Synthesis of 1,4-Dicarbonyl Compounds by Visible-Light-Mediated Cross-Coupling Reactions of α-Chlorocarbonyls and Enol Acetates

Article abstract of DOI:10.1002/adsc.202000791

Herein, we report a protocol for visible-light-mediated radical coupling reactions of α-chloroketones and enol acetates to afford 1,4-dicarbonyl compounds, which are important precursors and intermediates in organic synthesis. The reaction involves photoredox-catalyzed activation of the α-chloroketone upon photoelectron transfer, carbon–chlorine bond cleavage, and coupling of the resulting radical with the carbon–carbon double bond of the enol acetate. This mild protocol has a wide substrate scope and moderate to good yields. (Figure presented.).

Full text of DOI:10.1002/adsc.202000791

Title: Synthesis of 1,4-Dicarbonyl Compounds by Visible-Light-
Mediated Cross-Coupling Reactions of α Chlorocarbonyls and
Enol Acetates
Authors: Qiang Liu, Rui-Guo Wang, Hongjian Song, Yuxiu Liu, and
Qing-Min Wang
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000791
Link to VoR: https://doi.org/10.1002/adsc.202000791

10.1002/adsc.202000791
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Synthesis of 1,4-Dicarbonyl Compounds by Visible-Light-
Mediated Cross-Coupling Reactions of α-Chlorocarbonyls and
Enol Acetates
Qiang Liu,[a] Rui-Guo Wang,[a] Hong-Jian Song,*[a] Yu-Xiu Liu,[a] and Qing-Min
Wang*[a,b]
a
State Key Laboratory of Elemento-Organic Chemistry, Research Institute of Elemento-Organic Chemistry, College of
Chemistry, Nankai University, Tianjin 300071, People’s Republic of China
b
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300071, People’s Republic of
China
E-mail: songhongjian@nankai.edu.cn; wangqm@nankai.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.
Abstract: Herein, we report a protocol for visible-light-
mediated radical coupling reactions of α-chloroketones and
enol acetates to afford 1,4-dicarbonyl compounds, which
are important precursors and intermediates in organic
Several methods have been developed for the
preparation of unsymmetrical 1,4-dicarbonyl
compounds, and three of the most commonly used are
synthesis. The reaction involves photoredox-catalyzed shown in Scheme 1. The classical catalytic method is
the Stetter reaction,[3] an umpolung reaction that
involves addition of an aldehyde to an α,β-
activation of the α-chloroketone upon photoelectron
transfer, carbon–chlorine bond cleavage, and coupling of
the resulting radical with the carbon–carbon double bond of
unsaturated carbonyl compound with catalysis by
cyanide ions or thiazolium salts (Path a). However,
an undesired benzoin side reaction occurs, and
modified Stetter-type reactions between an anion or
acyl radical and α,β-unsaturated carbonyl compounds
have been developed to avoid this side reaction.[4]
Additional applications of this umpolung strategy
have recently been reported.[5] Another method
involves oxidative cross-coupling reactions of
enolates,[6] enol silanes,[7] and enamines (Path b);[8]
and this method has been used in natural product
synthesis. However, the utility of this method is
reduced by the occurrence of competing homo-
coupling reactions. Another method is nucleophile–
electrophile coupling (Path c),[9] which has been used
to synthesize diketones for years. However, it
generally requires the use of transition metals or toxic
reagents as catalysts. For example, the Lei group[9a]
and the Baba group[9b] separately reported metal-
catalyzed cross-coupling reactions of α-chloroketones
with organotin enolates or zinc ketone enolates to
form diketones.
the enol acetate. This mild protocol has a wide substrate
scope and moderate to good yields.
Keywords: α-Chlorocarbonyls; Cross-coupling; 1,4-
Dicarbonyl compounds; Photocatalysis; Unsymmetrical
diketones
1,4-Dicarbonyl moieties are present in a wide
variety of natural products and bioactive compounds
(Figure 1),[1] and 1,4-dicarbonyl compounds are
versatile synthetic precursors to bioactive 5-
membered heterocycles—such as pyrroles, furans,
thiophenes, and cyclopentenones—with unique
biological properties.[2]
Figure 1. Natural products containing 1,4-dicarbonyl
moieties.
1
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10.1002/adsc.202000791
Advanced Synthesis & Catalysis
(%)b
1
2
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
fac-Ir(ppy)3
K2HPO4
K2HPO4
K2HPO4
K2HPO4
K2HPO4
K2HPO4
K2HPO4
K2HPO4
K2HPO4
K2HPO4
Na2CO3
NaHCO3
K2CO3
DMF
DMSO
dioxane
THF
48
70
77
72
NR
37
32
39
33
83
31
28
17
3
3
4
5
CH3OH
CHCl3
DCM
Scheme 1. Retrosynthetic Strategies for Synthesis of
Unsymmetrical 1,4-Dicarbonyl Compounds.
6
7
We were interested in exploring the use of
photocatalytic reduction reactions for the synthesis of
1,4-dicarbonyl compounds. These reactions have
attracted much attention because they proceed under
mild conditions and nontraditional bonding ways.[10]
For example, the Xiao group reported that
photocatalytic cleavage of the C–S bonds of
sulfonylketones generates carbon radicals that can
form 1,4-dicarbonyls by means of radical coupling.[11]
However, this method gives low yields of
unsymmetric diketones. The Yasuda group reported
8
DCE
9
toluene
acetone
acetone
acetone
acetone
acetone
acetone
acetone
acetone
acetone
10
11
12
13
14
15
16
17
18
Cs2CO3
KOAc
that
bromocarbonyl
compounds
can
be
photocatalytically cleaved to generate carbon radicals,
which can undergo Eosin Y–accelerated coupling
with silyl enol ethers to form 1,4-dicarbonyl
compounds.[12] However, their approach seems to be
limited to substrates with activated C–Br bonds. We
nevertheless hypothesized that with the proper choice
of photocatalyst and reaction conditions, α-
chloroketones could serve as radical precursors.
Recently, many methods to form ketones have been
reported through radical additions to the double bond
of enol acetate and proved to be a practical method to
construct functionalized ketones.[13] Indeed we herein
report that we have successfully developed a protocol
for visible-light-mediated cleavage of the C–Cl bonds
of α-chloroketones and subsequent radical coupling
reactions with enol acetates to afford 1,4-dicarbonyl
compounds (Scheme 1, this work).
36
NR
NR
NR
TMEDA
Et3N
DIPEA
Ru(bpy)3Cl2·6H
2O
19
K2HPO4
acetone
NR
20
21
Eosin Y
fac-Ir(ppy)3
None
K2HPO4
None
acetone
acetone
acetone
acetone
NR
34
22
K2HPO4
K2HPO4
NR
NR
23c
fac-Ir(ppy)3
aGeneral conditions, unless otherwise noted: 1a (0.2 mmol),
2a (1.0 mmol), photocatalyst (2 mol %), and base (0.2
mmol) in 2 mL of solvent in an 8 mL bottle were irradiated
by a 5 W blue LED (approximately 5 cm away from the
light source) with stirring at rt under Ar atmosphere for 24
Table 1. Optimization of the Reaction Conditions.a
b
c
h. Isolated yield are given; NR = no reaction. Reaction
performed in the absence of light.
entry photocatalyst
base
solvent
yield
2
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10.1002/adsc.202000791
Advanced Synthesis & Catalysis
To test our hypothesis, we explored reactions of
benzyl 2-chloro-2-phenylacetate (1a) as the radical
precursor and 1-phenylvinyl acetate (2a) as the
radical acceptor (Table 1). To our delight, irradiation
of the two substrates with a blue LED in dry DMF in
the presence of fac-Ir(ppy)3 as the photocatalyst and
K2PHO4 as the base at room temperature under argon
afforded desired product 3aa in 48% yield (entry 1).
Evaluation of other solvents (entries 2–10) revealed
that acetone was the most effective, increasing the
yield of 3aa to 83% (entry 10). None of the other
bases we tried (Na2CO3, NaHCO3, K2CO3, Cs2CO3,
KOAc, tetramethylethylenediamine, Et3N, and
diisopropylethylamine; entries 11–18) performed
better than K2HPO4. We also tested two other
photoredox catalysts, but they failed to catalyze the
desired reaction (entries 19 and 20). Finally, we
performed some control experiments, which indicated
that the base, the blue light, and the photocatalyst
were necessary for the reaction (entries 21–23).
aReaction conditions A, unless otherwise noted: 1 (0.2
mmol), 2a (1.0 mmol), fac-Ir(ppy)3 (2 mol %), and
K2PHO4 (0.2 mmol) in 2 mL of acetone were stirred in an
8 mL bottle with irradiation by a 5 W blue LED at rt under
Ar atmosphere for 24 h. Isolated yields are given.
bReaction conditions B: 1 (0.6 mmol), 2a (0.3 mmol), fac-
Ir(ppy)3 (2 mol %), and K2PHO4 (0.3 mmol) in 3 mL of
acetone were stirred in an 8 mL bottle with irradiation by a
5 W blue LED at rt under Ar atmosphere for 24 h.
Using the optimized reaction conditions (Table 1,
entry 10), we examined the scope of the reaction with
respect to the α-chlorocarbonyl (Scheme 2). In
reactions with 1-phenylvinyl acetate (2a), substrates
with R1 = alkoxy and R2 = phenyl were well-tolerated,
affording 3ba–3ha in 47–82% yields. Notably,
substrate 1c, which had an I atom on the aryl ring of
the R1 group, underwent selective dehalogenation of
the Cl atom to afford 3ca. When R1 was a phenyl
group or a benzyl group, products 3ia and 3ja were
obtained in 74% and 83% yields, respectively. When
R1 or R2 was a methyl group and the other substituent
was a phenyl group, moderate to good yields of the
corresponding products (3ka–3oa) were obtained.
Furthermore, the reaction conditions were also
suitable for acetophenone substrates. Specifically,
when 2-chloroacetophenone was used as the radical
precursor (considering the relatively poor stability of
Next, we used benzyl 2-chloro-2-phenylacetate (1a)
as a radical precursor to investigate the reactions of
various enol acetates 2 (Scheme 3). When R4 was
hydrogen and R3 was a phenyl group with a methoxyl,
methyl, tert-butyl, or fluoro substituent, the
corresponding products (3ab–3ak) were obtained in
good yields. The electronic properties of the
substituent on the phenyl group affected the yield:
substrates with electron-donating substituents
generally showed higher yields than those with
electron-withdrawing substituents (compare 3ac and
3ae with 3aj). The position of the substituent also
affected the yield (compare 3ab and 3ac with 3ad,
compare 3ae with 3af, and compare 3ai with 3aj).
We also tried alkyl-type enol acetate for this reaction,
but no positive results were got.
the phenyl acetyl radical,
2
equivalent 2-
chloroacetophenone was used), 3pa was obtained in
85% yield. Encouraged by this result, we tested a
series of phenyl chloromethyl ketones containing
various functional groups (fluoro, chloro, bromo, and
methoxyl) and obtained products 3qa–3wa in 52–
82% yields.
Scheme 3. Scope of the Reaction with Respect to the Enol
Acetatea
Scheme 2. Scope of the Reaction with Respect to the α-
Chlorocarbonyls
3
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10.1002/adsc.202000791
Advanced Synthesis & Catalysis
NMR and high-resolution mass spectrometry.
Furthermore, when TEMPO was added to a mixture
containing 1p and 1-phenylethenyl acetate (2a) under
the standard conditions, none of the desired product
formed, and the TEMPO adduct of the acetophenone
radical was obtained in 65% yield. These results
confirm that the reaction proceeded via radical
intermediates. To determine whether radical
propagation was involved, we performed light on/off
experiments with 1a and 2a as substrates (see the
Supporting Information for details), which showed
the irradiation dependence of the reaction yield and
thus ruled out the involvement of radical chain
pathway.
Scheme 5. Control Experiments.
aReaction conditions A: 1a (0.2 mmol), 2 (1.0 mmol), fac-
Ir(ppy)3 (2 mol %), and K2PHO4 (0.2 mmol) in 2 mL of
acetone were stirred in an 8 mL bottle with irradiation by a
5 W blue LED at rt under Ar atmosphere for 24 h. Isolated
yields are given.
To demonstrate the utility of our protocol, we
carried out a gram-scale reaction of 1p and 2a, which
afforded 3pa in 71% isolated yield (Scheme 4). In
addition, we demonstrated that a furan, a thiophene,
and a pyrrole could be readily synthesized from
3pa.[11,14]
On the basis of these control experiments and
literature precedent,[13g, 13k, 15] a plausible mechanism
for this transformation is shown for 1p in Scheme 6.
Upon irradiation with the blue LED, the ground-state
photocatalyst is excited to a strongly reducing
red
excited-state Ir(ppy)3* species (E1/2 [Ir(IV)/*Ir(III)]
= −1.73 V vs SCE). This species is oxidatively
quenched by means of single electron transfer to
generate Ir(ppy)3 and cleave the C–Cl bond of 1p to
+
Scheme 4. Gram-scale Reaction and Synthetic
Applications of a Diketone Product
form carbon radical A. Radical A couples with the
enol double bond of 2a to generate radical
intermediate B,[6k] which is oxidized by single
electron transfer to produce cation C and regenerate
ox
Ir(ppy)3 (E1/2 (Ir(IV)/Ir(III) = 0.78 V vs SCE).
Finally, desired product 3pa is generated from the
hydrolysis of intermediate C, the produced AcOH
react with K2HPO4 to generate AcOK as by-product.
The final hydrolysis is accelerated under basic
conditions.
Scheme 6. Proposed Reaction Mechanism.
To gain insight into the reaction mechanism, we
carried out two control experiments (Scheme 5).
When
the
radical
inhibitor
(2,2,6,6-
tetramethylpiperidin-1-yl)oxyl (TEMPO) was added
to a mixture containing 2-chloroacetophenone (1p)
but no enol acetate under the standard conditions, a
73% yield of the TEMPO adduct of the acetophenone
radical (7p), the structure of which was confirmed by
4
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10.1002/adsc.202000791
Advanced Synthesis & Catalysis
H. Takikawa, A. Fürstner, Angew. Chem. 2013, 125,
9713-9717; Angew. Chem. Int. Ed. 2013, 52, 9534-
9538; c) T. Mukaiyama, K. Narasaka, M. Furusato, J.
Am. Chem. Soc. 1972, 94, 8641-8642; d) M.
Whittaker, C. D. Floyd, P. Brown, A. J. H. Gearing,
Chem. Rev. 1999, 99, 2735–2776; e) T. Fujisawa, K.
Igeta, S. Odake, Y. Morita, J. Yasuda, T. Morikawa,
Bioorg. Med. Chem. 2002, 10, 2569–2581.
[2] a) H. S. P. Rao, S. Jothilingam, J. Org. Chem. 2003,
68, 5392-5394; b) M. Biava, G. C. Porretta, D.
Deidda, R. Pompei, A. Tafi, F. Manetti, Bioorg. Med.
Chem. 2004, 12, 1453-1458; c) J. B. Chaires, J. Ren,
D. Hamelberg, A. Kumar, V. Pandya, D. W. Boykin,
W. D. Wilson, J. Med. Chem. 2004, 47, 5729-5742; d)
C.-S. Li, Y.-H. Tsai, W.-C. Lee, W.-J. Kuo, J. Org.
Chem. 2010, 75, 4004-4013; e) F. Guo, L. C. Konkol,
R. J. Thomson,J. Am. Chem. Soc. 2011, 133, 18-20; f)
E. O'Reilly, C. Iglesias, D. Ghislieri, J. Hopwood, J. L.
Galman, R. C. Lloyd, N. J. Turner, Angew. Chem.
2014, 126, 2479-2482; Angew. Chem. Int. Ed. 2014,
53, 2447-2450; g) G. Hua, J. B. Henry, Y. Li, A. R.
Mount, A. M. Z. Slawin, J. D. Woollins, Org. Biomol.
Chem. 2010, 8, 1655-1660; h) D. C. Cole, J. R. Stock,
R. Chopra, R. Cowling, J. W. Ellingboe, K. Y. Fan, B.
L. Harrison, Y. Hu, S. Jacobsen, L. D. Jennings, G.
Jin, P. A. Lohse, M. S. Malamas, E. S. Manas, W. J.
Moore, M.-M. O’Donnell, A. M. Olland, A. J.
Robichaud, K. Svenson, J. Wu, E. Wagner, J. Bard,
Bioorg. Med. Chem. Lett. 2008, 18, 1063-1066.
In summary, we have developed a protocol for
visible-light mediated cross-coupling reactions of
readily accessible α-chlorocarbonyls and enol
acetates for the synthesis of unsymmetrical 1,4-
dicarbonyl compounds, some of which are difficult to
obtain by traditional methods. The coupling products
could be used as precursors for substituted
heterocycles. The mild conditions, broad substrate
scope, and moderate to good yields of this novel
protocol make it an advance in the synthesis of
diketones.
Experimental Section
To an 8 mL glass vial was added Ir(ppy)3 (2.3 mg,
0.004 mmol), α-chlorocarbonyls (0.2 mmol), enol acetate
(1.0 mmol, 5.0 equiv), K2HPO4 (69.7 mg, 0.4 mmol), 2 mL
of acetone. The reaction mixture was degassed by bubbling
with argon for 30 s with an outlet needle and the vial was
sealed with PTFE cap. The mixture was then stirred
[3] H. Setter, Angew Chem. 1976, 88, 695-704; Angew
Chem. Int. Ed. 1976, 15, 639-647.
rapidly and irradiated with
a
5
W
Blue LED
(approximately 5 cm away from the light source) at room
temperature for 24 h. The reaction mixture was
concentrated in vacuum to remove the solvent. The
mixture was diluted with 10 mL H2O, and extracted with
EtOAc (3 × 8 mL). The combined organic extracts were
washed with brine (10 mL), dried over Na2SO4, and
concentrated in vacuo. Purification of the crude product by
flash chromatography on silica gel using the indicated
solvent system afforded the desired product (Petroleum
ether/EtOAc from 50:1 to 10:1).
[4] a) M. C. Myers, A. R. Bharadwaj, B. C. Milgram, K.
A. Scheidt, J. Am. Chem. Soc. 2005, 127, 14675-
14680; b) A. T. Biju, N. E. Wurz, F. Glorius, J. Am.
Chem. Soc. 2010, 132, 5970-5971; c) M. M. D. Wilde,
M. Gravel, Angew. Chem. 2013, 125, 12883-12886;
Angew. Chem. Int. Ed. 2013, 52, 12651-12654.
[5] a) G. Goti, B. Bieszczad, A. Vega-Peñaloza, P.
Melchiorre, Angew. Chem. 2019, 131, 1226-1230;
Angew. Chem. Int. Ed. 2019, 58, 1213-1217; b) T.
Morack, C. Mück-Lichtenfeld, R. Gilmour, Angew.
Chem. 2019, 131, 1221-1225; Angew. Chem. Int. Ed.
2019, 58, 1208-1212; c) J.-J. Zhao, H.-H. Zhang, X.
Shen, S. Yu, Org. Lett. 2019, 21, 913-916.
Acknowledgements
We are grateful to the National Natural Science Foundation of
China (21977056, 21732002) and the Fundamental Research
Funds for the Central Universities, Nankai University
(63201043) for generous financial support for our programs.
[6] a) P. S. Baran, M. P. DeMartino, Angew. Chem. 2006,
118, 7241-7244. Angew. Chem. Int. Ed. 2006, 45,
7083-7086; b) Y. Ito, T. Konoike, T. Saegusa, J. Am.
Chem. Soc. 1975, 97, 2912-2914; c) M. W. Rathke, A.
Lindert, J. Am. Chem. Soc. 1971, 93, 4605-4606; d) B.
M. Casey, R. A. Flowers, J. Am. Chem. Soc. 2011,
133, 11492-11495; e) Y. Ito, T. Konoike, T. Harada,
5
References
[1] a) S.-H. Li, J. Wang, X.-M. Niu, Y.-H. Shen, H.-J.
Zhang, H.-D. Sun, M.-L. Li, Q.-E. Tian, Y. Lu, P.
Cao, Q.-T. Zheng, Org. Lett. 2004, 6, 4327-4330; b)
G. Valot, C. S. Regens, D. P. O'Malley, E. Godineau,
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000791
Advanced Synthesis & Catalysis
T. Saegusa, J. Am. Chem. Soc. 1977, 99, 1487-1493;
6711; Angew. Chem. Int. Ed. 2004, 43, 6547-6549; g)
C. Che, Z. Qian, M. Wu, Y. Zhao, G. Zhu, J. Org.
Chem. 2018, 83, 5665-5673; h) J. Xie, Z.-Z. Huang,
Chem. Commun. 2010, 46, 1947-1949; i) X.-W. Lan,
N.-X. Wang, W. Zhang, J.-L. Wen, C.-B. Bai, Y.
Xing, Y.-H. Li, Org. Lett. 2015, 17, 4460-4463; j) Y.
Zhu, L. Zhang, S. Luo, J. Am. Chem. Soc. 2014, 136,
14642-14645.
f) R. Imbos, M. H. G. Brilman, M. Pineschi, B. L.
Feringa, Org. Lett. 1999, 1, 623-625; g) V.
Rautenstrauch, Bull. Soc. Chim. Fr. 1994, 131, 515-
524. h) R. Shintani, N. Tokunaga, H. Doi, T. Hayashi,
J. Am. Chem. Soc. 2004, 126, 6240-6241; i) P. Q.
Nguyen, H. J. Schäfer, Org. Lett. 2001, 3, 2993-2995;
J) A. A. N. de Souza, N. S. Silva, A. V. Müller, A. S.
Polo, T. J. Brocksom, K. T. de Oliveira, J. Org. Chem.
2018, 83, 15077-15086; k) L. Wang, P. Cheng, X.
Wang, W. Wang, J. Zeng, Y. Liang, O. Reiser, Org.
Chem. Front. 2019, 6, 3771-3775; l) T. Foell, J.
Rehbein, O. Reiser, Org. Lett. 2018, 20, 5794-5798;
m) Y. Onishi, Y. Yoneda, Y. Nishimoto, M. Yasuda,
A. Baba, Org. Lett. 2012, 14, 5788-5791; n) T. Hering,
D. P. Hari, B. Koenig, J. Org. Chem. 2012, 77,
10347-10352.
[10] a) C.-J. Wallentin, J. D. Nguyen, P. Finkbeiner, C. R.
J. Stephenson, J. Am. Chem. Soc. 2012, 134, 8875-
8884; b) J. D. Nguyen, J. W. Tucker, M. D.
Konieczynska, C. R. J. Stephenson, J. Am. Chem. Soc.
2011, 133, 4160-4163; c) M. Pirtsch, S. Paria, T.
Matsuno, H. Isobe, O. Reiser, Chem. Eur. J. 2012, 18,
7336-7340; d) J. W. Tucker, J. D. Nguyen, J. M. R.
Narayanam, S. W. Krabbe, C. R. J. Stephenson, Chem.
Commun. 2010, 46, 4985-4987; e) J. M. R.
Narayanam, J. W. Tucker, C. R. J. Stephenson, J. Am.
Chem. Soc. 2009, 131, 8756-8757; f) L. Furst, J. M. R.
Narayanam, C. R. J. Stephenson, Angew. Chem. 2011,
123, 9829-9833; Angew. Chem. Int. Ed. 2011, 50,
9655-9659; g) M. Nappi, G. Bergonzini, P.
Melchiorre, Angew. Chem. 2014, 126, 5021-5025;
Angew. Chem. Int. Ed. 2014, 53, 4921-4925; h) E.
Arceo, I. D. Jurberg, A. Álvarez-Fernández, P.
Melchiorre, Nat. Chem. 2013, 5, 750-756; i) E. Arceo,
A. Bahamonde, G. Bergonzini, P. Melchiorre, Chem.
Sci. 2014, 5, 2438-2442.
[7] a) C. T. Avetta, L. C. Konkol, C. N. Taylor, K. C.
Dugan, C. L. Stern, R. J. Thomson, Org. Lett. 2008,
10, 5621-5624; b) M. D. Clift, C. N. Taylor, R. J.
Thomson, Org. Lett. 2007, 9, 4667-4669; c) M.
Schmittel, A. Burghart, W. Malisch, J. Reising, R.
Söllner, J. Org. Chem. 1998, 63, 396-400; d) H. M. R.
Hoffmann, I. Münnich, O. Nowitzki, H. Stucke, D. J.
Williams, Tetrahedron 1996, 52, 11783-11798; e) M.
Schmittel, A. Haeuseler, J. Organomet. Chem. 2002,
661, 169-179; f) M. D. Clift, R. J. Thomson, J. Am.
Chem. Soc. 2009, 131, 14579-14583.
[8] a) A. B. Paolobelli, D. Latini, R. Ruzziconi,
Tetrahedron Lett. 1993, 34, 721–724; b) T. Fujii, T.
Hirao, Y. Ohshiro, Tetrahedron Lett. 1992, 33, 5823–
5826; c) Y. Ito, T. Konoike, T. Saegusa, J. Am. Chem.
Soc. 1975, 97, 649–651; d) Q. Li, A. Fan, Z. Lu, Y.
Cui, W. Lin, Y. Jia, Org. Lett. 2010, 12, 4066–4069;
e) E. Baciocchi, A. Casu, R. Ruzziconi, Tetrahedron
Lett. 1989, 30, 3707–3710; f) H.-Y. Jang, J.-B. Hong,
D. W. C. MacMillan, J. Am. Chem. Soc. 2007, 129,
7004–7005; g) K. Ryter, T. Livinghouse, J. Am. Chem.
Soc. 1998, 120, 2658– 2659.
[11] J. Xuan, Z.-J. Feng, J.-R. Chen, L.-Q. Lu, W.-J. Xiao,
Chem. Eur. J. 2014, 20, 3045-3049.
[12] N. Esumi, K. Suzuki, Y. Nishimoto, M. Yasuda, Org.
Lett. 2016, 18, 5704-5707.
[13] a) Y. Tang, Y. Fan, H. Gao, X. Li, X. Xu,
Tetrahedron Lett. 2015, 56, 5616-5618; b) L.
Buglioni, P. Riente, E. Palomares, M. A. Pericàs, Eur.
J. Org. Chem. 2017, 6986-6990; c) H. Jiang, Y.
Cheng, Y. Zhang, S. Yu, Eur. J. Org. Chem., 2013,
2013, 5485-5492; d) T. Hering, D. P. Hari, B. König,
J. Org. Chem. 2012, 77, 10347-10352; e) D. Felipe-
Blanco, J. C. Gonzalez-Gomez, Adv. Synth. Catal.
2018, 360, 2773-2778; f) C.-X. Song, G.-X. Cai, T. R.
Farrell, Z.-P. Jiang, H. Li, L.-B. Gan, Z.-J. Shi, Chem.
Comm. 2009, 6002-6004; g) T. Föll, J. Rehbein, O.
Reiser, Org. Lett. 2018, 20, 5794-5798; h) Y. Tang, Y.
Fan, Y. Zhang, X. Li, X. Xu, Synlett. 2016, 27, 1860-
1863; i) P. Panday, P. Garg, A. Singh, Asian J. Org.
Chem. 2018, 7, 111-115; j) P. Cheng, W. Wang, L.
Wang, J. Zeng, O. Reiser, Y. Liang, Tetrahedron
Letters 2019, 60, 1408-1412; k) L. Wang, P. Cheng,
X. Wang, W. Wang, J. Zeng, Y. Liang, O. Reiser,
Org. Chem. Front. 2019, 6, 3771-3775.
[9] a) C. Liu, Y. Deng, J. Wang, Y. Yang, S. Tang, A. Lei,
Angew. Chem. 2011, 123, 7475-7479; Angew. Chem.
Int. Ed. 2011, 50, 7337-7341; b) M. Yasuda, S. Tsuji,
Y. Shigeyoshi, A. Baba, J. Am. Chem. Soc. 2002, 124,
7440-7447; c) P. Setzer, A. Beauseigneur, M. S. M.
Pearson-Long, P. Bertus, Angew. Chem. 2010, 122,
8873-8876; Angew. Chem. Int. Ed. 2010, 49, 8691-
8694; d) Z.-L. Shen, K. K. K. Goh, H.-L. Cheong, C.
H. A. Wong, Y.-C. Lai, Y.-S. Yang, T.-P. Loh, J. Am.
Chem. Soc. 2010, 132, 15852-15855; e) B. B. Parida,
P. P. Das, M. Niocel, J. K. Cha, Org. Lett. 2013, 15,
1780-1783; f) M. Rössle, T. Werner, A. Baro, W.
Frey, J. Christoffers, Angew. Chem. 2004, 116, 6709-
6
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Advanced Synthesis & Catalysis
[14] X. Zheng, S. Lu, Z. Li, Org. Lett. 2013, 15, 5432-
[15] J.-N. Zhu, W.-K. Wang, Y. Zhu, Y.-Q. Hu, S.-Y.
5435.
Zhao, Org. Lett. 2019, 21, 6270-6274.
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Advanced Synthesis & Catalysis
COMMUNICATION
Synthesis of 1,4-Dicarbonyl Compounds by
Visible-Light-Mediated Cross-Coupling Reactions
of α-Chlorocarbonyls and Enol Acetates
Adv. Synth. Catal. Year, Volume, Page – Page
Qiang Liu, Rui-Guo Wang, Hong-Jian Song,* Yu-
Xiu Liu and Qing-Min Wang*
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