Silver-catalyzed stereoselective cyclization to polysubstituted (z)-1,2-dihydrobenzo [cd] indoles

Article abstract of DOI:10.1021/acs.joc.7b03257

Silver-catalyzed stereoselective synthesis of polysubstituted (Z)-1,2-dihydrobenzo[cd]indoles from 8-ethynylnaphthalen-1-amines is reported. In this protocol, a series of nitrogen-containing heterocyclic compounds were synthesized by silver-catalyzed α-ad

Full text of DOI:10.1021/acs.joc.7b03257

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Silver-Catalyzed Stereoselective Cyclization to
Polysubstituted (Z)-1,2-Dihydrobenzo[cd]indoles
Qiqi Wang, Lianpeng Zhang, Jinzhong Yao, Guanyinsheng Qiu, Xiaofang Li, and Hongwei Zhou
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b03257 • Publication Date (Web): 06 Mar 2018
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Silver-Catalyzed Stereoselective Cyclization to
Polysubstituted (Z)-1,2-Dihydrobenzo[cd]indoles
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Qiqi Wang, † Lianpeng Zhang,*,† Jinzhong Yao, † Guanyinsheng Qiu, † Xiaofang Li, ‡
Hongwei Zhou*,†
† College of Biological, Chemical Science and Engineering, Jiaxing University, 118
Jiahang Road, Jiaxing 314001, China
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‡ School of Chemistry and Chemical Engineering, Hunan University of Science and
Technology, Xiangtan, 411201, China
ABSTRACT: Silverꢀcatalyzed stereoselective synthesis of polysubstituted
(Z)ꢀ1,2ꢀdihydrobenzo[cd]indoles from 8ꢀethynylnaphthalenꢀ1ꢀamines is reported. In
this protocol, a series of nitrogenꢀcontaining heterocyclic compounds were
synthesized by silverꢀcatalyzed αꢀaddition of alkyne bond with high selectivity and
high yields. The synthesized polysubstituted 1,2ꢀdihydrobenzo[cd]indoles could be
easily converted to benzo[cd]indolꢀ2(1H)ꢀones, and both 1,2ꢀdihydrobenzo[cd]indoles
and benzo[cd]indolꢀ 2(1H)ꢀones are biological and pharmaceutical cores.
Nitrogenꢀcontaining heterocyclic compounds are very important because their
structures are regularly found in natural products,1 material sciences2 and
pharmaceuticals.3ꢀ6 In the family of nitrogenꢀcontaining heterocycles,
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1,2ꢀdihydrobenzo[cd]indoles are widely applied in life, materials and dyes.8 For
example, compound 1 was designed and synthesized in 2003, and their kinase
inhibitory activity against CDK2 was evaluated (Scheme 1).9 Compound 2 exhibited
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efficient antitumor activities and exhibited potent toxicity against MCFꢀ7 cells with
IC50 at 0.003 µM and against 7721 cells at 0.115 µM.10 Compound 3 was used as a
chiral ligand in the asymmetric aldol reactions.11 Compound 4 is a Nꢀheteroarene BF2
dyes which was used as fluorescent material and cellꢀimaging probe.12 In recent years,
1,2ꢀdihydrobenzo[cd]indoles have attracted increasing attention due to their
extraordinary biological and pharmaceutical properties.13
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Scheme 1. Useful structures of 1,2-dihydrobenzo[cd]indoles.
However, there are few synthetic routes to access these polysubstituted
1,2ꢀdihydrobenzo[cd]indoles. Published approaches for the synthesis of these
derivatives mainly include benzo[cd]indolꢀ2(1H)ꢀones as intermediates.7ꢀ8 Reaction of
1,8ꢀnaphthalic anhydride with hydroxylammonium chloride is the most popular
method to prepare benzo[cd]indolꢀ2(1H)ꢀone derivatives (Scheme 2).7 Recently, two
other strategies for synthesizing of benzo[cd]indolꢀ2(1H)ꢀone derivatives had been
implemented. One is based on a sequential Stille coupling and prolineꢀcatalyzed
cyclization/aromatization process.14 The other one is a palladiumꢀcatalyzed
intramolecular aerobic oxidative amineꢀdirected CꢀH bond activation/Nꢀdealkylative
carbonylation of tertiary naphthalenꢀ1ꢀamines.15 Basically, it still remains a
challenging task to develop an efficient and general synthetic approach to
polysubstituted 1,2ꢀdihydrobenzo[cd]indoles.
Scheme 2. Published approaches to 1,2-dihydrobenzo[cd]indoles.
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In recent years, transitionꢀmetalꢀcatalysis for the construction of nitrogen ꢀcontaining
heterocyclic compounds based on anthranilic phenylacetylenes have attracted more
and more attention,16 and a series of unique heterocycles had been constructed by
sequential reactions.17 On the basis of our understanding of synthesis of polycyclic
aromatic hydrocarbons,18 we wish to report a concise protocol to construct
1,2ꢀdihydrobenzo[cd]indoles using 8ꢀethynylꢀ1ꢀnaphthylamines as the starting
materials, which could be readily prepared with 8ꢀiodonaphthalenꢀ1ꢀamine via a
Sonogashira process.19
We envisaged that the various 1,2ꢀdihydrobenzo[cd]indoles could be obtained in two
ways. Method a is the activation of acetylenic bonds via a triple bond promotor (TBP)
to construct (Z)-1,2ꢀdihyꢀdrobenzo[cd]indoles. Method b involves the TBP activation
of the acetylenic bond with
a
coordination of the nitrogen to build
(E)-1,2ꢀdihydrobenzo[cd]indoles (Scheme 3).
Scheme 3. Two strategies for construction of 1,2-dihydrobenzo[cd]indoles.
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Our initial attempt was launched with the Nꢀ(8ꢀ((4ꢀchlorophenyl)ethynyl)naphꢀ
thalenꢀ1ꢀyl)ꢀ4ꢀmethylbenzenesulfonamide as the starting material. First, we used
.
BF3 Et2O as the catalyst and potassium carbonate as the base, in 2 mL of acetonitrile
in air at room temperature for 5 h (Table 1, entry 1). Unfortunately, no reaction was
observed. Then, we tested other Lewis acids such as ZnCl2 or FeCl3 and obtained the
similar results (Table 1, entries 2 and 3). To our delight, when we used AgNO3 as the
catalyst in the presence of potassium carbonate, the expected product 2a was isolated
in 82% yield (Table 1, entry 4). By changing the Ag(I) source to AgOAc and AgTFA,
similar yields were observed (Table 1, entries 5–6). Use of AgOTf as the catalyst
offered 2a in 87% yield (Table 1, entry 7). Control experiment in absence of AgOTf
gave negative result (Table 1, entry 8). While subsequent screening of other bases,
such as Na2CO3, NaHCO3, Et3N, Pyridine or DBU, furnished decreased yields (Table
1, entries 9–13). By removal of base, we only obtained 2a in 10% yield (Table 1,
entry 14). Among the solvents tested, acetonitrile was the optimal choice (Table 1,
entries 7, 15−17). Increasing the amount of AgOTf to 20 mol % or decreasing the
amount of AgOTf to 5 mol % did not improve the yields (Table 1, entries 7, 18 and
o
19). Raising the reaction temperature to 50 C did not change the yield of 2a
significantly (Table 1, entry 21). Finally, the following reaction conditions were
established as optimum for all subsequent reactions: a mixture of 1 (0.1 mmol),
AgOTf (10 mol %) and K2CO3 (0.12 mmol) in 2 mL CH3CN were stirred at room
temperature in air.
Table 1. Optimization of the reaction conditionsa
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Entry
Catalyst (mol %)
Base (equiv)
K2CO3 (1.2)
K2CO3 (1.2)
K2CO3 (1.2)
K2CO3 (1.2)
K2CO3 (1.2)
K2CO3 (1.2)
Solvent
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
T (oC)
r.t.
Yield (%)
N.R.
N.R.
N.R.
82
.
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BF3 Et2O(10)
ZnCl2(10)
FeCl3(10)
r.t.
r.t.
AgNO3 (10)
AgOAc(10)
AgTFA(10)
r.t.
r.t.
78
r.t.
81
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8
K2CO3 (1.2)
K2CO3 (1.2)
Na2CO3 (1.2)
NaHCO3 (1.2)
Et3N(1.2)
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
Toluene
DMSO
THF
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
50
87
N.R.
81
76
61
19
74
10
43
61
12
87
84
86
85
AgOTf(10)
ꢀ
9
AgOTf(10)
AgOTf(10)
AgOTf(10)
AgOTf(10)
AgOTf(10)
AgOTf(10)
AgOTf(10)
AgOTf(10)
AgOTf(10)
AgOTf(20)
AgOTf(5)
AgOTf(10)
AgOTf(10)
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11
12
13
14
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16
17
18
19
20b
21
Pyridine(1.2)
DBU (1.2)
ꢀ
K2CO3 (1.2)
K2CO3 (1.2)
K2CO3 (1.2)
K2CO3 (1.2)
K2CO3 (1.2)
K2CO3 (1.2)
K2CO3 (1.2)
CH3CN
CH3CN
CH3CN
CH3CN
a Reaction conditions: the mixture of 1a (0.1 mmol, 43.1 mg), base (1.2 equiv) and catalyst (10
mol %) in 2 ml of solvent was stirred at r.t. under air. b N2 atmosphere was applied.
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With the optimized reaction conditions in hand, we examined the scope of the
substituents on nitrogen of the 8ꢀ(phenylethynyl)naphthalenꢀ1ꢀamines (Table 2). The
R1 could be arylsulfonyls (Table 2, 2aꢀ2c), methylsulfonyl (Table 2, 2d) or
heterocyclic sulfonyls (Table 2, 2eꢀ2f). By changing the sulfonyls to acetyl or
2ꢀchlorobenzoyl, the corresponding products 2g and 2h could be obtained in 78% and
81% yields, respectively. When R1 was alkyl such as allyl, 2i was produced in 82%
yield. To our delight, if we used 8ꢀ(phenylethynyl)naphthalenꢀ1ꢀamine as the
substrate, 2j could be obtained in 77% yield. This protocol could be conducted on the
gram scale. Reaction of Nꢀ(8ꢀ((4ꢀchlorophenyl)ethynyl)naphthalenꢀ1ꢀyl)ꢀ4ꢀ
methylbenzenesulfonamide (1.29 g, 3.0 mmol), AgOTf (0.3 mmol), K2CO3 (3.6 mmol)
in CH3CN (50 mL) in air at room temperature for 12 h gave 1.10 g of 2a in 85%
isolated yield.
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Table 2. Synthesis of (Z)-2-benzylidene-1,2-dihydrobenzo[cd]indole derivativesa
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a Reaction conditions: 1 (0.1 mmol), AgOTf (10 mol %, 2.6 mg) and K2CO3 (1.2 equiv, 16.5 mg)
4
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in 2 ml of CH3CN was stirred at r.t. under air.
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Next, different substituents on the alkynyl groups were examined (Table 3). The R2
could be phenyl groups optionally substituted with an electronꢀdonating (Table 3, 3b
and 3c) or an electronꢀwithdrawing group (Table 3, 3d). Changing the substituent
from phenyl to naphthylethynyl, 2ꢀthiophene ethynyl, or alkyl group, the
corresponding products were obtained in good yields (Table 3, 3e - 3h). Using
4ꢀmethylꢀNꢀ(8ꢀ((trimethylsilyl)ethynyl)naphthalenꢀ1ꢀyl)benzenesulfonamide as the
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starting material, 3i was afforded in 78% yield. The structure of the products was
confirmed by the single crystal structure of 3b.20 Notably, stereoselective construction
of the (Z)ꢀexoꢀcyclic geometry may be generally difficult because the two large
substituents locate on the same side.
Table 3. Synthesis of 1-(phenylsulfonyl)-1,2-dihydrobenzo[cd]indole derivativesa
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a Reaction conditions: 1 (0.1 mmol), AgOTf (10 mol %, 2.6 mg) and K2CO3 (1.2 equiv, 16.5 mg)
in 2 ml of CH3CN was stirred at r.t. under air.
According to the facts that the single crystal structure of 3b shows Z configuration,
we postulated a plausible mechanism shown in Scheme 4. Triple bond assisted with
Ag(I) forms A, then a selective nitrogen addition to the αꢀposition of alkyne affords
B.21 Subsequently, protonolysis of B delivers the final product 2 or 3.
Scheme 4. Plausibe Mechanism.
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Using mꢀCPBA as the oxidant, 2c and 2j could be selectively converted to
1ꢀ(naphthalenꢀ2ꢀylsulfonyl)benzo[cd]indolꢀ2(1H)ꢀone (4) and benzo[cd]indolꢀ2(1H)ꢀ
one (5) in 89% and 87% yields, respectively (Scheme 5). And
benzo[cd]indolꢀ2(1H)ꢀone derivatives, containing an unique heterocyclic moiety,
could be used in the transformations to antitumor agent, BET bromodomain inhibitor
or PDT photosensitizer.
Scheme 5. Preparation of 4 and its applications.
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In conclusion, we have developed a silverꢀcatalyzed one pot facile protocol for the
synthesis of polysubstituted (Z)ꢀ1,2ꢀdihydrobenzo[cd]indoles. Many substituents
tolerate the reaction conditions and produce (Z)ꢀ1,2ꢀdihydrobenzo[cd]indoles in good
yields. In this reaction, silver catalyzed selective addition of αꢀalkyne is the key
intermediate. Moreover, benzo[cd]indolꢀ2(1H)ꢀones could be obtained just by adding
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mꢀCPBA
as
the
oxidant,
both
1,2ꢀdihydrobenzo[cd]indoles
and
benzo[cd]indolꢀ2(1H)ꢀones have the extraordinary biological and pharmaceutical
properties. Further studies on the synthetic application are currently ongoing.
EXPERIMENTAL SECTION
General information
Unless stated otherwise, reactions were conducted in dried glassware. Commercially
available reagents and solvents were used as received. 300ꢀ400 Mesh silica gel was
used for flash column chromatography. Visualization on TLC was achieved by the
1
use of UV light (254 nm). 400 MHz and 100 MHz were used for the record of H
NMR and 13C NMR spectra. Chemical shifts (δ ppm) were reported in parts per
million referring to either the internal standard of TMS or the residue of the
deuterated solvents. Splitting pattern was described as follows: s for singlet, d for
doublet, t for triplet, q for quartet, and m for multiplet. Coupling constants were
reported in Hz. The highꢀresolution mass spectrum (HRMS) was performed on
Waters Xevo G2ꢀS QTof mass spectrometer.
Typical procedure for the synthesis of 2a. A mixture of 1a (0.1 mmol), AgOTf (10
mol %, 2.6 mg) and K2CO3 (1.2 equiv, 16.5 mg) in CH3CN (2 ml) was stirred at r.t.
for 5 h (monitored by TLC). After the substrate 1a was completely consumed, the
reaction mixture was filtrated and concentrated under reduced pressure. The residue
was purified by column chromatography on silica gel (8:1 petroleum ether/ethyl
acetate) to afford the desired product 2a as yellow solid (37.5 mg, 87%).
(Z)-2-(4-chlorobenzylidene)-1-tosyl-1,2-dihydrobenzo[cd]indole (2a)
Yellow solid, 37.5 mg, 87%. Mp: 162ꢀ164 oC. 1H NMR (400 MHz, CDCl3) δ 7.84 (d,
J = 8.4 Hz, 2H), 7.70 (dd, J = 6.5, 1.4 Hz, 1H), 7.52 (dd, J = 7.9, 3.4 Hz, 1H), 7.50 –
7.45 (m, 2H), 7.43 – 7.34 (m, 4H), 7.28 (d, J = 8.3 Hz, 2H), 6.92 (s, 1H), 6.82 (d, J =
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8.0 Hz, 2H), 2.12 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 144.5, 141.9, 138.9, 135.3,
134.9, 133.6, 132.8, 131.6, 131.1, 130.2, 129.1, 128.9, 128.7, 128.6, 128.0, 124.8,
122.1, 117.8, 115.6, 114.0, 21.7; IR (neat) 3437, 1362, 818 cmꢀ1; HRMS (ESIꢀTOF)
calcd for C25H19ClNO2S(M+H): 432.0825, found 432.0829.
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(Z)-2-(4-chlorobenzylidene)-1-(4-fluorophenylsulfonyl)-1,2-dihydrobenzo[cd]indo
le (2b)
Yellow solid, 38.7 mg, 89%. Mp: 177ꢀ179 oC. 1H NMR (400 MHz, CDCl3) δ 7.84 (d,
J = 8.5 Hz, 2H), 7.71 (dd, J = 5.4, 2.5 Hz, 1H), 7.55 (dd, J = 6.5, 2.0 Hz, 1H), 7.52 –
7.47 (m, 2H), 7.45 – 7.35 (m, 6H), 6.93 (s, 1H), 6.70 (t, J = 8.6 Hz, 2H); 13C NMR
(100 MHz, CDCl3) δ 165.7 (JCꢀF = 255.0 Hz), 141.6, 138.7, 134.8 (JCꢀF = 38.0 Hz),
133.8, 131.6, 131.4 (JCꢀF = 3.0 Hz), 131.1, 130.7, 130.6, 130.1, 129.2, 128.7, 128.7,
125.0, 122.5, 118.3, 115.7 (JCꢀF = 4.0 Hz), 115.5, 114.1; IR (neat) 3436, 1364, 822
cmꢀ1; HRMS (ESIꢀTOF) calcd for C24H16ClFNO2S (M+H): 436.0574, found
436.0571.
(Z)-2-(4-chlorobenzylidene)-1-(naphthalen-2-ylsulfonyl)-1,2-dihydrobenzo[cd]ind
ole (2c)
Yellow solid, 39.2 mg, 84%. Mp: 120ꢀ122 oC. 1H NMR (400 MHz, CDCl3) δ 8.00 (s,
1H), 7.88 (d, J = 8.4 Hz, 2H), 7.78 (d, J = 7.3 Hz, 1H), 7.67 (d, J = 7.4 Hz, 1H), 7.59
(d, J = 7.7 Hz, 1H), 7.52 – 7.28 (m, 11H), 6.95 (s, 1H); 13C NMR (100 MHz, CDCl3)
δ 141.7, 138.9, 135.1, 135.1, 134.8, 133.7, 132.8, 131.6, 131.6, 131.0, 123.0, 129.8,
129.6, 129.5, 129.1, 129.1, 128.6, 128.5, 127.9, 127.5, 124.8, 122.8, 122.3, 117.8,
115.7, 113.9; IR (neat) 3431, 1362, 822 cmꢀ1; HRMS (ESIꢀTOF) calcd for
C24H16ClFNO2S (M+H): 436.0574, found 436.0571.
(Z)-2-(4-chlorobenzylidene)-1-(methylsulfonyl)-1,2-dihydrobenzo[cd]indole (2d)
o
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Yellow solid, 30.9 mg, 87%. Mp: 176ꢀ178 C. H NMR (400 MHz, CDCl3) δ 7.79 –
7.70 (m, 3H), 7.66 – 7.49 (m, 5H), 7.33 (d, J = 8.6 Hz, 2H), 6.97 (s, 1H), 2.46 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 142.0, 138.1, 135.1, 134.6, 133.8, 131.6, 131.4, 130.6,
129.6, 129.2, 128.6, 125.3, 122.6, 118.1, 116.3, 113.2, 34.9; IR (neat) 3446, 1346,
816 cmꢀ1; HRMS (ESIꢀTOF) calcd for C19H15ClNO2S (M+H): 356.0512, found
356.0516.
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Yellow solid, 35.9 mg, 85%. Mp: 203ꢀ205 oC. 1H NMR (400 MHz, CDCl3) δ 7.83 (d,
J = 8.5 Hz, 2H), 7.74 (dd, J = 4.8, 3.2 Hz, 1H), 7.58 (dd, J = 6.4, 2.2 Hz, 1H), 7.56 –
7.51 (m, 2H), 7.47 – 7.40 (m, 2H), 7.37 (d, J = 8.6 Hz, 2H), 7.18 (dd, J = 5.0, 1.3 Hz,
1H), 7.13 (dd, J = 3.8, 1.3 Hz, 1H), 6.97 (s, 1H), 6.62 (dd, J = 4.9, 3.9 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 141.7, 138.5, 135.1, 134.6, 134.5, 134.0, 133.8, 133.4,
131.6, 131.1, 130.3, 129.2, 128.8, 128.6, 126.6, 124.9, 122.7, 118.8, 115.7, 114.6; IR
(neat) 3440, 1362, 822 cmꢀ1; HRMS (ESIꢀTOF) calcd for C22H15ClNO2S2 (M+H):
424.0233, found 424.0229.
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(Z)-2-(4-chlorobenzylidene)-1-(1-methyl-1H-pyrazol-4-ylsulfonyl)-1,2-dihydrobe
nzo[cd]indole (2f)
Yellow solid, 34.9 mg, 83%. Mp: 166ꢀ168 oC. 1H NMR (400 MHz, CDCl3) δ 7.81 (d,
J = 8.6 Hz, 2H), 7.71 (dd, J = 4.8, 3.0 Hz, 1H), 7.61 (dd, J = 6.5, 2.1 Hz, 1H), 7.56 –
7.53 (m, 2H), 7.49 – 7.45 (m, 2H), 7.35 (d, J = 8.5 Hz, 2H), 7.21 (s, 1H), 7.14 (s, 1H),
6.94 (s, 1H), 3.53 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 141.9, 139.2, 138.4, 135.2,
134.6, 133.7, 132.3, 131.6, 131.3, 130.3, 129.3, 128.7, 128.6, 125.0, 122.6, 118.4,
117.3, 115.8, 114.1, 39.5; IR (neat) 3438, 1361, 820 cmꢀ1; HRMS (ESIꢀTOF) calcd
for C22H17ClN3O2S (M+H): 422.0730, found 422.0732.
(Z)-(2-(4-chlorobenzylidene)benzo[cd]indol-1(2H)-yl)(2-chlorophenyl)methanone
(2g)
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Yellow solid, 32.4 mg, 78%. Mp: 155ꢀ157 C. H NMR (400 MHz, CDCl3) δ 7.73 –
7.61 (m, 2H), 7.58 (dd, J = 6.0, 2.5 Hz, 1H), 7.50 – 7.47 (m, 2H), 7.44 – 7.36 (m, 5H),
7.33 – 7.18 (m, 3H), 7.17 – 7.09 (m, 1H), 7.07 (d, J = 7.3 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 167.2, 140.2, 140.0, 138.7, 137.0, 135.0, 133.8, 131.9, 131.4, 130.7,
130.6, 129.9, 129.6, 129.2, 129.1, 129.0, 128.7, 128.1, 125.7, 120.8, 119.4, 117.0,
109.2; IR (neat) 3438, 1751, 821 cmꢀ1; HRMS (ESIꢀTOF) calcd for C25H16Cl2NO
(M+H): 416.0609, found 416.0608.
(Z)-1-(2-(4-chlorobenzylidene)benzo[cd]indol-1(2H)-yl)ethanone (2h)
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Yellow solid, 25.8 mg, 81%. Mp: 95ꢀ97 C. H NMR (400 MHz, CDCl3) δ 7.88 (s,
1H), 7.65 (d, J = 8.2 Hz, 1H), 7.49 – 7.46 (m, 2H), 7.45 – 7.38 (m, 5H), 7.29 (t, J =
7.8 Hz, 1H), 7.04 (d, J = 7.4 Hz, 1H), 2.73 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
170.8, 140.5, 140.4, 135.3, 133.7, 131.6, 131.3, 130.7, 129.7, 128.7, 128.6, 128.4,
125.6, 120.6, 119.4, 117.2, 109.7, 27.9; IR (neat) 3440, 1721, 826 cmꢀ1; HRMS
(ESIꢀTOF) calcd for C20H15ClNO (M+H): 320.0842, found 320.0841.
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(Z)-2-(4-chlorobenzylidene)-1-allyl-1,2-dihydrobenzo[cd]indole (2i)
Yellow oil, 26.0 mg, 82%. 1H NMR (400 MHz, CDCl3) δ 7.58 (dd, J = 12.1, 7.7 Hz,
2H), 7.49 (d, J = 8.4 Hz, 2H), 7.39 – 7.27 (m, 4H), 7.11 (d, J = 8.3 Hz, 1H), 6.42 (d, J
= 7.2 Hz, 1H), 6.00 – 5.89 (m, 2H), 5.25 (s, 1H), 5.21 (d, J = 5.0 Hz, 1H), 4.46 – 4.39
(m, 2H); 13C NMR (100 MHz, CDCl3) δ 144.9, 142.8, 136.0, 132.4, 132.3, 132.2,
131.4, 130.5, 129.3, 129.2, 128.3, 128.2, 125.7, 119.3, 117.0, 115.2, 102.3, 98.9, 45.5;
IR (neat) 3451, 887, 815 cmꢀ1; HRMS (ESIꢀTOF) calcd for C21H17ClN (M+H):
318.1050, found 318.1048.
(Z)-2-benzylidene-1,2-dihydrobenzo[cd]indole (2j)
1
Yellow oil, 18.7 mg, 77%. H NMR (400 MHz, CDCl3) δ 8.53 (s, 1H), 8.44 (d, J =
7.9 Hz, 2H), 8.24 (s, 1H), 8.17– 8.02 (m, 2H), 7.81 (s, 1H), 7.77–7.69 (m, 1H),
7.70–7.62 (m, 1H), 7.57 (t, J = 7.4 Hz, 2H), 7.53– 7.42 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 134.0, 132.6, 132.5, 131.9, 131.9, 131.2, 131.1, 130.6, 129.9, 129.8,
129.7, 129.3, 128.9, 128.9, 128.8, 127.9; IR (neat) 3454, 889, 814cmꢀ1; HRMS
(ESIꢀTOF) calcd for C18H14N (M+H): 244.1126, found 244.1121.
(Z)-2-benzylidene-1-tosyl-1,2-dihydrobenzo[cd]indole (3a)
Yellow solid, 33.7 mg, 85%. Mp: 177ꢀ179 oC. 1H NMR (400 MHz, CDCl3) δ 7.91 (d,
J = 7.4 Hz, 2H), 7.70 (dd, J = 6.6, 1.1 Hz, 1H), 7.62 – 7.36 (m, 7H), 7.36 – 7.26 (m,
3H), 6.99 (s, 1H), 6.82 (d, J = 8.0 Hz, 2H), 2.12 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 144.4, 138.4, 136.5, 136.3, 132.9, 131.1, 130.6, 130.4, 129.0, 128.9, 128.7, 128.4,
128.2, 128.1, 128.0, 124.5, 122.0, 119.3, 115.4, 113.9, 21.7; IR (neat) 3442, 1366,
817 cmꢀ1; HRMS (ESIꢀTOF) calcd for C25H20NO2S (M+H): 398.1215, found
398.1216.
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(Z)-2-(4-methybenzylidene)-1-tosyl-1,2-dihydrobenzo[cd]indole (3b)
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Yellow solid, 35.8 mg, 87%. Mp: 175ꢀ177 oC. 1H NMR (400 MHz, CDCl3) δ 7.83 (d,
J = 8.1 Hz, 2H), 7.70 (d, J = 6.9 Hz, 1H), 7.52 – 7.42 (m, 3H), 7.39 (d, J = 2.9 Hz,
1H), 7.29 (d, J = 8.3 Hz, 2H), 7.26 – 7.21 (m, 3H), 6.96 (s, 1H), 6.81 (d, J = 8.3 Hz,
2H), 2.39 (s, 3H), 2.11 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 144.3, 142.1, 138.2,
137.7, 135.8, 133.3, 132.9, 131.1, 130.4, 130.2, 129.1, 129.0, 128.8, 128.6, 128.0,
124.2, 121.9, 119.5, 115.2, 113.8, 21.9, 21.7; IR (neat) 3442, 1364, 817 cmꢀ1; HRMS
(ESIꢀTOF) calcd for C26H22NO2S (M+H): 412.1371, found 412.1370.
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(Z)-2-(4-methoxybenzylidene)-1-tosyl-1,2-dihydrobenzo[cd]indole (3c)
Yellow solid, 36.7 mg, 86%. Mp: 170ꢀ172 oC. 1H NMR (400 MHz, CDCl3) δ 7.89 (d,
J = 8.8 Hz, 2H), 7.69 (d, J = 6.9 Hz, 1H), 7.50 – 7.42 (m, 3H), 7.40 – 7.33 (m, 2H),
7.29 (d, J = 8.2 Hz, 2H), 7.00 – 6.91 (m, 3H), 6.81 (d, J = 8.0 Hz, 2H), 3.85 (s, 3H),
2.11 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.6, 144.3, 142.2, 136.7, 136.0, 132.8,
132.0, 131.2, 130.3, 129.0, 128.8, 128.7, 128.6, 128.0, 123.9, 121.9, 119.5, 114.9,
113.8, 113.8, 55.6, 21.7; IR (neat) 3446, 1364, 821 cmꢀ1; HRMS (ESIꢀTOF) calcd for
C26H22NO3S (M+H): 428.1320, found 428.1319.
(Z)-2-(4-fluorobenzylidene)-1-tosyl-1,2-dihydrobenzo[cd]indole (3d)
1
Yellow solid, 36.9 mg, 89%. Mp: 182ꢀ184 oC. H NMR (400 MHz, CDCl3) δ 7.90 (t,
J = 6.8 Hz, 2H), 7.70 (d, J = 6.7 Hz, 1H), 7.54 – 7.44 (m, 3H), 7.42 – 7.36 (m, 2H),
7.29 (d, J = 7.2 Hz, 2H), 7.10 (t, J = 8.4 Hz, 2H), 6.93 (s, 1H), 6.81 (d, J = 7.7 Hz,
2H), 2.10 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 162.4 (JCꢀF = 247.0 Hz), 144.5,
141.9, 138.2, 135.4, 132.7, 132.4 (JCꢀF = 4.0 Hz), 132.1, 132.1, 131.1, 130.1, 128.8
(JCꢀF = 13.0 Hz), 128.9, 127.9, 124.6, 122.1, 118.1, 115.4 (JCꢀF = 7.0 Hz), 115.3, 113.9,
21.7; IR (neat) 3442, 1368, 829 cmꢀ1; HRMS (ESIꢀTOF) calcd for C25H19FNO2S
(M+H): 416.1121, found 416.1123.
(Z)-2-(naphthalen-1-ylmethylene)-1-tosyl-1,2-dihydrobenzo[cd]indole (3e)
Yellow solid, 38.4 mg, 86%. Mp: 155ꢀ157 oC. 1H NMR (400 MHz, CDCl3) δ 8.22 (d,
J = 8.3 Hz, 1H), 8.07 (d, J = 7.2 Hz, 1H), 7.92 (d, J = 8.1 Hz, 1H), 7.84 (d, J = 8.1 Hz,
1H), 7.75 – 7.71 (m, 1H), 7.64 – 7.58 (m, 2H), 7.56 – 7.55 (m, 1H), 7.55 – 7.51 (m,
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5H), 7.48 – 7.44 (m, 1H), 7.25 (d, J = 8.0 Hz, 2H), 6.87 (d, J = 8.2 Hz, 2H), 2.16 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 144.3, 142.1, 140.0, 135.2, 134.1, 133.9, 133.5,
132.2, 131.2, 130.0, 129.3, 129.1, 129.0, 128.9, 128.3, 128.1, 127.8, 126.4, 126.0,
125.9, 124.8, 124.6, 121.6, 115.8, 114.9, 113.3, 21.8; IR (neat) 3446, 1354, 795 cmꢀ1;
HRMS (ESIꢀTOF) calcd for C29H22NO2S (M+H): 448.1371, found 448.1367.
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(Z)-2-(thiophen-2-ylmethylene)-1-tosyl-1,2-dihydrobenzo[cd]indole (3f)
Yellow solid, 35.1 mg, 87%. Mp: 128ꢀ130 oC. 1H NMR (400 MHz, CDCl3) δ 7.70 (d,
J = 6.8 Hz, 1H), 7.54 – 7.51 (m, 1H), 7.49 – 7.42 (m, 3H), 7.42 – 7.39 (m, 1H), 7.38 –
7.33 (m, 2H), 7.31 – 7.26 (m, 2H), 7.16 (s, 1H), 7.08 – 7.02 (m, 1H), 6.78 (d, J = 7.4
Hz, 2H), 2.10 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 144.4, 142.1, 139.3, 137.0,
135.5, 132.6, 131.1, 130.6, 130.4, 129.1, 128.7, 128.5, 128.2, 127.7, 127.0, 124.2,
122.3, 115.1, 114.4, 114.4, 21.7; IR (neat) 3446, 1364, 808 cmꢀ1; HRMS (ESIꢀTOF)
calcd for C23H18NO2S2 (M+H): 404.0779, found 404.0779.
(Z)-2-(cyclopropylmethylene)-1-tosyl-1,2-dihydrobenzo[cd]indole (3g)
1
Yellow oil, 28.5 mg, 79%. H NMR (400 MHz, CDCl3) δ 7.64 (d, J = 6.9 Hz, 1H),
7.48 – 7.39 (m, 3H), 7.35 (d, J = 8.3 Hz, 2H), 7.32 – 7.27 (m, 1H), 7.13 (d, J = 7.1 Hz,
1H), 6.86 (d, J = 8.0 Hz, 2H), 5.45 (d, J = 10.4 Hz, 1H), 2.73 – 2.57 (m, 1H), 2.14 (s,
3H), 1.13 – 1.06 (m, 2H), 0.67 – 0.61 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 144.2,
137.8, 133.3, 131.2, 130.5, 129.7, 129.0, 128.8, 128.6, 128.1, 127.9, 127.5, 123.4,
121.5, 113.9, 113.3, 21.8, 13.3, 9.3, 8.8; IR (neat) 3441, 1261, 804 cmꢀ1; HRMS
(ESIꢀTOF) calcd for C22H20NO2S (M+H): 362.1215, found 362.1211.
(Z)-2-pentylidene-1-tosyl-1,2-dihydrobenzo[cd]indole (3h)
1
Yellow oil, 30.5 mg, 81%. H NMR (400 MHz, CDCl3) δ 7.62 (d, J = 6.7 Hz, 1H),
7.48 – 7.41 (m, 3H), 7.34 (d, J = 7.7 Hz, 1H), 7.31 (d, J = 8.1 Hz, 2H), 7.24 (d, J =
7.2 Hz, 1H), 6.84 (d, J = 8.3 Hz, 2H), 6.08 (t, J = 7.4 Hz, 1H), 2.83 (dd, J = 14.9, 7.4
Hz, 2H), 2.12 (s, 3H), 1.57 – 1.50 (m, 2H), 1.43 (dd, J = 15.0, 7.2 Hz, 2H), 0.95 (t, J =
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 144.2, 139.0, 135.2, 133.4, 131.1, 129.7,
129.0, 128.8, 128.6, 127.8, 127.5, 124.1, 123.8, 121.7, 114.6, 113.4, 32.3, 30.3, 22.9,
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21.7, 14.4; IR (neat) 2998, 1357, 819 cmꢀ1; HRMS (ESIꢀTOF) calcd for C23H24NO2S
(M+H): 378.1528, found 378.1525.
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2-Methylene-1-tosyl-1,2-dihydrobenzo[cd]indole (3i)
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1
Yellow solid, 25.0 mg, 78%. Mp: 80ꢀ82 oC. H NMR (400 MHz, CDCl3) δ 7.76 (d, J
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= 8.3 Hz, 2H), 7.49 (d, J = 7.7 Hz, 1H), 7.34 – 7.08 (m, 7H), 6.71 (d, J = 6.3 Hz, 1H),
6.11 – 5.99 (m, 1H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 145.3, 135.4, 131.4,
130.2, 128.1, 127.5, 127.0, 126.4, 124.5, 122.5, 121.7, 121.2, 121.1, 118.0, 111.7,
111.5, 22.0; IR (neat) 3325, 1285, 884 cmꢀ1; HRMS (ESIꢀTOF) calcd for C19H16NO2S
(M+H): 322.0902, found 322.0901.
1-(Naphthalen-2-ylsulfonyl)benzo[cd]indol-2(1H)-one (4)
Yellow solid, 31.9 mg, 89%. Mp: 197ꢀ199 oC. 1H NMR (400 MHz, CDCl3) δ 8.78 (s,
1H), 8.08 (t, J = 9.4 Hz, 2H), 8.04 – 7.97 (m, 3H), 7.91 (d, J = 8.8 Hz, 1H), 7.85 (d, J
= 7.8 Hz, 1H), 7.74 – 7.66 (m, 2H), 7.66 – 7.52 (m, 3H); 13C NMR (100 MHz, CDCl3)
δ 165.4, 135.9, 135.6, 135.3, 132.8, 132.2, 130.4, 130.0, 129.9, 129.9, 129.8, 129.4,
129.1, 128.2, 128.0, 126.5, 125.8, 124.0, 122.8, 122.6, 111.4; IR (neat) 3451, 1362,
1678 cmꢀ1; HRMS (ESIꢀTOF) calcd for C21H14NO3S (M+H): 360.0694, found
360.0692.
Benzo[cd]indol-2(1H)-one (5)
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Known compound. Yellow solid, 14.7 mg, 87%. Mp: 180ꢀ182 C. H NMR (400
MHz, CDCl3) δ 8.40 (s, 1H), 8.14 – 8.02 (m, 2H), 7.79 – 7.70 (m, 1H), 7.57 (d, J =
8.5 Hz, 1H), 7.46 (t, J = 7.7 Hz, 1H), 7.00 (d, J = 7.0 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 170.2, 144.4, 137.3, 131.6, 129.7, 129.1, 129.0, 126.7, 124.8, 120.7, 106.8.
ASSOCIATED CONTENT
Supporting Information
1H and 13C NMR spectra of all new compounds. This material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
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Corresponding Author
Eꢀmail: lpz@zju.edu.cn
zhouhw@zju.edu.cn.
Notes
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The authors declare no competing financial interest.
ACKNOWLEDGEMENTS
This work was supported by the Natural Science Foundation of Zhejiang Province
(No. LQ18B020005), National Natural Science Foundation of China (Nos: 21502069
and 21772067), Science and Technology Project of Jiaxing (No. 2017AY13019) and
Ph.D. Scientific Research Starting Foundation of Jiaxing University (No. 70516046).
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