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

The synthesis and transformation of indoles have been and
continue to be a focus of research efforts for synthetic organic
chemists because the indole nucleus is found in countless
biologically active molecules and medicinally relevant structures
[1]. Indol-3-yl aryl ketones represent an important class of
nitrogen-containing heterocycles, which are the basic constituents
of numerous natural products, biologically active alkaloids,
functional materials and pharmaceuticals [2]. Consequently, the
development of synthetic methods for the preparation of indol-3-
yl aryl ketones has received considerable attention [3]. Among the
numerous methods that have been developed, the most commonly
used methods are Friedel–Crafts reactions [4], Vilsmeier–Haack
type reactions [5], and Grignard reactions [6]. Recently, transition-
metal-catalyzed acylation of C–H bonds has been developed as
promising protocols for the construction of indol-3-yl aryl ketones
[7]. However, these reactions employ acids, bases or transition
* Corresponding author at: Yunnan Minzu University, Key Laboratory of
Chemistry in Ethnic Medicinal Resources, State Ethnic Affairs Commission &
Ministry of Education, Kunming 650500, China.
** Corresponding author.
E-mail addresses: gulijun2005@126.com (L.-J. Gu), ganpeng_li@sina.com
(G.-P. Li).
under acid-free, base-free and transition-metal-free conditions has
not yet been realized.
Recently visible light photoredox catalysis attracted much
attention due to the rich resource of visible light, the fact that it is
environment-friendly, and high efficiency [8]. After having
garnered little interest for about one century since being sponsored
by Ciamician, reports on visible light photoredox catalysis
exploded since 2008, which exhibited powerful ability in organic
synthesis and material chemistry [9]. Many visible-light photo-
redox catalysts such as metal or none-metal complexes have been
used to solve the problem of visible light absorption efficiency
[10]. In these methods, readily available, reactive aryl diazonium
salts have been widely utilized as a convenient aryl radical source
[11]. As a result, many unusual transformations of these reagents
have been carried out by photocatalysis. Recently, Wangelin and
Xiao independently reported a visible-light-mediated redox
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
efficiently converted into acyl radicals that can be further oxidized
to benzylidyneoxonium salts by the oxidized dye radical cation.
We envisioned that indoles might serve as a platform to trap
benzylidyneoxonium ions. To explore the application of photo-
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
apparatus and uncorrected. IR spectra were recorded on an
EQUINOX-55 spectrometer in a KBr matrix. NMR spectra were
recorded on an INOVA-400 NMR instrument at room temperature
using TMS as an internal standard. Coupling constants (J) were
measured in Hz. Chemical shift values (d) are given in ppm. High
Resolution mass spectrometer (HRMS) spectra were recorded on a
Bruker micrOTOF-Q II analyzer. A 200–300 mesh silica gel was
used for column chromatography.
General procedure: To an 8 mL vial equipped with a magnetic
stir bar was charged with 1 (0.3 mmol), 2 (0.4 mmol), Eosin Y
(1 mol%), dry MeCN (3.0 mL). The vial was purged with N2 in the
dark and transferred into an autoclave with a Quartz window
bottom. The autoclave was flushed three times and slowly filled
with 70 atm of CO. The reaction was irradiated with external LEDs
at room temperature for 16 h. After the reaction was finished, the
gas was carefully released and the vial retrieved, the reaction
mixture was diluted with 5 mL of H2O, extracted with ethyl acetate
(10 mL  3). The organic portion was washed with a saturated
solution of brine, dried (Na2SO4) and concentrated in vacuum, and
the resulting residue was purified by silica gel column chroma-
tography (hexane/ethyl acetate) to provide the desired products
3. The characterization data of products 3 were provided in
Supporting information.
3. Results and discussion
At the outset of our investigation, phenyl diazonium tetra-
fluoroborate 1a, N-methylindole 2a were chosen as the model
substrates to survey the reaction conditions. Gratifyingly, when a
mixture of 1a (0.3 mmol), 2a (0.4 mmol), Eosin Y (1 mol%) in MeCN
was irradiated with 5 W white LED light under a CO pressure of
70 atm at room temperature for 16 h, the desired product 3aa
formed in 66% yield (Table 1, entry 1). Interestingly, the yield of 3aa
was dramatically enhanced to 82% when the reaction was
performed with 5 W green LED light (Table 1, entry 2). A brief
survey of solvents such as MeCN, DMSO, THF, EtOAc and PhCF3 led
to the observation that MeCN gave the highest yield of 3aa (Table 1,
entries 2–6). Subsequently, various organic dyes were further
investigated and the results showed that Eosin Y was more
effective in producing the desired product (Table 1, entries 2, 7–9).
Lower pressure of CO resulted in low conversion (Table 1, entry
10). Both visible-light photoredox catalysts and visible light are
essential for the reaction to take place (Table 1, entries 11–12).
With this preliminary result in hand, the generality of the
method was explored under the optimized conditions. The scope of
aryldiazonium salts 1 was initially explored in the presence of N-
methylindole 2a, Eosin Y (1 mol%) under irradiation with 5 W
green LED light and a CO pressure of 70 atm in MeCN at room
temperature, and the results are summarized in Table 2. In general,
a variety of functional groups on the phenyl ring of aryldiazonium
salts were compatible in this procedure, affording the desired
products in good to excellent yields. The electron-donating groups
such as methoxy and methyl groups on the aryl ring allowed the
aryldiazonium salts to react with 2a efficiently and gave the
desired products 3ab–3ac in good yields. Aryldiazonium salts
bearing electron-withdrawing halogen, CF3 and NO2 groups
reacted smoothly to give the corresponding products in good
yields (3ad–3af). Furthermore, the substituent at the meta position
on the arene group did not affect the reaction efficiency (Table 2,
entry 6). However, a substituent at the ortho position of the phenyl
ring gave the corresponding product 3ah in a lower yield (Table 2,
entry 7). These results indicated that the steric effects affected the
efficiency of the reactions. Interestingly, a polysubstituted
aryldiazonium salt gave the desired product 3ai in moderate
yield (Table 1, entry 8). Notably, indol-3-yl naphthyl ketones are
high affinity binding to the cannabinoid CB1 and CB2 receptors.
The visible-light-induced acylation process allowed the synthesis
of indol-3-yl naphthyl ketones 3aj in 54% yield directly.
The substrate scope was further investigated by reacting phenyl
diazonium tetrafluoroborate 1a with different indoles. Apart from
2a, 1-ethyl-2-methyl-1H-indole 2b smoothly reacted with 1a to
give the corresponding product 3ba in 69% yield. 1,5-Dimethyl-1H-
indole 2c and 6-chloro-1-methyl-1H-indole 2d were all suitable
substrates generating the corresponding products 3ca and 3da in
82% and 63% yields, respectively. However, 4-methoxy-substituted
N-methylindole 2e gave the desired indol-3-yl phenyl ketone 3ea
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
Scheme 3. Plausible mechanism.
On the basis of these preliminary results, and those of
previous studies [11b, 12–14], we propose a mechanism shown
in Scheme 3. Initially, photoexcitation of Eosin Y by visible light
generates excited [Eosin Y*]. Then the electron-deficient phenyl
diazonium tetrafluoroborate 1a accepts one electron from the
excited [Eosin Y*]. This single-electron transfer (SET) results in
the generation of a phenyl radical (Ph) and the oxidized dye
radical cation [Eosin Y+]. The resulting phenyl radical (Ph) is
rapidly trapped by CO to give a benzoyl radical A. Further
oxidation of A by [Eosin Y+] results in the benzylidyneoxonium
B. Finally, electronic trapping of B by 2a gives the desired
product 3aa.
4. Conclusion
In summary, we have developed a visible-light-mediated
carbonylation for the synthesis of indol-3-yl aryl ketones, which
is a ubiquitous component of many natural products, biomolecules
and materials. Most importantly, simple and readily available
Eosin Y emerges as an efficient catalyst. Metal catalysts, which are
often expensive and difficult to be completely removed from
products and can be a challenge in the synthesis of pharmaceutical
compounds, were avoided. Mechanistic studies support the
sequential operation of SET reduction, carbonylation, and back
electron transfer to give aroylium cations. Further investigations of
the mechanism of the reaction and its applications are ongoing in
our laboratory.
Acknowledgments
We are grateful for the financial support from the Educational
Bureau of Yunnan Province (No. 2010Y431) and the State Ethnic
Affairs Commission (No. 12YNZ05).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cclet.2015.10.
012.
References
[1] (a) G.L. Regina, T. Sarkar, R. Bai, et al., New arylthioindoles and related bioisosteres
at the sulfur bridging group. 4. Synthesis, tubulin polymerization, cell growth
inhibition, and molecular modeling studies, J. Med. Chem. 52 (2009) 7512–7527;
(b) I. Nicolaou, V.J. Demopoulos, Substituted pyrrol-1-ylacetic acids that combine
aldose reductase enzyme inhibitory activity and ability to prevent the nonenzy-
matic irreversible modification of proteins from monosaccharides, J. Med. Chem. 46
(2003) 417–426;
(c) P.M. Fresneda, P. Molina, M.A. Saez, The first synthesis of the bis(indole) marine
alkaloid caulersin, Synlett 1999 (1999) 1651–1653;
259
(d) L.J. Zhang, X. Xue, C.H. Xu, et al., Rhodium-catalyzed decarbonylative direct C2-
arylation of indoles with aryl carboxylic acids, ChemCatChem 6 (2014) 3069–3074;
(e) S. Kathiravan, I.A. Nicholls, Rhodium(III)-catalysed aerobic synthesis of highly
functionalized indoles from N-arylurea under mild conditions through C–H activa-
tion, Chem. Commun. 50 (2014) 14964–14967;
(f) M. Kim, N.K. Mishra, J. Park, et al., Decarboxylative acylation of indolines with a-
keto acids under palladium catalysis: a facile strategy for the synthesis of 7-
substituted indoles, Chem. Commun. 50 (2014) 14249–14252;
For a few selected references, see:
[2] (a) J.E. Saxton, Recent progress in the chemistry of the monoterpenoid indole
alkaloids, Nat. Prod. Rep. 14 (1997) 559–590;
(b) M. Toyota, M. Ihara, Recent progress in the chemistry of non-monoterpenoid
indole alkaloids, Nat. Prod. Rep. 15 (1998) 327–340;
(c) M. Bandini, A. Eichholzer, Catalytic functionalization of indoles in a new
dimension, Angew. Chem. Int. Ed. 48 (2009) 9608–9644;
(d) Q.Q. Yang, C. Xiao, L.Q. Lu, et al., Synthesis of indoles through highly efficient
cascade reactions of sulfur ylides and N-(ortho-chloromethyl)aryl amides, Angew.
Chem. Int. Ed. 51 (2012) 9137–9140;
(e) X. Zhang, Y.F. Li, H. Shi, et al., Rhodium(III)-catalyzed intramolecular amidoar-
ylation and hydroarylation of alkyne via C–H activation: switchable synthesis of 3,4-
fused tricyclic indoles and chromans, Chem. Commun. 50 (2014) 7306–7309;
(f) M. Inman, C.J. Moody, Indole synthesis-something old, something new, Chem.
Sci. 4 (2013) 29–41;
(g) G.R. Humphrey, J.T. Kuethe, Practical methodologies for the synthesis of indoles,
Chem. Rev. 106 (2006) 2875–2911;
(h) L.J. Gu, C. Jin, H.T. Zhang, L.Z. Zhang, Copper-catalyzed aerobic oxidative cleavage
of C–C bonds in epoxides leading to aryl ketones, J. Org. Chem. 79 (2014) 8453–8456;
(i) R. Leurs, P.L. Chazot, F.C. Shenton, H.D. Lim, I.J.D. Esch, Molecular and biochemical
pharmacology of the histamine H4 receptor, Br. J. Pharmacol. 157 (2009) 14–23;
(j) P. Sang, Z.K. Chen, J.W. Zou, Y.H. Zhang, K2CO3 promoted direct sulfenylation of
indoles: a facile approach towards 3-sulfenylindoles, Green Chem. 15 (2013) 2096–
2100;
For selected examples, see:
[3] (a) M.M. Faul, L.L. Winnerosk, Palladium-catalyzed acylation of a 1,2-disubsti-
tuted 3-indolylzinc chloride, Tetrahedron Lett. 38 (1997) 4749–4752;
(b) S.K. Guchhait, M. Kashyap, H. Kamble, ZrCl4-mediated regio- and chemose-
lective Friedel–Crafts acylation of indole, J. Org. Chem. 76 (2011) 4753–4758;
(c) H. Johansson, A. Urruticoechea, I. Larsen, D.S. Pedersen, A scalable method for
regioselective 3-acylation of 2-substituted indoles under basic conditions, J. Org.
Chem. 80 (2015) 471–478;
(d) N.N. Wan, Y.H. Hui, Z.F. Xie, J.D. Wang, Friedel-crafts alkylation of indoles with
nitroalkenes catalyzed by Zn(II)–thiourea complex, Chin. J. Chem. 30 (2012) 311–
315;
(e) P. Zhang, T.B. Xiao, S.W. Xiong, X.C. Dong, L. Zhou, Synthesis of 3-acylindoles
by visible-light induced intramolecular oxidative cyclization of o-alkynylated
N,N-dialkylamines, Org. Lett. 14 (2014) 3264–3267;
(f) L. Yu, P.H. Li, L. Wang, Copper-promoted decarboxylative direct C3-acylation of
N-substituted indoles with a-oxocarboxylic acids, Chem. Commun. 49 (2013)
2368–2370;
For selected examples, see:
[4] (a) J.H. Wynne, C.T. Lloyd, S.D. Jensen, S. Boson, W.M. Stalick, 3-Acylindoles via a
one-pot, regioselective Friedel–Crafts reaction, Synthesis 14 (2004) 2277–2282;
(b) K. Yeung, M.E. Farkas, Z.L. Qiu, Z. Yang, Friedel-crafts acylation of indoles in
acidic imidazolium chloroaluminate ionic liquid at room temperature, Tetrahe-
dron Lett. 43 (2002) 5793–5795;
(c) T. Okauchi, M. Itonaga, T. Minami, et al., General method for acylation of
indoles at the 3-position with acyl chlorides in the presence of dialkylaluminum
chloride, Org. Lett. 2 (2000) 1485–1487;
For selected examples, see:
[5] W. Anthony, Novel synthesis of heterocyclic ketones, J. Org. Chem. 25 (1960)
2049–2053.
[6] J. Bergman, L. Venemalm, Intramolecular, ring closure of a,b-unsaturated 3-
acylindoles, Tetrahedron Lett. 28 (1987) 3741–3744.
[7] (a) Y.H. Ma, J.S. You, F.J. Song, Facile access to 3-acylindoles through palladium-
catalyzed addition of indoles to nitriles: the one-pot synthesis of indenoindo-
lones, Chem. Eur. J. 19 (2013) 1189–1193;
(b) M.N. Zhao, L.F. Ran, M. Chen, et al., Palladium-catalyzed carbonylation of
indoles for synthesis of indol-3-yl aryl ketones, ACS Catal. 5 (2015) 1210–1213;
(c) W.L. Wu, W.P. Su, Mild and selective Ru-catalyzed formylation and Fe-cata-
lyzed acylation of free (N–H) indoles using anilines as the carbonyl source, J. Am.
Chem. Soc. 133 (2011) 11924–11927;
(d) L.J. Gu, J.Y. Liu, L.Z. Zhang, Y. Xiong, R. Wang, Synthesis of 3-acylindoles via
decarboxylative cross-coupling reaction of free (N–H) indoles with a-oxocar-
boxylic acids, Chin. Chem. Lett. 25 (2014) 90–92;
For selected examples, see:
[8] (a) J. Xuan, W.J. Xiao, Visible-light photoredox catalysis, Angew. Chem. Int. Ed. 51
(2012) 6828–6838;
(b) T.P. Yoon, M.A. Ischay, J. Du, Visible light photocatalysis as a greener approach
to photochemical synthesis, Nat. Chem. 2 (2010) 527–532;
(c) C.K. Prier, D.A. Rankic, D.W.C. MacMillan, Visible light photoredox catalysis
with transition metal complexes: applications in organic synthesis, Chem. Rev.
113 (2013) 5322–5363;
(d) K. Zeitler, Photoredox catalysis with visible light, Angew. Chem. Int. Ed. 48
(2009) 9785–9789;
(e) L. Shi, W. Xia, Photoredox functionalization of C–H bonds adjacent to a
nitrogen atom, Chem. Soc. Rev. 41 (2012) 7687–7697;
260 H.-T. Zhang et al. / Chinese Chemical Letters 27 (2016) 256–260
(f) J.W. Tucker, C.R.J. Stephenson, Shining light on photoredox catalysis: theory
and synthetic applications, J. Org. Chem. 77 (2012) 1617–1622;
(g) D.M. Schultz, T.P. Yoon, Solar synthesis: prospects in visible light photocata-
lysis, Science 343 (2014) 1239176;
(h) M. Majek, F. Filace, A.J. Wangelin, On the mechanism of photocatalytic
reactions with eosin Y, Beilstein J. Org. Chem. 10 (2014) 981–989;
For selected reviews on visible-light photoredox catalysis, see:
[9] D.A. Nicewicz, D.W.C. MacMillan, Merging photoredox catalysis with organoca-
talysis: the direct asymmetric alkylation of aldehydes, Science 322 (2008) 77–80.
[10] (a) H.J. Jiang, Y.Z. Cheng, R.Z. Wang, Y. Zhang, S.Y. Yu, Synthesis of isoquinolines
via visible light-promoted insertion of vinyl isocyanides with diaryliodonium
salts, Chem. Commun. 50 (2014) 6164–6166;
(b) Y. Xu, W. Zhang, Ag/AgBr-grafted graphite-like carbon nitride with enhanced
plasmonic photocatalytic activity under visible light, ChemCatChem 5 (2013)
2343–2351;
(c) G.B. Deng, Z.Q. Wang, J.D. Xia, et al., Tandem cyclizations of 1,6-enynes with
arylsulfonyl chlorides by using visible-light photoredox catalysis, Angew. Chem.
Int. Ed. 52 (2013) 1535–1538;
(d) J.D. Xia, G.B. Deng, M.B. Zhou, et al., Reusable visible light photoredox
catalysts: catalyzed benzylic C(sp3)–H functionalization/carbocyclization reac-
tions, Synlett 18 (2012) 2707–2713;
(e) E.L. Tyson, Z.L. Niemeyer, T.P. Yoon, Redox mediators in visible light photo-
catalysis: photocatalytic radical thiol–ene additions, J. Org. Chem. 79 (2014)
1427–1436;
(f) L.J. Gu, C. Jin, J.Y. Liu, H.Y. Ding, B.M. Fan, Transition-metal-free, visible-light
induced cyclization of arylsulfonyl chlorides with 2-isocyanobiphenyls to produce
phenanthridines, Chem. Commun. 50 (2014) 4643–4645;
(g) J. Xuan, X. Xia, T. Zeng, et al., Visible-light-induced formal [3 + 2] cycloaddition
for pyrrole synthesis under metal-free conditions, Angew. Chem. Int. Ed. 53 (2014)
5653–5656;
(h) J. Liu, Q. Liu, H. Yi, et al., Visible-light-mediated decarboxylation/oxidative
amidation of a-keto acids with amines under mild reaction conditions using O2,
Angew. Chem. Int. Ed. 53 (2014) 502–506;
(i) D.P. Hari, B. König, Synthetic applications of eosin Y in photoredox catalysis,
Chem. Commun. 50 (2014) 6688–6699;
(j) A.K. Yadav, V.P. Srivastava, L.D.S. Yadav, Visible-light-mediated eosin Y catalyzed
aerobic desulfurization of thioamides into amides, New J. Chem. 37 (2013)
4119–4124;
(k) T.B. Xiao, L.Y. Li, G.L. Lin, et al., Synthesis of 6-substituted phenanthridines by
metal-free, visible-light induced aerobic oxidative cyclization of 2-isocyanobiphe-
nyls with hydrazines, Green Chem. 16 (2014) 2418–2421;
(l) M.N. Hopkinson, B. Sahoo, J. Li, F. Glorius, Dual catalysis sees the light: combining
photoredox with organo-, acid, and transition-metal catalysis, Chem. Eur. J. 20
(2014) 3874–3886;
(m) C. Yu, N. Iqbal, S. Park, E.J. Cho, Selective difluoroalkylation of alkenes by using
visible light photoredox catalysis, Chem. Commun. 50 (2014) 12884–12887;
(n) J.C. Tellis, D.N. Primer, G.A. Molander, Single-electron transmetalation in orga-
noboron cross-coupling by photoredox/nickel dual catalysis, Science 345 (2014)
433–436;
(o) Z. Zuo, D.T. Ahneman, L. Chu, et al., Merging photoredox with nickel catalysis:
coupling of a-carboxyl sp3-carbons with aryl halides, Science 345 (2014) 437–440;
For recent selected examples for visible-light photoredox catalysts, see:
[11] (a) D.P. Hari, P. Schroll, B. König, Metal-free, visible-light-mediated direct C–H
arylation of heteroarenes with aryl diazonium salts, J. Am. Chem. Soc. 134 (2012)
2958–2961;
(b) M. Majek, A.J. Wangelin, Metal-free carbonylations by photoredox catalysis,
Angew. Chem. Int. Ed. 54 (2015) 2270–2274;
(c) W. Guo, L.Q. Lu, Y. Wang, et al., Metal-free, room-temperature, radical
alkoxycarbonylation of aryldiazonium salts through visible-light photoredox
catalysis,, Angew. Chem. Int. Ed. 54 (2015) 2265–2269;
(d) T. Hering, D.P. Hari, B. König, Visible-light-mediated a-arylation of enol
acetates using aryl diazonium salts, J. Org. Chem. 77 (2012) 10347–10352;
(e) F.P. Crisóstomo, T. Martin, R. Carrillo, ascorbic acid as an initiator for the direct
C–H arylation of (hetero)arenes with anilines nitrosated in situ, Angew. Chem. Int.
Ed. 53 (2014) 2181–2185;
(f) L.J. Gu, C. Jin, J.Y. Yan, Metal-free, visible-light-mediated transformation of aryl
diazonium salts and (hetero)arenes: an efficient route to aryl ketones, Green
Chem. 17 (2015) 3733–3736.
[12] T. Kawamoto, T. Okada, D.P. Curran, I. Ryu, Efficient hydroxymethylation reactions
of iodoarenes using CO and 1,3-dimethylimidazol-2-ylidene borane, Org. Lett. 15
(2013) 2144–2147.
[13] B. Sahoo, M.N. Hopkinson, F. Glorius, Combining gold and photoredox catalysis:
visible light-mediated oxy- and aminoarylation of alkenes, J. Am. Chem. Soc. 135
(2013) 5505–5508.
[14] D.P. Hari, B. König, The photocatalyzed Meerwein arylation: classic reaction of
aryl diazonium salts in a new light, Angew. Chem. Int. Ed. 52 (2013) 4734–4743.