou University,
Changzhou 213164, People's Republic of
China
2
School of Petrochemical Engineering,
Changzhou University, Changzhou 213164,
People's Republic of China
KEYWORDS
cyclic diaryliodoniums, cyclocarbonylation, fluorenones
Correspondence
Jian Li, School of Pharmaceutical
Engineering & Life Sciences, Changzhou
University, Changzhou, 213164, P.R. China.
Email: lijianchem@cczu.edu.cn
Chunbao Miao, School of Petrochemical
Engineering, Changzhou University,
Changzhou, 213164, P.R. China.
Email: mcb@cczu.edu.cn
Funding Information
NSF of China, Grant/Award Number:
2
1402013; NSF of Jiangsu Province, Grant/
Award Number: BK20140259; Jiangsu Key
Laboratory of Advanced Catalytic Materials
[
15]
1
| INTRODUCTION
between cyclic dibenziodoniums and arylboronic acids.
Very recently, Shimizu reported that dibenziodolium triflates
smoothly react with potassium thioacetate in the presence of
CuCl to afford the corresponding dibenzothiophenes in good
Linear diaryliodonium salts have received much attention due
to their unique properties as electrophilic arylating reagents
in modern organic synthesis,
2
[1–7]
[16]
but all these reactions were
yields.
characterized by poor atom economy with generating one
equivalent of an iodoarene as waste. Cyclic diaryliodoniums
can avoid this problem because the iodoarenes remains as a
Due to their unique biological properties, fluorenones
have gained considerable attention in agricultural science
[
17–19]
and medicinal chemistry.
from the oxidation of fluorenes,
They can be accessible
[8]
[20,21]
part of the arylated product. Moreover, the iodoarenes
could go further transformation to provide more complicated
intramolecular acyla-
[
22]
tion of biarylcarboxylic acids,
cyclization of benzophe-
[9–11]
[23–27]
[28]
molecules under the same reaction conditions.
Recently,
none,
biphenyl‐2‐carbonitriles
and benzoic
[
29,30]
Detert, Nachtsheim and their coworkers disclosed Pd
catalyzed reaction of cyclic diphenyleneiodoniums with
anhydrides.
The Larock group developed a direct route
to fluorenones by palladium‐catalyzed cyclocarbonylation of
o‐halobiaryls, which Pd(PCy ) and anhydrous cesium
[12,13]
anilines to synthesis of carbazole derivatives.
In 2014,
3
2
[
31,32]
the group of Huang and Wen reported an atom and step
picalate were employed.
We wish to report at this time
economical three‐component reaction involving cyclic
a palladium‐catalyzed cyclocarbonylation of cyclic diary-
liodoniums which offers a highly efficient, atom‐economical
route to the fluoren‐9‐one skeleton.
[14]
diphenyleneiodoniums.
In 2015, the Liu group developed
palladium‐catalyzed double‐Suzuki‐Miyaura couplings
Appl Organometal Chem. 2017;e3817.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
1 of 7
https://doi.org/10.1002/aoc.3817

2
of 7
LIU ET AL.
2
| RESULTS AND DISCUSSION
120°C gave the best yield 97% (entry 18). Finally, the
effect of solvents was investigated (entries 19‐23), different
We first carried out a cyclocarbonylation reaction with
solvents including DMSO, MeCN, THF, CH OH and
3
cyclic diaryliodoniums 1a and carbon monoxide in the
toluene were employed, DCE was chosen as solvent. Thus,
our final optimal reaction conditions used 2 mol% Pd(OAc)2
and 5 mol % L5 in DCE at 120°C for 8 h.
presence of 2 mol % of Pd(OAc) in DCE at 100°C for 8
2
h. As shown in Table 1, the target product 2a was obtained
in 47% yield without ligand (entry 1). Other copper species
including Cu(OTf) , CuCl and CuI were examined (entries
With the optimal reaction conditions in hand, we first
explored the scope of cyclic iodoniums 1 (Table 2).
Under the reaction conditions, all the cyclic
diaryliodoniums provided the expected products at modest
to good yields. Use of cyclic diaryliodoniums bearing
electron‐withdrawing groups such as F and CF3 at the
3‐position afforded the corresponding fluorenones 2b
and 2d in high yields, respectively (Table 2). Substrates
with electron‐donating groups such as Me, OMe and Et
in the 3‐position gave lower yields (2e, 2f, 2g). Substrates
with 4‐position substituents 1h, 1i and lj also reacted
smoothly to afford 2h, 2i and 2j in modest yields,
respectively. The scope of the reaction was further
extended to di‐substituted diaryliodoniums. The salts bear-
ing two functional groups in the same side or different
side were also converted into the desired products
smoothly (2k‐2n). Next, we investigated whether hetero-
cyclic cyclic diaryliodoniums could be reacted in the
cyclocarbonylation. To our delight, cyclic diaryliodoniums
bearing thiophene also gave the expected fluorenones in
modest yields (2o and 2p).
2
2
2‐4), they all provided low yields. It seemed that ligand
favored the reaction, the desired product 2a was obtained
in the presence of 5 mol % of L1 (PPh ). Then, a screen-
3
ing of ligands was carried out (entries 6‐14), and the
results indicated that L5 (1,10‐phenanthroline) was the
most effective ligand and gave 2a in a 79% isolated yield
(entry 11). Our further studies indicated that heating at
a
TABLE 1 Optimization of reaction conditions
entry catalyst
Pd(OAc)
Cu(OTf)
ligand solvent
temp (°C) yield (%)b
1
2
3
4
5
6
7
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
none
none
none
none
none
L1
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DMSO
MeCN
THF
100
100
100
100
100
100
100
100
100
100
100
100
100
25
47
12
1
2
CuCl
CuI
2
9
FeCl
3
5
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
2
2
2
2
2
2
2
2
2
2
2
46
62
59
68
79
74
35
25
5
TABLE 2 Palladium‐catalyzed cyclocarbonylation of cyclic
a,b
L2
diaryliodoniums
L3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
L4
L5
L6
L7
L8
L5
L5
80
32
79
97
32
40
87
68
91
L5
100
120
120
120
120
120
120
Pd(OAc)
2
L5
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
2
L5
2
L5
2
2
2
L5
L5
3
CH OH
L5
Toluene
a
a
Reaction conditions: 1a (0.2 mmol), CO (1 atm), catalyst (2 mol%), ligand (5 mol%)
Reaction conditions: 1 (0.2 mmol), CO (1 atm), Pd(OAc) (2 mol%), L5 (5 mol%)
2
in solvents (2 mL), 8 h.
in DCE (2 mL), 120 °C, 8 h.
b
b
Isolated yields.
Isolated yields.

LIU ET AL.
3 of 7
It is notable that complicated cyclic diaryliodonium
including phenanthrene skeleton was well tolerated in the
reaction, providing 2q in 65% yield (Scheme 1), which could
be utilized in the synthesis of optoelectronic materials.
Furthermore, the cyclocarbonylation of 2‐Iodobiphenyl
under the optimal reaction conditions was also investigated,
the reaction provided fluorenone in only 5% yield
SCHEME
diaryliodonium
1
Cyclocarbonylation of phenanthrene skeleton
(Scheme 2).
To further explore the synthetic versatility of the
cyclocarbonylation reaction, we examined the scope of
indole cyclic diaryliodonium.
It is regretful that indole cyclic diaryliodoniums were not
obtained from 1‐(2‐iodophenyl)‐1H‐indole 3a under
[
33]
traditional synthesis procedure.
However, to our satisfac-
SCHEME 2 Cyclocarbonylation of 2‐Iodobiphenyl
tion, combining the cyclic diaryliodonium syntheses and
cyclocarbonylation, one pot strategy was used, the
corresponding product 10H‐indolo[1,2‐a]indol‐10‐one 4a
was obtained in 61% yield. To explore the general utility of
this method, a variety of nitrogenous heterocyclic compounds
were investigated for this transformation. It appears that all
the substrates were found to perform well in the reaction
a,b
TABLE 3 One‐pot strategy of cyclocarbonylation of o‐iodobiaryls
(Table 3).
Finally, we proposed a possible reaction mechanism for
this palladium‐catalyzed cyclocarbonylation of cyclic
diaryliodoniums (Scheme 3). Initially, oxidative addition of
the cyclic diaryliodonium to Pd (0) to form palladium
species A, CO insertion to generate the palladium
intermediate B. A further oxidative addition of the neighbor-
ing aryl C‐I to the palladium to formation of a Pd(IV)
intermediate C and subsequent elimination of ligand and
iodine anion to generate intermediate D, and the final product
fluorenone is obtained from reductive elimination of the
ketone with simultaneous regeneration of the Pd(0)
a
Reaction conditions: 3 (0.2 mmol), mCPBA (0.3 mmol), CO (1 atm), Pd(OAc)
2 mol%), L5 (5 mol%) in DCE (2 mL), 120 °C, 8 h.
2
(
b
Isolated yields.
[
31,32]
catalyst.
3
| CONCLUSION
In summary, we developed a direct route to fluorenones
by palladium‐catalyzed cyclocarbonylation of cyclic
SCHEME 3 Proposed mechanism

4
of 7
LIU ET AL.
diaryliodoniums with CO. The reaction outcomes provide
straightforward access to synthetically and medicinally
fluorenone derivatives in up to 97% yield. In addition, one
pot strategy was developed from 1‐(2‐iodophenyl)‐1H‐indole
to syntheses indolo fluorenones in modest yields via the
formation of cyclic diaryliodoniums. Further studies to
extend the scope and synthetic utility for synthesis of
substituted fluorenones are in progress in our laboratory.
4.2.3 | 2‐chloro‐9H‐fluoren‐9‐one 2c
yellow solid; (38.5 mg, 90%); H NMR (300 MHz, CDCl )
1
3
δ 7.69 – 7.59 (m, 2H), 7.56 – 7.41 (m, 4H), 7.39 – 7.28
13
(
m, 1H). C NMR (75 MHz, CDCl ) δ 192.5, 143.6,
3
1
42.6, 135.6, 135.1, 134.2, 129.3, 124.7, 121.4, 120.4.
4
.2.4 | 2‐(trifluoromethyl)‐9H‐fluoren‐9‐one 2d
1
yellow solid; (46.6 mg, 94%); H NMR (300 MHz, CDCl )
3
4
| EXPERIMENTAL
.1 | General procedure
δ 7.96 – 7.85 (m, 1H), 7.74 (ddt, J = 13.2, 7.4, 0.9 Hz, 2H),
13
7
.68 – 7.52 (m, 3H), 7.39 (td, J = 7.3, 1.4 Hz, 1H).
C
4
NMR (75 MHz, CDCl
) δ 191.8, 147.4, 142.9, 135.0,
3
1
34.2, 131.5, 130.1, 124.4, 121.1, 120.5, 53.6.
Various reagents were purchased from Aldrich, Acros or
Alfa. The cyclic diaryliodonium 1,
indole 3
Flash column chromatography was performed using silica
gel (200–300 mesh). Analytical thin‐layer chromatography
was performed using glass plates pre‐coated with 200–300
mesh silica gel impregnated with a fluorescent indicator
[34]
iodophenyl‐1H‐
[
35]
were prepared according to literature procedure.
4.2.5 | 2‐methyl‐9H‐fluoren‐9‐one 2e
1
yellow solid; (33.0 mg, 85%); H NMR (300 MHz, CDCl )
3
δ 7.62 (dt, J = 7.3, 1.0 Hz, 1H), 7.50 – 7.34 (m, 4H), 7.31
13
–
7.21 (m, 2H), 2.37 (s, 3H, ‐CH3). C NMR (75 MHz,
CDCl ) δ 194.3, 144.6, 141.8, 139.3, 135.1, 134.6, 134.3,
1
13
3
(254 nm). H NMR and C NMR spectra were recorded
1
28.6, 125.0, 124.2, 120.1, 21.5.
on Bruker 300 (300 MHz) or 500 (500 MHz) spectrometer,
using CDCl as solvent and TMS as an internal reference.
3
4
.2.6 | 2‐methoxy‐9H‐fluoren‐9‐one 2f
1
yellow solid; (27.3 mg, 65%); H NMR (300 MHz, CDCl ) δ
4
.2 | Typical procedure for cyclocarbonylation
3
7
.60 (t, J = 7.5 Hz, 1H), 7.47 – 7.38 (m, 3H), 7.24 – 7.16 (m, 2
13
of cyclic diaryliodoniums
H), 6.98 (dd, J = 8.2, 2.5 Hz, 1H), 3.86 (s, 3H, ‐OCH3).
NMR (75 MHz, CDCl ) δ 193.9, 160.8, 144.9, 136.9,
C
In the pressure tube, a solution of cyclic diaryliodonium 1
3
(0.2 mmol), Pd(OAc) (0.004 mmol) and ligand (0.01 mmol)
2
1
35.8, 134.9, 124.3, 121.4, 120.3, 119.6, 109.3, 55.7.
in solvent (2 ml) was stirred at 120°C for 8 h under 1 atm of
CO. After completion of the reaction (observed on TLC), the
solvent was evaporated under reduced pressure to obtain the
crude mixture. The residues was purified by silica‐gel
column chromatography (Ethyl acetate / Petroleum ether
4
.2.7 | 2‐ethyl‐9H‐fluoren‐9‐one 2g
1
yellow solid; (21.2 mg, 51%); H NMR (300 MHz, CDCl )
δ 7.64 (dt, J = 7.3, 1.0 Hz, 1H), 7.54 – 7.38 (m, 4H), 7.34
3
=
1/50 ‐ 1/10) to afford the pure product 2. The obtained
–
2
7.29 (m, 1H), 7.28 – 7.23 (m, 1H), 2.67 (t, J = 7.6 Hz,
1 13
product was analyzed by H NMR and C NMR.
13
H, ‐CH ‐), 1.26 (t, J = 7.6 Hz, 3H, ‐CH ). C NMR (75
2
3
MHz, CDCl ) δ 194.3, 145.7, 144.6, 142.1, 134.6, 134.1,
3
1
28.6, 124.3, 123.9, 120.0, 28.8, 15.4.
4
.2.1 | 9H‐fluoren‐9‐one 2a
1
yellow solid; (35.0 mg, 97%); H NMR (300 MHz, CDCl )
δ 7.66 (dt, J = 7.4, 1.0 Hz, 2H), 7.55 – 7.45 (m, 4H), 7.29
3
4
.2.8 | 3‐fluoro‐9H‐fluoren‐9‐one 2h
1
3
1
(td, J = 7.2, 1.7 Hz, 2H). C NMR (75 MHz, CDCl ) δ 194.0,
3
yellow solid; (22.6 mg, 57%); H NMR (300 MHz,
CDCl ) δ 7.71 – 7.58 (m, 2H), 7.54 – 7.43 (m, 2H),
144.4, 134.7, 134.1, 129.1, 124.3, 120.3.
3
7
2
.32 (ddd, J = 7.3, 6.6, 1.9 Hz, 1H), 7.17 (dd, J = 8.3,
13
.2 Hz, 1H), 6.94 (ddd, J = 9.0, 8.1, 2.2 Hz, 1H).
C
4
.2.2 | 2‐fluoro‐9H‐fluoren‐9‐one 2b
NMR (75 MHz, CDCl ) δ 192.1, 168.9, 165.6, 147.5, 142.8,
134.7, 130.2, 129.8, 126.5, 124.3, 120.6, 115.4, 108.3.
3
1
yellow solid; (33.7 mg, 85%); H NMR (300 MHz, CDCl )
3
δ 7.56 (d, J = 7.2 Hz, 1H), 7.46 – 7.32 (m, 3H), 7.29 – 7.15
1
3
(
m, 2H), 7.07 (ddd, J = 8.9, 8.1, 2.5 Hz, 1H). C NMR
4
.2.9 | 3‐chloro‐9H‐fluoren‐9‐one 2i
(
1
1
75 MHz, CDCl ) δ 192.5, 163.5 (d, J = 245.2 Hz),
61.9, 143.9, 140.1, 135.1, 128.7 (d, J = 32.2 Hz),
24.6, 121.7, 121.0, 120.7, 120.1, 111.8 (d, J = 21.2 Hz).
3
1
yellow solid; (23.1 mg, 54%); H NMR (300 MHz, CDCl )
δ 7.68 (d, J = 7.2 Hz, 1H), 7.59 (d, J = 7.9 Hz, 1H), 7.51
3

LIU ET AL.
5 of 7
1
3
(
ddd, J = 5.6, 2.4, 1.3 Hz, 3H), 7.34 (ddd, J = 7.3, 5.4, 3.2
7.22 – 7.09 (m, 4H). C NMR (75 MHz, CDCl ) δ 187.4,
3
1
3
Hz, 1H), 7.30 – 7.26 (m, 1H). C NMR (75 MHz, CDCl3)
δ 192.5, 146.1, 143.1, 141.0, 134.8, 134.3, 132.4, 129.8,
159.1, 142.0, 138.8, 136.5, 133.9, 129.1, 128.6, 123.7,
121.5, 119.4.
129.0, 125.4, 124.6, 121.0, 120.0.
4
.2.16 | 7‐fluoro‐4H‐indeno[1,2‐b]thiophen‐4‐
4
.2.10 | 3‐methyl‐9H‐fluoren‐9‐one 2j
one 2p
1
1
yellow solid; (27.9 mg, 72%); H NMR (300 MHz, CDCl )
δ 7.64 (dd, J = 7.3, 1.0 Hz, 1H), 7.55 (d, J = 7.5 Hz, 1H),
3
yellow solid; (22.4 mg, 55%); H NMR (300 MHz, CDCl )
δ 7.44 (dd, J = 8.0, 5.1 Hz, 1H), 7.26 (d, J = 3.1 Hz, 1H),
3
13
7
.51 – 7.45 (m, 2H), 7.36 – 7.26 (m, 2H), 7.09 (d, J = 7.5
7
.14 (d, J = 4.9 Hz, 1H), 6.90 – 6.77 (m, 2H). C NMR
13
Hz, 1H), 2.43 (s, 3H, ‐CH3).
C NMR (75 MHz, CDCl3)
(75 MHz, CDCl ) δ 185.7, 167.7, 165.7, 156.5, 143.2,
3
δ 187.4, 159.1, 142.0, 138.8, 136.5, 133.9, 129.1, 128.6,
23.7, 121.5, 119.4.
1
41.5, 132.3, 130.1, 125.5, 121.6, 114.1, 108.4.
1
4
.2.17 | 9H‐indeno[1,2‐l]phenanthren‐9‐one 2q
4
.2.11 | 2,3‐dimethoxy‐9H‐fluoren‐9‐one 2k
1
yellow solid; (36.4 mg, 65%); H NMR (300 MHz, CDCl )
δ 9.25 (d, J = 7.5 Hz, 1H), 8.74 (d, J = 9.6 Hz, 1H), 8.64
3
1
yellow solid; (40.3 mg, 84%); H NMR (300 MHz, CDCl ) δ
3
7.52 (d, J = 8.0, 1H), 7.37 (dd, J = 8.0, 1H), 7.28 (d, J = 8.0
(dd, J = 13.6, 7.8 Hz, 2H), 8.06 (d, J = 7.6 Hz, 1H),
Hz, 1H), 7.17 (m, 2H), 6.96 (s, 1H), 3.99 ( s, 3H, ‐OCH ),
3
7
.83 – 7.59 (m, 5H), 7.54 – 7.45 (m, 1H), 7.32 (t, J = 7.0
1
3
3
1
1
.90 (s, 3H, ‐OCH3). C NMR (75 MHz, CDCl ) δ 193.2,
54.5, 149.7, 143.9, 139.4, 134.7, 134.2, 128.1, 126.8,
23.7, 119.1, 107.1, 103.4, 56.3, 56.2.
13
3
Hz, 1H). C NMR (75 MHz, CDCl ) δ 196.0, 144.7, 143.9,
3
1
1
37.7, 134.4, 134.0, 131.0, 129.3, 128.9, 128.4, 127.7,
27.4, 127.3, 126.1, 125.8, 125.3, 124.0, 123.6, 123.4, 122.7.
4
.2.12 | 2‐chloro‐6‐fluoro‐9H‐fluoren‐9‐one 2l
4
.3 | Typical procedure for one‐pot strategy of
1
yellow solid; (23.7 mg, 51%); H NMR (300 MHz, CDCl )
δ 7.52 (d, J = 7.2, 1.2, 0.7 Hz, 1H), 7.37 – 7.31 (m, 1H),
3
cyclocarbonylation of o‐iodobiaryls
1
3
In the pressure tube, a solution of o‐iodobiaryls 3 (0.2 mmol),
mCPBA (0.3 mmol), Pd(OAc) (0.004 mmol) and ligand
7
1
1
.22 – 7.09 (m, 4H). C NMR (75 MHz, CDCl ) δ 187.4,
59.1, 142.0, 138.8, 136.5, 133.9, 129.1, 128.6, 123.7,
21.5, 119.4.
3
2
(
0.01 mmol) in solvent (2 ml) was stirred at 120°C for 8 h
under 1 atm of CO. After completion of the reaction
observed on TLC), the solvent was evaporated under
(
4
.2.13 | 6‐fluoro‐2‐methyl‐9H‐fluoren‐9‐one 2m
reduced pressure to obtain the crude mixture. The residues
was purified by silica‐gel column chromatography
1
yellow solid; (31.4 mg, 74%); H NMR (300 MHz, CDCl )
δ 7.62‐7.60 (m, 2H), 7.45 (s, 1H), 7.35 (d, J = 7.8 Hz, 1H),
3
(Ethyl acetate / Petroleum ether = 1/50 ‐ 1/10) to afford the
pure product 4. The obtained product was analyzed by
7.29 (d, J = 7.8 Hz, 1H), 7.13 (d, J = 8.4 Hz, 1H), 6.90
1
13
1
3
H NMR, C NMR.
(m, 1H), 2.38 (s, 3H, ‐CH3). C NMR (75 MHz, CDCl ) δ
3
192.3, 168.6, 166.0, 147.7, 147.6, 140.1, 140.1, 135.1, 134.9,
1
30.3, 126.3, 125.0, 120.4, 115.1, 114.8, 108.2, 108.0, 21.4.
4
.3.1 | 10H‐indolo[1,2‐a]indol‐10‐one 4a
1
dark yellow solid; (26.7 mg, 61%); H NMR (300 MHz,
CDCl ) δ 7.68 – 7.56 (m, 2H), 7.58 ‐ 7.49 (m, 2H), 7.48
4
.2.14 | 6‐fluoro‐2‐methoxy‐9H‐fluoren‐9‐one 2n
3
13
1
–
7.35 (m, 2H), 7.19 – 7.05 (m, 3H). C NMR (75 MHz,
yellow solid; (27.4 mg, 60%); H NMR (300 MHz, CDCl )
δ 7.57 (ddd, J = 7.2, 1.2, 0.7 Hz, 1H), 7.34 – 7.31 (m, 1H),
3
CDCl ) δ 181.7, 145.6, 135.8, 135.6, 134.3, 132.6, 129.4,
3
1
28.1, 125.2, 123.9, 122.0, 111.4, 108.1.
7
.16 (m, 1H), 7.04 – 6.82 (m, 3H), 3.83 (s, 3H, ‐OCH ) .
3
1
3
C NMR (75 MHz, CDCl ) δ 191.9, 168.7, 166.1, 161.3,
3
1
1
47.9, 136.4, 135.1, 130.2, 126.3, 121.5, 120.0, 114.2,
14.0, 109.3, 107.8, 107.5.
4
4
.3.2 | 2‐bromo‐10H‐indolo[1,2‐a]indol‐10‐one
b
1
dark yellow solid; (27.9 mg, 47%); H NMR (300 MHz,
4
.2.15 | 4H‐indeno[1,2‐b]thiophen‐4‐one 2o
CDCl ) δ 7.83 (d, J = 1.9 Hz, 1H), 7.69 (dt, J = 7.5, 0.9
3
1
yellow solid; (25.3 mg, 68%); H NMR (300 MHz, CDCl )
δ 7.45 (ddd, J = 7.2, 1.2, 0.7 Hz, 1H), 7.37‐7.31 (m, 1H),
Hz, 1H), 7.60 – 7.51 (m, 2H), 7.47 – 7.35 (m, 2H),
3
13
7.18 – 7.07 (m, 2H). C NMR (125 MHz, CDCl ) δ 181.1,
3

6
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LIU ET AL.
1
1
45.3, 136.6, 135.7, 134.1, 132.7, 130.9, 129.2, 127.4,
25.4, 124.3, 115.0, 112.5, 111.4, 106.7.
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.3.3 | 3‐bromo‐10H‐indolo[1,2‐a]indol‐10‐
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one 4c
3
063.
1
yellow solid; (32.1 mg, 54%); H NMR (300 MHz, CDCl )
δ 7.66 – 7.58 (m, 2H), 7.51 – 7.43 (m, 2H), 7.31
3
[
[
7] V. V. Zhdankin, Wiley, Chichester, 2013.
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(dt, J = 8.0, 0.8 Hz, 1H), 7.22 ‐7.16 (m, 1H), 7.12 – 7.02
13
[9] P. S. Postnikov, O. A. Guselnikova, M. S. Yusubov, A.
(m, 2H). C NMR (125 MHz, CDCl ) δ 181.2, 145.1,
3
Yoshimura, V. N. Nemykin, V. V. Zhdankin, J. Org. Chem.
1
1
36.2, 135.7, 134.6, 131.4, 130.1, 129.3, 126.0, 125.5,
24.4, 122.1, 114.2, 111.5, 107.7.
2
015, 80, 5783.
[
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4
.3.4 | 3‐chloro‐10H‐indolo[1,2‐a]indol‐10‐one 4d
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P. Huang, S. Wen, Org. Lett. 2014, 16, 2350.
1
dark yellow solid; (32.9 mg, 65%); H NMR (300 MHz,
CDCl ) δ 7.62 – 7.59 (m, 1H), 7.54 – 7.46 (m, 3H), 7.30
[
[
[
12] J. Lettessier, D. Schollmeyer, H. Detert, Acta Crystallogr. 2011, 67,
494.
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202.
3
2
1
3
(dt, J = 7.9, 0.8 Hz, 1H), 7.10 – 7.02 (m, 3H). C NMR
(125 MHz, CDCl ) δ 181.2,145.1, 136.4, 135.6, 134.3,
3
1
1
1
34.2, 131.1, 129.4, 125.7, 125.4, 124.4, 122.9, 111.4,
07.7.
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4
.3.5 | 7‐ methyl ‐10H‐indolo[1,2‐a]indol‐10‐
[
16] M. Shimizu, M. Ogawa, T. Tamagawa, R. Shigitani, M. Nakatan,
one 4e
Y. Nakano, Eur. J. Org. Chem. 2016, 16, 2785.
1
[17] M. L. Greenlee, J. B. Laub, G. P. Rouen, F. DiNinn,
M. L. Hammond, J. L. Huber, J. G. Sundelof, G. G. Hammond,
Bioorg. Med. Chem. Lett. 1999, 9, 3225.
white solid; (26.6 mg, 57%); H NMR (300 MHz, CDCl )
3
δ 7.85 – 7.83 (m, 1H), 7.77 – 7.75 (m, 1H), 7.71 – 7.69
m, 1H), 7.62 – 7.60 (m, 1H), 7.59 – 7.56 (m, 1H),
(
[18] P. J. Perry, M. A. Read, R. T. Davies, S. M. Gowan, A. P. Reszka,
7
(
.47 – 7.45 (m, 1H), 7.16‐7.13 (m, 1H), 7.13 – 7.10
1
3
A. A. Wood, L. R. Kelland, S. Neidle, J. Med. Chem. 1999, 42,
m, 1H), 2.50 (s, 3H, ‐CH3). C NMR (75 MHz, CDCl3)
δ 178.1, 140.1, 135.8, 133.3, 132.6, 131.7, 128.6, 128.5,
24.1, 123.4, 122.8, 121.5, 121.3, 111.7, 110.6, 9.6.
2
679.
[
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1
[
2
63.
4
.3.6 | 9H‐pyrrolo[1,2‐a]indol‐9‐one 4f
[
[
[
21] A. J. Catino, J. M. Nichols, H. Choi, S. Gottipamula, M. P. Doyle,
1
Org. Lett. 2005, 7, 5167.
dark yellow solid; (13.9 mg, 41%); H NMR (300 MHz,
CDCl ) δ 7.58‐7.56 (m, 1H), 7.43 (td, J = 7.7, 1.3 Hz, 1H),
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3
1
6, 3216.
7.19 – 7.05 (m, 3H), 6.78 (dd, J = 3.8, 0.9 Hz, 1H), 6.31
13
23] D. E. Ames, A. Opalko, Tetrahedron 1984, 40, 1919.
(dd, J = 3.8, 2.6 Hz, 1H). C NMR (125 MHz, CDCl ) δ
3
1
1
79.7, 143.8, 134.1, 132.0, 130.3, 125.5, 124.5, 119.4,
15.9, 114.0, 110.3.
[24] R. A. Haggam, Tetrahedron 2013, 69 6488.
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4
8, 9379.
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4, 4850.
[
[
ACKNOWLEDGEMENTS
1
We are grateful to NSF of China (21402013), the NSF of
Jiangsu Province (BK20140259) and Jiangsu Key Laboratory
of Advanced Catalytic Materials for generous financial
support for our research.
27] Z. Zhang, V. Kodumuru, S. Sviridov, S. Liu, M. Chafeev,
S. Chowdhury, N. Chakka, J. Sun, S. J. Gauthier, M. Mattice,
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