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Chinese Chemical Letters 27 (2016) 256–260

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Chinese Chemical Letters


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Original article

Synthesis of indol-3-yl aryl ketones through visible-light-mediated


carbonylation
Hong-Tao Zhang a, Li-Jun Gu a,b,*, Xiang-Zhong Huang a, Rui Wang a, Cheng Jin c,
Gan-Peng Li a,**
a
Key Laboratory of Chemistry in Ethnic Medicinal Resources, State Ethnic Affairs Commission & Ministry of Education, Yunnan Minzu University,
Kunming 650500, China
b
Engineering Research Center of Biopolymer Functional Materials of Yunnan, Yunnan Minzu University, Kunming 650500, China
c
New United Group Company Limited, Changzhou 213166, China

A R T I C L E I N F O A B S T R A C T

Article history: A visible-light-catalyzed synthesis of indol-3-yl aryl ketones from aryldiazonium salts, CO and indoles at
Received 20 July 2015 room temperature was developed. This process provides a useful method for the preparation of diverse
Received in revised form 18 September 2015 indol-3-yl aryl ketones from readily accessible reactants under base-free, acid-free and transition-metal-
Accepted 24 September 2015
free conditions.
Available online 26 October 2015
ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.
Keywords:
Indol-3-yl aryl ketones
Carbonylation
Visible-light
Aryldiazonium salts
Indoles

1. Introduction metals as the catalysts. The synthesis of indol-3-yl aryl ketones


under acid-free, base-free and transition-metal-free conditions has
The synthesis and transformation of indoles have been and not yet been realized.
continue to be a focus of research efforts for synthetic organic Recently visible light photoredox catalysis attracted much
chemists because the indole nucleus is found in countless attention due to the rich resource of visible light, the fact that it is
biologically active molecules and medicinally relevant structures environment-friendly, and high efficiency [8]. After having
[1]. Indol-3-yl aryl ketones represent an important class of garnered little interest for about one century since being sponsored
nitrogen-containing heterocycles, which are the basic constituents by Ciamician, reports on visible light photoredox catalysis
of numerous natural products, biologically active alkaloids, exploded since 2008, which exhibited powerful ability in organic
functional materials and pharmaceuticals [2]. Consequently, the synthesis and material chemistry [9]. Many visible-light photo-
development of synthetic methods for the preparation of indol-3- redox catalysts such as metal or none-metal complexes have been
yl aryl ketones has received considerable attention [3]. Among the used to solve the problem of visible light absorption efficiency
numerous methods that have been developed, the most commonly [10]. In these methods, readily available, reactive aryl diazonium
used methods are Friedel–Crafts reactions [4], Vilsmeier–Haack salts have been widely utilized as a convenient aryl radical source
type reactions [5], and Grignard reactions [6]. Recently, transition- [11]. As a result, many unusual transformations of these reagents
metal-catalyzed acylation of C–H bonds has been developed as have been carried out by photocatalysis. Recently, Wangelin and
promising protocols for the construction of indol-3-yl aryl ketones Xiao independently reported a visible-light-mediated redox
[7]. However, these reactions employ acids, bases or transition reaction that affords alkyl benzoates from arenediazonium salts,
carbon monoxide, and alcohols [11b,c]. They found that in the
presence of a certain amount of CO, aryl radicals can be easily and
* Corresponding author at: Yunnan Minzu University, Key Laboratory of efficiently converted into acyl radicals that can be further oxidized
Chemistry in Ethnic Medicinal Resources, State Ethnic Affairs Commission & to benzylidyneoxonium salts by the oxidized dye radical cation.
Ministry of Education, Kunming 650500, China.
** Corresponding author.
We envisioned that indoles might serve as a platform to trap
E-mail addresses: gulijun2005@126.com (L.-J. Gu), ganpeng_li@sina.com benzylidyneoxonium ions. To explore the application of photo-
(G.-P. Li). catalysts and to overcome the drawbacks of the synthesis of

http://dx.doi.org/10.1016/j.cclet.2015.10.012
1001-8417/ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
H.-T. Zhang et al. / Chinese Chemical Letters 27 (2016) 256–260 257

Table 1
Optimization of the reaction conditionsa.

e.g. O
solvent, catalysis Ph
PhN2 BF4 +
N CO (70 atm), 16 h N
1a 2a 3aa

Entry Catalyst Solvent Yield (%)b

1 Eosin Y CH3CN 66
2c Eosin Y CH3CN 82
3 Eosin Y DMSO 52
4 Eosin Y THF 17
5 Eosin Y EtOAc Trace
6 Eosin Y PhCF3 Trace
Scheme 1. Synthetic route to indol-3-yl aryl ketones. 7 Fluorescein CH3CN 62
8 Rhodamine B CH3CN 40
indol-3-yl aryl ketones, herein, we disclose our preliminary results 9 RB CH3CN 27
10d Eosin Y CH3CN 64
on visible light-promoted transformation of aryldiazonium salts 11 None CH3CN 0
and indoles in the synthesis of indol-3-yl aryl ketones under base- 12e Eosin Y CH3CN 0
free, acid-free and transition-metal-free conditions in carbon a
Reaction conditions: 1a (0.3 mmol), 2a (0.4 mmol), catalyst (1 mol%), solvent
monoxide atmosphere. The method involves a redox reaction (3.0 mL), room temperature, CO (70 atm), 5 W white LED light for 16 h.
driven by visible light and catalyzed by Eosin Y (Scheme 1). b
Isolated yield.
c
5 W green LED light.
d
CO (60 atm).
2. Experimental e
In the dark.

Reagents were obtained commercially and used as received.


Solvents were purified and dried by the standard methods. The
melting points were determined on an XT-4 micro melting point investigated and the results showed that Eosin Y was more
apparatus and uncorrected. IR spectra were recorded on an effective in producing the desired product (Table 1, entries 2, 7–9).
EQUINOX-55 spectrometer in a KBr matrix. NMR spectra were Lower pressure of CO resulted in low conversion (Table 1, entry
recorded on an INOVA-400 NMR instrument at room temperature 10). Both visible-light photoredox catalysts and visible light are
using TMS as an internal standard. Coupling constants (J) were essential for the reaction to take place (Table 1, entries 11–12).
measured in Hz. Chemical shift values (d) are given in ppm. High With this preliminary result in hand, the generality of the
Resolution mass spectrometer (HRMS) spectra were recorded on a method was explored under the optimized conditions. The scope of
Bruker micrOTOF-Q II analyzer. A 200–300 mesh silica gel was aryldiazonium salts 1 was initially explored in the presence of N-
used for column chromatography. methylindole 2a, Eosin Y (1 mol%) under irradiation with 5 W
General procedure: To an 8 mL vial equipped with a magnetic green LED light and a CO pressure of 70 atm in MeCN at room
stir bar was charged with 1 (0.3 mmol), 2 (0.4 mmol), Eosin Y temperature, and the results are summarized in Table 2. In general,
(1 mol%), dry MeCN (3.0 mL). The vial was purged with N2 in the a variety of functional groups on the phenyl ring of aryldiazonium
dark and transferred into an autoclave with a Quartz window salts were compatible in this procedure, affording the desired
bottom. The autoclave was flushed three times and slowly filled products in good to excellent yields. The electron-donating groups
with 70 atm of CO. The reaction was irradiated with external LEDs such as methoxy and methyl groups on the aryl ring allowed the
at room temperature for 16 h. After the reaction was finished, the aryldiazonium salts to react with 2a efficiently and gave the
gas was carefully released and the vial retrieved, the reaction desired products 3ab–3ac in good yields. Aryldiazonium salts
mixture was diluted with 5 mL of H2O, extracted with ethyl acetate bearing electron-withdrawing halogen, CF3 and NO2 groups
(10 mL  3). The organic portion was washed with a saturated reacted smoothly to give the corresponding products in good
solution of brine, dried (Na2SO4) and concentrated in vacuum, and yields (3ad–3af). Furthermore, the substituent at the meta position
the resulting residue was purified by silica gel column chroma- on the arene group did not affect the reaction efficiency (Table 2,
tography (hexane/ethyl acetate) to provide the desired products entry 6). However, a substituent at the ortho position of the phenyl
3. The characterization data of products 3 were provided in ring gave the corresponding product 3ah in a lower yield (Table 2,
Supporting information. entry 7). These results indicated that the steric effects affected the
efficiency of the reactions. Interestingly, a polysubstituted
3. Results and discussion aryldiazonium salt gave the desired product 3ai in moderate
yield (Table 1, entry 8). Notably, indol-3-yl naphthyl ketones are
At the outset of our investigation, phenyl diazonium tetra- high affinity binding to the cannabinoid CB1 and CB2 receptors.
fluoroborate 1a, N-methylindole 2a were chosen as the model The visible-light-induced acylation process allowed the synthesis
substrates to survey the reaction conditions. Gratifyingly, when a of indol-3-yl naphthyl ketones 3aj in 54% yield directly.
mixture of 1a (0.3 mmol), 2a (0.4 mmol), Eosin Y (1 mol%) in MeCN The substrate scope was further investigated by reacting phenyl
was irradiated with 5 W white LED light under a CO pressure of diazonium tetrafluoroborate 1a with different indoles. Apart from
70 atm at room temperature for 16 h, the desired product 3aa 2a, 1-ethyl-2-methyl-1H-indole 2b smoothly reacted with 1a to
formed in 66% yield (Table 1, entry 1). Interestingly, the yield of 3aa give the corresponding product 3ba in 69% yield. 1,5-Dimethyl-1H-
was dramatically enhanced to 82% when the reaction was indole 2c and 6-chloro-1-methyl-1H-indole 2d were all suitable
performed with 5 W green LED light (Table 1, entry 2). A brief substrates generating the corresponding products 3ca and 3da in
survey of solvents such as MeCN, DMSO, THF, EtOAc and PhCF3 led 82% and 63% yields, respectively. However, 4-methoxy-substituted
to the observation that MeCN gave the highest yield of 3aa (Table 1, N-methylindole 2e gave the desired indol-3-yl phenyl ketone 3ea
entries 2–6). Subsequently, various organic dyes were further in moderate yield. Treatment of substrate 2f with 1a afforded the
258 H.-T. Zhang et al. / Chinese Chemical Letters 27 (2016) 256–260

Table 2 Table 3
Scope of aryldiazonium salts 1a. Scope of indoles 2a.

O O
5 W green LED 5 W green LED
Ar Ph
Eosin Y (1 mol%) Eosin Y (1 mol%)
ArN2 BF4 PhN 2 BF 4 + R R
+ N
N CO (70 atm), 16 h N CO (70 atm), 16 h N
2a MeCN, r.t. 3 1a 2 R1 MeCN, r.t. 3
1 R1

. .

Entry Aryldiazonium salts 1 Product 3 b


Yield (%) Entry Indoles 2 Product 3 Yield (%)b

1 O 66 1 O 69
MeO OMe
N
1b 2b Et
N 3ab 3ba
N

2 O 73
2 O 82
1c 3ac N
N 2c 3ca
N
3 O 79
Br Br
3 O 63
1d 3ad
N Cl N
2d Cl 3da
N
4 O 74
O 2N NO
4 OMe OMe 51
1e 3ae O
N

N
5 O 70 2e
N
3ea
F 3C CF

1f
5 O 54
3af
N
N
N
6 F3C O 72 2f 3f a

6 O 59
CF
N 3ag N
1g N N
N
2g 3ga
7 Cl O 57
7 O 51

Cl N
1h N 3ah 2h H HN
3ha
8 F O 59 8 O 49
F
F N
F 2i H
N 3ia
1i 3ai N

9 54 9 H 42
O F O
F N
2j H
1j HN
N 3aj 3ja

a
a
Reaction conditions: 1a (0.3 mmol), 2 (0.4 mmol), Eosin Y (1 mol%), MeCN
Reaction conditions: 1 (0.3 mmol), 2a (0.4 mmol), Eosin Y (1 mol%), MeCN (3.0 mL), room temperature, CO (70 atm), 5 W green LED light for 16 h.
(3.0 mL), room temperature, CO (70 atm), 5 W green LED light for 16 h. b
Isolated yield.
b
Isolated yield.

A
desired product 3fa in moderate yield. In addition, 1-methyl-1H-
pyrrolo[2,3-b]pyridine 2g could also provide the expected product
3ga in 59% yield. It was found that reactions of free NH-indoles 2h–
2j with 1a proceeded well and gave the desired 3-acylindoles 2ha,
2ia and 2ja in 51%, 49% and 42% yields, respectively (Table 3,
entries 7–9).
To gain insight into the mechanism of the reaction, we B
conducted a series of control experiments [11b,c]. It has been
reported that the reaction of aryldiazonium tetrafluoroborate with
N-methylindoles can deliver azo-coupling products. We evaluated
the possibility of the formation of 3-arylsulfonyl-indoles by the
reactions in Tables 1–3, but no azo-coupling products or related Scheme 2. Control experiment.
intermediates were found under our conditions. When a radical-
trapping reagent, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)
(1.0 equiv.), was added to the model reaction, no aryl ketone was the reaction and/or under dark conditions. Reactions in the dark
obtained (Scheme 2A). These results suggest that the photoreac- and at increased temperature (up to 80 8C) gave no desired
tion proceeds via a radical pathway. Furthermore, the product products (Scheme 2B), which excludes homolytic bond cleavage of
yields dropped precipitously when no photocatalyst was present in the starting material to an aryl radical under these conditions.
H.-T. Zhang et al. / Chinese Chemical Letters 27 (2016) 256–260 259

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