Regioselective oxidative ring-opening of cyclopropenyl carboxylates by visible light photoredox catalysis

Article abstract of DOI:10.1016/j.tetlet.2018.05.047

Catalyzed by Ir(dFCF₃ppy)₂(dtbbpy)PF₆, several aroyl methylidenemalonates were synthesized in good to excellent yields via visible light photoredox-catalyzed the oxidative ring-opening of cyclopropenyl carboxylate derivatives. The possible mechanism of oxidative quenching cycle was proposed.

Full text of DOI:10.1016/j.tetlet.2018.05.047

Accepted Manuscript
Regioselective Oxidative Ring-Opening of Cyclopropenyl Carboxylates by
Visible Light Photoredox Catalysis
Qianwen Ye, Hongqiang Ye, Dongping Cheng, Xiaonian Li, Xiaoliang Xu
PII:
S0040-4039(18)30661-0
https://doi.org/10.1016/j.tetlet.2018.05.047
TETL 49994
DOI:
Reference:
Tetrahedron Letters
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Received Date:
Revised Date:
Accepted Date:
17 February 2018
17 May 2018
18 May 2018
Please cite this article as: Ye, Q., Ye, H., Cheng, D., Li, X., Xu, X., Regioselective Oxidative Ring-Opening of
Cyclopropenyl Carboxylates by Visible Light Photoredox Catalysis, Tetrahedron Letters (2018), doi: https://
doi.org/10.1016/j.tetlet.2018.05.047
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Tetrahedron Letters
Regioselective Oxidative Ring-Opening of Cyclopropenyl Carboxylates by
Visible Light Photoredox Catalysis
Qianwen Ye,a Hongqiang Ye,a Dongping Cheng,*b Xiaonian Li,*a and Xiaoliang Xua
aCollege of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, P. R. China
bCollege of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310014, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Catalyzed by Ir(dFCF3ppy)2(dtbbpy)PF6, several aroyl methylidenemalonates were synthesized
in good to excellent yields via visible light photoredox-catalyzed the oxidative ring-opening of
cyclopropenyl carboxylate derivatives. The possible mechanism of oxidative quenching cycle
was proposed.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Visible light photoredox catalysis
Oxygen
Cyclopropenyl carboxylates
Aroyl methylidenemalonates
 Corresponding author. Tel.: +86-571-88320920; e-mail: chengdp@zjut.edu.cn; xnli@zjut.edu.cn; xuxiaoliang@zjut.edu.cn

2
Tetrahedron
Table 1: Optimization of the reaction conditionsa
Introduction
Visible light catalysis has attracted tremendous attention from
chemists owing to its wide applications in organic synthesis and
its significance in sustainable chemistry.1 Without stoichiometric
activated reagents, this catalytic strategy make it easier to get
access to various radical ions and/or radicals by photo-excited
single electron-transfer under very mild conditions.2-3 These
highly active in situ formed intermediates could participate in the
innovative valuable reactions and transform into numerous
interesting molecules in a controllable manner.4 Among the
various reactions mediated by visible light catalysis, the
oxidation of carbon-carbon double bonds and its subsequent
transformation have drawn much attention. For example, Yoon
group reported several [2+2] cross-cycloadditions through the
photocatalytic oxidation of olefins to give a range of cyclobutane
derivatives.5 Most noteworthy was that the oxidative
entry
1
photocatalyst
oxidant
PhN2BF4
-
time/h Yield (%)b
Ir(ppy)3
14
4
36
2
Ir(ppy)3
16
3
Ir(ppy)3
CBr4
10
14
24
24
65
4
Ir(ppy)3
CCl4
65
5
Ir(ppy)3
Na2S2O8
K2S2O8
67
6
Ir(ppy)3
26
7
Ir(ppy)3
(NH4)2S2O8 24
trace
dehydrogenative coupling of alkenes induced by photo-oxidation
was also explored, such as the selective oxidative [4+2]
annulation of imine and alkene for the synthesis of substituted
dihydroisoquinolines,6a the C-H/C-H cross-coupling between
electron-rich arenes and styrene derivatives affording various
substituted aryl alkenes,6b and the cross-coupling of alkenes with
alcohols or azoles generating multi-substituted enol ether.6c
8
Ru(bpy)3(BF4)2
Ru(bpy)3Cl2-6H2O
Ru(bpz)3(PF6)2
Ir(dFCF3ppy)2(dtbbpy)PF6
Ir(dFCF3ppy)2(dtbbpy)PF6
Ir(dFCF3ppy)2(dtbbpy)PF6
Ir(dFCF3ppy)2(dtbbpy)PF6
Ir(dFCF3ppy)2(dtbbpy)PF6
Na2S2O8
2
48
9
Na2S2O8
2
46
10
11
12c
13d
14e
15f
O2
O2
O2
O2
-
24
5
20
52
36
6
trace
Cyclopropenes, the smallest unsaturated carbocycles, are
readily prepared molecules. Because of the highly strained
double bond, they have unique and higher reactivity than olefins,
allenes and alkynes.7 With regard to the many types of
63
36
10
trace
O2
see footnote
cyclopropenes, substituted cyclopropene carboxylates have
frequently been the focus of study. They easily undergo
intramolecular cyclizations8 as well as C-C bond cleavage9 to
arouse ring expansion and afford ring-opening products.
Substantive studies showed that the 1,3 or 2,3 carbon-carbon
bond cleavage of cyclopropene carboxylates is feasible, which
gave totally different products. Under the nucleophilic attack of
Grignard reagents,9c halide ions,8d,10 organolithium,8b,9b
organocuprate,9d the 2,3 cleavage of cyclopropene carboxylates
was attained extensively. In contrast, reports regarding the 1,3
bond cleavage of cyclopropylene carboxylates were very rare.
For instance, the tri- and tetrasubstituted alkenes were
a1a (0.3mmol), oxidant (0.3mmol), photocatalyst (0.003mmol, 1mol%), 4mL
DCE (AR), 45W compact fluorescent light (CFL) irradiation under O2 at
room temperature unless otherwise noted. bYield of isolated product based on
1a. cNo photocatalyst or no light. d7W blue LED instead of 45W CFL. eUnder
N2 atmosphere. fDistilled water (1eq, 2eq, 3eq) was added to absolute DCE
to give the product in 70%, 73%, 74% yield respectively.
In order to obtain optimal conditions for the synthesis of aroyl
methylidenemalonate derivatives, a variety of conditions were
attempted (Table 1). Firstly dimethyl 2-phenylcycloprop-2-ene-
1,1-dicarboxylate 1a with 1eq of PhN2BF4 in the presence of
1mol% Ir(ppy)3 was illuminated under air by a 45W white CFL at
room temperature (entry 1). To our delight, the reaction afforded
the desired 2a in 36% yield. Without PhN2BF4, the reaction
turned to be complicated and several unidentified by-products
could be observed (entry 2). Then several oxidants were
examined. CBr4, CCl4 and Na2S2O8 all worked (entries 3-5). And
67% yield of 2a could be obtained when Na2S2O8 was used as an
oxidant (entry 5). However, the reaction did not proceed well
with K2S2O8 or (NH4)2S2O8 (entries 6-7). Catalyzed by
synthesized by Fe(acac)3-catalyzed ring-opening reactions of
cyclopropene carboxylates with trialkylaluminum reagents.9a Ma
reported the ring-opening cycloisomerization of
cyclopropenyldicarboxylates for the synthesis of 2,3,5-
trisubstituted furans via tri(2-furanyl)phosphine catalysis.8a On
the other hand, aroyl methylidenemalonates have found a wide
range of applications due to their bioactive11 and pharmaceutical
significance.12 They can be used as Michael acceptors or starting
materials for the synthesis of different compounds such as
pyrroles13a, furans,13b pyridazines,14 indoles,15 enonediesters,16
oxazoles,17 and etc. Generally, the preparation of aroyl
methylidenemalonates was achieved by (1) BF3·OEt2-mediated
ring-opening of D-A nitrocyclopropanes;18a (2) one-pot reaction
of 2-diazomalonate with epoxypropane catalyzed by Rh2(OAc)4
and subsequently Wittig olefination;18b and (3) oxidative radical
reaction of aryl-substituted allenes with dimethylmalonate
catalyzed by Mn(OAc)3.18c Although these procedures are all
good, they have also some obvious shortcomings such as
multistep reactions, unaccessible starting materials and etc.
Ru(bpy)3(BF4)2 or Ru(bpy)3Cl2, moderate yield of 2a was
obtained with Na2S2O8 as the oxidant (entries 8-9). It ocurred to
us that if the oxidizing ability of the photocatalyst was strong
enough, the desired transformation may proceed as well even in
the absence of extra oxidant. Based on the redox potential values
of the photocatalysts,19 Ir(dFCF3ppy)2(dtbbpy)PF6
(E1/2III*/II=+1.21V vs SCE in CH3CN) and Ru(bpz)3(PF6)2
(E1/2III/II=+1.86V vs SCE in CH3CN) were attempted under O2
atmosphere (entries 10-11). To our delight, the desired target
product could be obtained in 52% yield with
Ir[dF(CF3)ppy]2(dtbbpy)PF6 as the catalyst (entry11). Almost no
2a was observed in the absence of light or photocatalyst
(entry12). Under the illumination of 7W blue LED for 6hrs the
target product was isolated in 63% yield (entry13). The reaction
could not proceed under N2 atmosphere (entry14). When the
reaction was carried out in DMSO, DMF and THF, only
complicated mixtures were obtained. Other solvents such as
DCM, diethyl ether, toluene, MeCN, or acetone, could give 2a in
42%, 10%, 50%, 52% and 53% yield respectively. Moreover,
Result and discussion
Herein we wish to report a facile access to aroyl
methylidenemalonate derivatives via visible light photocatalytic
regioselective ring-opening reaction of cyclopropenyl
carboxylates.

when 1-3 equiv. of water was added to the absolute DCE, the
yield is almost same as the results of entries 3-5 which the AR
grade DCE was used as the solvent (entry15).
In order to elucidate the mechanism, two control experiments
were conducted (Scheme 3). When D2O was added, 2a was
isolated in 70% yield and the deuterium product was not found.
The replacement of H2O with H2O18, the heavy oxygen
substituted product 2o was obtained in 65% yield. Moreover,
when TEMPO was added as radical scavenger, the product was
obtained in 10% yield for 24hrs.
Scheme 1: Regioselective ring-opening reaction of
cyclopropenyl carboxylatesa,b
Scheme 3: The control experiments with D2O and H2O18
Based on the literatures21 and the above experiments, a
plausible mechanism was proposed in Scheme 4. At first,
illumination by a 7W blue LED, the ground state of Ir2+ was
excited to provide Ir*2+. Then Ir3+ was formed by the oxidation of
Ir*2+ by O2. Ir3+ captures one electron from substrate 1 to give the
radical cation 5, which itself was reduced to the initial
photocatalyst Ir2+. The nucleophilic attack of H2O to 5 provides
intermediate 6, which subsequently losses one electron and one
proton by the oxidation of Ir3+, and then undergoes ring opening
to give the intermediate 7. At last 7 loses one proton and affords
product 2.
Scheme 4: A plausible mechanism
a1(0.5 mmol), Ir(dFCF3ppy)2(dtbbpy)PF6 (0.005 mmol, 5.6mg, 1mol%), 10hrs,
7W blue LED, O2, 4mL DCE (AR), r.t. bYield of isolated product. cCBr4
(1eq).
To explore the scope of the reaction, a series of cyclopropenyl
carboxylates were tested under the optimized conditions (Scheme
1). The para-halogen on the aryl of 1 generated the
corresponding products 2b, 2c or 2d in moderate to reasonalbe
yields. Substrates 1 with an aryl substituted by electron-donating
group at the para position, such as Me, n-C5H11, t-Bu or MeO,
afforded good yields (2e-2h). The target product 2j was isolated
in 90% yield when the substrate bearing 2-MeO on the phenyl
ring was used, which showed no obvious steric effect on the
reaction. Especially heterocyclic substituted dimethyl 2-(3-
thienyl)cycloprop-2-ene-1,1-dicarboxylate 1i also underwent the
reaction smoothly to afford 2i in 77% yield. When the ethyl, i-
propyl and t-butyl esters were used as the substrates, moderate
yields were also obtained (2l-2n). Unfortunately alkyl substituted
substrate dimethyl 2-n-hexylcycloprop-2-ene-1,1-dicarboxylate is
inert in this reaction, which was in accordance with the results
reported.20
Conclusions
In summary, a visible-light photoredox catalyzed aerobic
oxidative ring-opening of cyclopropenyl carboxylates has been
developed for the synthesis of aroyl methylidene malonates. The
simple and mild conditions make the method attractive,
especially the visible light as a clean and renewable energy
source makes it as a good substitute for the existing conventional
synthetic reagents. Further investigations on the interesting
reactivity of cyclopropenes are ongoing in our laboratory.
Scheme 2: The oxidative ring-opening reaction of 3
Acknowledgments
It is worth mentioning that methyl 1,2-diphenylcycloprop-2-
ene-1-carboxylate 3 could not give the corresponding oxidative
ring-opening product (Scheme 2). Instead, the 2-oxo-2-
phenylacetic acid methyl ester 4 and methyl benzoate 5 were
obtained in 63% and 12% yields, respectively, which may be
formed by the oxidative cleavage of ring opening product and
subsequent intermolecular transesterification. Without additional
oxidant CBr4, the reaction could not proceed.
The authors are grateful to Zhejiang Provincial Natural
Science Foundation of China (No. LY18B020018) and National
Science Foundation of China (No. 21602197).

4
Tetrahedron
8. (a) Chen, J.; Ni, S.; Ma, S. Synlett. 2011, 7, 931; (b) Liu, Y.; Ma, Y.
Supplementary Material
Org. Lett. 2012, 14, 720; (c) Patel, P. R.; Boger, D. L. J. Am. Chem.
Soc. 2010, 132, 8527; (d) Ma, S.; Zhang, J. J. Am. Chem. Soc. 2003,
125, 12386;(e) Song, C.; Sun, D.; Peng, X.; Bai, J.; Zhang, R.; Hou, S.;
Wang, J.; Xu, Z. Chem. Commun. 2013, 49, 9167; (f) Zhu, P. L.; Tang,
X. Y.; Shi, M. Chem. Commun. 2016, 52, 7245.
Supplementary data (1H NMR, 13C NMR data and 1H NMR,
13CNMR spectra of all compounds) associated with this article
can be found, in the online version, at
9. (a) Wang, Y.; Fordyce, E. A. F.; Chen, F. Y.; Lam, H. W. Angew.
Chem. Int. Ed. 2008, 47, 7350; (b) Liu, Y.; Yu, Q.; Ma, S. Eur. J. Org.
Chem. 2013, 3033;(c) Liu, Y.; Ma, S. Chem. Sci. 2011, 2, 811; (d)
Song, C.; Sun, D.; Peng, X.; Bai, J.; Zhang, R.; Hou, S.; Wang, J.; Xu,
Z. Chem. Commun. 2013, 49, 9167; (e) Chuprakov, S.; Malyshev, D.
A.; Trofimov, A.; Gevorgyan, V. J. Am. Chem. Soc. 2007, 129, 14868.
10. (a) Wang, Y.; Lam, H. W. J. Org. Chem., 2009, 74, 1353; (b) Ma, S.;
Zhang, J.; Cai, Y.; Lu, L. J. Am. Chem. Soc. 2003,125, 13954; (c)
Chen. J.; Ma, S. M. J. Org. Chem. 2009, 74, 5595; (d) Ma, S.; Zhang, J.;
Lu, L.; Jin, X.; Cai, Y.; Hou, H. Chem. Commun. 2005, 909; (e) Chen,
S.; Ren, J.; Wang, Z. Tetrahedron 2009, 65, 9146.
11. (a) Gazar, H. A.; Bedir, E.; Takamatsu, S.; Ferreira, D.; Khan, I. A.
Phytochemistry 2004, 65, 2499; (b) Yamazaki, S.; Morikawa, S.; Iwata,
Y.; Yamamoto, M.; Kuramoto, K. Org. Biomol. Chem. 2004, 2, 3134;
(c) Hermanson, J. R.; Gunther, M. L.; Belletire, J. L.; Pinhas, A. R. J.
Org. Chem. 1995, 60, 1900.
12. (a) DeMartino, M. P.; Chen, K.; Baran, P. S. J. Am. Chem. Soc. 2008,
130, 11546. (b) Zhu, Y.; Cai, Q.; Gao, Q.; Jia, F.; Liu, M.; Gao, M.;
Wu, A. Tetrahedron 2013, 69, 6392;(c) Yu, J. Q.; Corey, E. J. J. Am.
Chem. Soc. 2003, 125, 3232; (d) Fouad, M.; Edrada, R. A.; Ebel, R.;
Wray, V.; Muller, W. E. G.; Lin, W. H.; Proksch, P. J. Nat. Prod. 2006,
69, 211.
13. (a) Morikawa, S.; Yamazaki, S.; Furusaki, Y.; Amano, N.; Zenke, K.;
Kakiuchi, K. J. Org. Chem. 2006, 71, 3540; (b) Morikawa, S.;
Yamazaki, S.; Tsukada, M.; Izuhara, S.; Morimoto, T.; Kakiuchi, K. J.
Org. Chem. 2007, 72, 6459.
14. Gao, Q.; Zhu, Y.; Lian, M.; Liu, M.; Yuan, J.; Yin, G.; Wu, A. J. Org.
Chem. 2012, 77, 9865.
15. (a) Weng, J. Q.; Fan, R. J.; Deng, Q. M.; Liu, R. R.; Gao, J. R.; Jia, Y.
X. J. Org. Chem. 2016, 81, 3023; (b) Yamazaki, S.; Iwata, Y. J. Org.
Chem. 2006, 71, 739.
16. Horwitz, M. A.; Fulton, J. L.; Johnson, J. S. Org. Lett. 2017, 19, 5783.
17. Selvi, T.; Srinivasan, K. Chem. Commun. 2014, 50, 10845.
18. (a) Selvi, T.; Srinivasan, K. J. Org. Chem. 2014, 79, 3653; (b) Horwitz,
M. A.; Fulton, J. L.; Johnson, J. S. Org. Lett. 2017, 19, 5783; (c) Wu,
Z.; Huang, X. Synthesis 2007, 1, 45; (d) Iesce, M. R.; Cermola, F.;
Piazza, A.; Scarpati, R.; Graziano, M. L. Synthesis 1995, 439. (e)
Hermanson, J. R.; Gunther, M. L.; Belletire, J. L.; Pinhas, A. R. J. Org.
Chem. 1995, 60, 1900.
19. (a) Tucker, J. W.; Stephenson, C. R. J. J. Org. Chem. 2012, 77, 1617-
1622; (b) Lowry, M. S.; Goldsmith, J. I.; Slinker, J. D. Rohl, R.; Pascal,
R. A.; Malliaras, G. G.; Bernhard, S. Chem. Mater. 2005, 17, 5712-
5719.
References and notes
1. (a) Johnston, C. P.; Smith, R. T.; Allmendinger. S.; MacMillan, D. W.
C. Nature 2016, 536, 322; (b) Yoon, T. P.; Ischay, M. A.; Du, J. Nat.
Chem. 2010, 2, 527; (c) Bosque, I.; Magallanes, G.; Rigoulet, M.;
Karkas, M. D.; Stephenson, C. R. J. ACS Cent. Sci. 2017, 3, 621; (d)
Reckenthaler, M.; Griesbeck, A. G. Adv. Synth. Catal. 2013, 355, 2727;
(e) Zhao, Q. Q.; Chen, J.; Yan, D. M.; Chen J. R.; Xiao, W. J. Org. Lett.
2017, 19, 3620; (f) Wang, L.; Lv, J.; Li, S.; Luo, S. Z. Org. Lett. 2017,
19, 3366.
2. Reviews on photocatalysis: (a) Levin, M. D.; Kim, S.; Toste, F. D. ACS.
Cent. Sci. 2016, 2, 293; (b) Romero, N. A.; Nicewicz, D. A. Chem. Rev.
2016, 116, 10075; (c) Schultz, D. M.; Yoon, T. P. Science. 2014, 343,
1239176; (d) Hoffmann, N.; J. Photochem. Photobiol. 2008, 9, 43; (e)
Ravelli, D.; Fagnoni, M.; Albini, A. Chem. Soc. Rev. 2013, 42, 97; (f)
Hari, D. P.; Konig, B. Chem. Commun. 2014, 50, 6688; (g) Zhang, N.;
Samanta, S. R.; Rosen, B. M.; Percec, V. Chem. Rev. 2014, 114, 5848;
(h) Shi, L.; Xia, W. Chem. Soc. Rev. 2012, 41, 7687; (i) Narayanam, J.
M. R.; Stephenson, C. R. J. Chem. Soc. Rev. 2011, 40, 102. (j) Xuan, J.;
Xiao, W. J. Angew. Chem., Int. Ed. 2012, 51, 6828. (k) Twilton, J.; Le,
C.; Zhang, P.; Shaw, M. H.; Evans, R. W.; MacMillan, D. W. C. Nat.
Rev. Chem. 2017, 1, 0052.
3. (a) Lin, S. S.; Lies, S. D.; Gravatt, C. S.; Yoon, T. P. Org. Lett.
2017, 19, 368; (b) Miyake, Y.; Ashida, Y.; Nakajima, K.; Nishibayashi,
Y. Chem. Commun. 2012, 48, 6966; (c) Rono, L. J.; Yayla, H. G.;
Wang, D. Y.; Armstrong, M. F.; Knowles, R. R. J. Am. Chem. Soc.
2013, 135, 17735.
4. (a) Huo, H.; Wang, C.; Harms, K.; Meggers, E. J. Am. Chem. Soc. 2015,
137, 9551; (b) Liu, W. Q.; Lei, T.; Song, Z. Q.; Yang, X. L.; Wu, C.;
Jiang, X.; Chen, B.; Tung, C. H.; Wu, L. Z. Org. Lett. 2017, 19, 3251;
(c) Jia, K.; Pan, Y.; Chen, Y. Angew. Chem. Int. Ed. 2017, 56, 2478; (d)
Huang, H.; Jia, K.; Chen, Y. ACS Catal. 2016, 6, 4983.
5. (a) Miller, Z. D.; Lee, B. J.; Yoon, T. P. Angew. Chem. Int. Ed. 2017,
56, 11891. (b) Hurtley, A. E.; Lu, Z.; Yoon, T. P. Angew. Chem. Int. Ed.
2014, 53, 8991; (c) Du, J.; Skubi, K. L.; Schultz, D. M.; Yoon, T. P.
Science 2014, 344, 392; (d) Ischay, M. A.; Ament, M. S.; Yoon, T. P.
Chem. Sci. 2012, 3, 2807; (e) Ischay, M. A.; Lu, Z.; Yoon, T. P. J. Am.
Chem. Soc. 2010, 132, 8572; (f) Ischay, M. A.; Anzovino, M. E.; Du, J.;
Yoon, T. P. J. Am. Chem. Soc. 2008, 130, 12886.
6. (a) Hu, X.; Zhang, G.; Bu, F.; Lei, A.; Angew. Chem. Int. Ed. 2018, 57,
1286. (b) Hu, X.; Zhang, G.; Bu, F.; Luo, X.; Yi, K.; Zhang, H.; Lei, A.;
Chem. Sci. DOI:10.1039/C7SC04634K; (c) Yi, H.; Niu, L.; Song, C.;
Li, Y.; Dou, B.; Singh, A. K.; Lei, A. Angew. Chem. Int. Ed. 2017, 56,
1120.
7. (a) Baird, M. S. Cyclopropenes: Transformations. InHouben-Weyl;
Thieme, Stuttgart, Germany, 1997, Vol. E17d/2, pp 2781; (b) Back, R.
D.; Dmitrenko, O. J. Am. Chem. Soc. 2004, 126, 4444; (c) Rubin, M.;
Rubina, M.; Gevorgyan, V. Chem. Rev. 2007, 107, 3117; (d) Fox, J. M.;
Yan, N. Curr. Org. Chem. 2005, 9, 719; (e) Archambeau, A.; Miege, F.;
Meyer, C.; Cossy, J. Acc. Chem. Res. 2015, 48, 1021; (f) Rubina, M.;
Rubin, M.; Gevorgyan, V. J. Am. Chem. Soc. 2003, 125, 7198.
20. Dange, N. S.; Jatoi, A. H.; Robert, F.; Landais, Y. Org. Lett. 2017, 19,
3652.
21. (a) Karkas, M. D.; Bosque, I.; Matsuura, B. S.; Stephenson, C. R. J.
Org. Lett. 2016, 18, 5166-5169.; (b) Nguyen, J. D.; Tucker, J. W.;
Konieczynska, M. D.; Stephenson, C. R. J. J. Am. Chem. Soc. 2011, 133,
4160.
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Regioselective Oxidative Ring-Opening of
Cyclopropenyl Carboxylates by Visible
Lightphotoredox Catalysis
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Qianwen Ye,a Hongqiang Ye,a Dongping Cheng,*b Xiaonian Li,*a and Xiaoliang Xu*a

Highlights
1. Regioselective oxidative ring-opening of
cyclopropenyl carboxylate derivatives via
visible light photoredox catalysis.
2. A variety of aroyl methylidenemalonates were
obtained in good to excellent yields.
3. The reaction has the advantage of simple
operation and mild conditions.