Time-Economical Synthesis of Diarylacetates Enabled by TfOH-Catalyzed Arylation of α-Aryl-α-Diazoesters with Arenes

Article abstract of DOI:10.1002/cctc.202100271

Diarylacetates are privileged structures of many bioactive natural products and pharmaceutical compounds. A time-economical synthesis of diarylacetates by TfOH-catalyzed arylation of α-aryl-α-diazoesters with arenes is described. This protocol provides a variety of diarylacetates in good yields with broad substrate scope, excellent functional group compatibility, and mild reaction conditions. Also, a new mechanism for the arylation reaction of α-aryl-α-diazoesters with arenes under TfOH catalysis is presented.

Full text of DOI:10.1002/cctc.202100271

Communications
doi.org/10.1002/cctc.202100271
ChemCatChem
Very Important Paper
Time-Economical Synthesis of Diarylacetates Enabled by
TfOH-Catalyzed Arylation of α-Aryl-α-Diazoesters with
Arenes
Sha Hu,[a, b] Jiale Wu,[a, b] Zuolin Lu,[c] Jiaqi Wang,[a, b] Yuan Tao,[a, b] Meifen Jiang,*[a, b] and
Fener Chen*[a, b, c]
Diarylacetates are privileged structures of many bioactive
natural products and pharmaceutical compounds. A time-
economical synthesis of diarylacetates by TfOH-catalyzed
arylation of α-aryl-α-diazoesters with arenes is described. This
protocol provides a variety of diarylacetates in good yields with
broad substrate scope, excellent functional group compatibility,
and mild reaction conditions. Also, a new mechanism for the
arylation reaction of α-aryl-α-diazoesters with arenes under
TfOH catalysis is presented.
Figure 1. Selected Biologically Active Diarylacetate Derivatives.
Diarylacetates are prominent scaffolds in natural products,
pharmaceuticals, and building blocks of complex molecules
(Figure 1).[1] For example, anti-cholinergic drugs, adiphenine
(I),[2] piperidolate (II),[3] and pipoxolan (III),[4] are used clinically to
relieve smooth muscle hypermotility and spasms. At the same
time, Pipoxolan (III) also inhibits the proliferation of human
lung cancer cells (CL 1–5), tumor cells, and leukemia cells (HL-
60, U937, and K-562). Asimadoline (IV),[5] a potent k-opioid
receptor agonist, reduces sensation to colonic distension and
irritable bowel syndrome. Benapryzine (V),[6] an anti-Parkinson’s
drug, inhibits dopamine absorption into corpus striatum in vitro.
Therefore, the development of diverse strategies for the
synthesis of diarylacetate derivatives is of great significance as a
result of their versatile pharmacological activities and their
utility in drug discovery.
anilines using K2S2O8-HFIP,[9] and the in-situ generated acetal-
assisted 1,2-aryl migration of benzoins under TfOH catalysis
(Scheme 1, a–d).[10] However, these processes suffer from many
drawbacks such as not easy available or not readily prepared
materials, harsh reaction conditions, and functional group
incompatibility, etc. Thus, developing a straightforward syn-
thetic procedure that can overcome these challenges is needed.
In recent years, diazo compounds are remarkably versatile and
useful building blocks for an array of chemical transformations
in organic synthesis.[11] In particular, a few research groups have
reported the efficient synthesis of diarylacetates by the carbene
transfer reactions of α-aryl-α-diazoesters with arenes using
Traditionally, diarylacetate derivatives have been synthe-
sized by the Pd-catalyzed α-arylation of phenyl- and ethyl-
acetates with monohalobenzenes,[7] the Friedel-Crafts alkylation
of α-bromoarylacetates with arenes in the presence of AgOTf,[8]
the double Friedel-Crafts alkylation of glycine esters with
transition metals (Fe,[12] Rh,[13] Ir,[14] Pd,[15] Cu,[16] and Au,[17]
)
(Scheme 1, e1). Despite these advances, they all have limita-
tions, such as the use of toxic transition-metal catalysts and the
requirement of using arenes with activated substituents (OH,
OMe, NMe2, Si(OMe)3, and I). Wang group and Jurberg group
independently achieved the metal-free arylation of α-aryl-α-
diazoesters with arylboron reagents under basic conditions at
[a] Dr. S. Hu, Dr. J. Wu, Dr. J. Wang, Dr. Y. Tao, Dr. M. Jiang, Prof. F. Chen
Engineering Center of Catalysis and Synthesis for Chiral Molecules
Department of Chemistry
°
100 C or blue light, leading to the corresponding diarylacetate
products (Scheme 1, e2).[18] Zhang group described (C6F5)3B-
catalyzed ortho-selective substitution of α-aryl-α-diazoesters
with phenols (Scheme 1, e2).[19]
Fudan University
200433 Shanghai (P. R. China)
E-mail: jiang_meifen@fudan.edu.cn
These boron substrates can be expensive and/or require
multistep preparation, thus rendering them less practical for
larger scale applications. Very recently, Burtoloso and co-work-
ers reported an elegant arylation of α-methoxy-phenyl-α-
diazoesters with arenes catalyzed by H2SO4À SiO2 for the syn-
thesis of electron-rich diarylacetates derivatives (Scheme 1,
e3).[20] However, in this protocol, only α-methoxy-phenyl-α-
rfchen@fudan.edu.cn
[b] Dr. S. Hu, Dr. J. Wu, Dr. J. Wang, Dr. Y. Tao, Dr. M. Jiang, Prof. F. Chen
Shanghai Engineering Center of Industrial Catalysis for Chiral Drugs
200433 Shanghai (P. R. China)
[c] Z. Lu, Prof. F. Chen
Institute of Pharmaceutical Science and Technology
Zhejiang University of Technology
310014 Hangzhou (P. R. China)
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/cctc.202100271
ChemCatChem 2021, 13, 1–6
1
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

Communications
doi.org/10.1002/cctc.202100271
ChemCatChem
We began studying the reaction under our previous
reaction conditions for the cascade CÀ H activation/lactonization
of α-aryl-α-diazoacetates with phenols[22] to check whether our
established method could be operative toward the arylation of
methyl α-(p-tolyl)-α-diazoacetate 1a with p-xylene 2a (Table 1).
To our delight, the desired diarylacetate product 3aa was
obtained in 83% yield when 10 mol% of TfOH was used as the
catalyst (entry 1). However, switching from TfOH to H2SO4
dramatically decreased the yield of 3aa to less than 10%, and a
long reaction time was needed (24 h, entry 2). The use of TsOH,
TFA, and MsOH also gave unsatisfied results 35%, 50%, and
43% yields, respectively (entries 3–5). Further solvent screening
was examined, the use of other chlorinated solvents such as
dichloroethane (DCE) or chloroform (CHCl3) was found to be
less effective than dichloromethane (DCM) (entries 6–7). Re-
placement of DCM with ethyl acetate (AcOEt) gave a poor yield
of 3aa (30%, entry 8). Reactions in acetone or acetonitrile
provided trace amounts of product 3aa (entries 9–10). When
decreasing the catalyst loading from 10 mol% to 5 mol%, a
similar yield of 3aa was obtained (entry 11).
With the optimized reaction conditions in hand, the
substrate scope of arenes was then investigated, and the results
are summarized in Table 2. The unsubstituted benzene pro-
ceeded smoothly to give the corresponding product 3ab in
72% yield. But the arylation reaction using anisole as the
substrate under the above optimized reaction conditions
afforded an inseparable mixture (3:1) of the regioisomers 3ac-1
and 3ac-2 in a combined yield of 78%. The disubstituted
benzene derivatives bearing electron-donating and electron-
withdrawing substituents at any of two positions on phenyl
ring were tolerant in this reaction, producing the corresponding
products 3aa–3ad in good to high yields (60–86%) as a single
isomer. The tri-substituted benzene derivatives mesitylene and
tetra-substituted benzene derivatives 1,2,4,5-tetrameth-
ylbenzene were suitable substrates to yield 3aj and 3ak in 74
Scheme 1. Strategies to Access Diarylacetates.
Table 1. Optimization of the Reaction Condition.[a]
diazoesters and electron-rich arenes, phenols or meth-
oxybenzenes were employed as the substrates.
We recently developed the TfOH-catalyzed NÀ H insertion[21]
of α-aryl-α-diazoesters with anilines, and CÀ H activation/
lactonization of α-aryl-α-diazoesters with phenols, in which
diazo compounds would be able to undergo ortho CÀ H
insertion with phenolic base nucleophiles.[22] Perceiving the
advantages of these approaches that Brønsted acid is very
important between diazo compounds and aromatic hydro-
carbons, we envisioned that Brønsted acid could be able to
expand methods for the preparation of various substituents
diarylacetates. Meanwhile, we focus on the economic methods
which are mainly driven by the atom economy, step economy,
and time economy.[23] Herein, we reported the TfOH-catalyzed
time-economical arylation of α- aryl-α-diazoesters with arenes
for the synthesis of diarylacetates. This methodology features
metal-free mild reaction conditions and demonstrates excellent
functional group compatibility. Additionally, we introduced a
different mechanism with Burtoloso’s work.
Entry
Brønsted acid
[mol%]
Solvent
Time[b] [h]
Yield[c] [%]
1
2
3
4
5
6
7
8
TfOH (10)
H2SO4 (10)
TsOH (10)
TFA (10)
MsOH (10)
TfOH (10)
TfOH (10)
TfOH (10)
TfOH (10)
TfOH (10)
TfOH (5)
DCM
DCM
DCM
DCM
DCM
DCE
CHCl3
AcOEt
Acetone
MeCN
DCM
0.17
24
24
83
<10
35
50
43
78
76
30
24
0.17
0.17
0.17
0.17
0.17
0.17
0.17
9
10
11
trace
trace
84
[a] Reaction conditions: methyl α-(p-tolyl)-α-diazoacetate 1a (0.2 mmol,
1.0 equiv), p-xylene 2a (0.2 mmol, 1.0 equiv), and catalyst (mmol%) in the
solvent (0.8 ml, 0.25 M) at 50 C under air. [b] Complete conversion reaction
°
time of 1a. [c] Isolated yield.
ChemCatChem 2021, 13, 1–6
www.chemcatchem.org
2
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

Communications
doi.org/10.1002/cctc.202100271
ChemCatChem
Table 2. Substrate Scope of Arenes.[a,b]
Table 3. Substrate Scope of α-Aryl-α-Diazoacetates.[a,b]
[a] Reaction conditions: α-aryl-α-diazoacetate 1 (0.2 mmol, 1.0 equiv), p-
xylene 2a (0.2 mmol, 1.0 equiv), and TfOH (5 mmol%) in DCM (0.8 ml,
°
0.25 M) at 50 C for 0.17 h under air. [b] Isolated yield.
methyl α-phenyl-α-diazoesters bearing electron-donating
(methyl, tert-butyl, phenyl, and methoxy) and electron-with-
drawing (fluoro, chloro, and bromo) at any of the positions of
phenyl ring were all reacted smoothly to furnish the corre-
sponding diarylacetate products 3aa–3ga in very good yields.
Remarkably, the unsubstituted benzene proved to be an
excellent substrate for this reaction, giving the diarylacetate
product 3ha in 90% yield. A disubstituted methyl α-aryl-α-
diazoester could be also tolerated under the standard con-
ditions to afford the arylation product 3ia in 84% yield. In
addition to methyl α-phenyl-α-diazoacetates, methyl α-2-
naphthyl-α-diazoacetate was also cleanly transformed into the
corresponding product 3ja in 72% yield. Gratifyingly, varying
the methyl ester group into ethyl ester group was also suitable
to this reaction, and giving the desired arylation products 3ka–
3ma in 72–81% yields.
To further evaluate the efficacy and synthetic utility of this
methodology, we carried out the scale-up experiment using
5.3 mmol (1.0 g) of methyl α-phenyl-α-diazoacetate and
5.3 mmol (0.43 g) of benzene under the optimal reaction
conditions, which provided the desired product methyl diphe-
nylacetate 3hb in 40% yield (Scheme 2).[18a] The diphenylace-
tate 3hb is a key intermediate for the preparation of anti-
parkinsonian drug benapryzine (V), which was derived from
3hb according to the protocol developed by Jurberg (CÀ H
hydroxylation followed by the hydrolysis 3hb as well as O-
alkylation).
[a] Reaction conditions: methyl α-(p-tolyl)-α-diazoacetate 1a (0.2 mmol,
1.0 equiv), arenes 2 (0.2 mmol, 1.0 equiv), and TfOH (5 mmol%) in DCM
°
(0.8 ml, 0.25 M) at 50 C for 0.17 h under air. [b] Isolated yield.
and 78% yields, respectively. When the phenyl ring was
replaced with sterically bulky fluorene or 9H-pyrene ring, as
expected, the reaction also worked smoothly to cleanly afford
the desired products 3al and 3am in 71% and 68% yields,
respectively. Similarly, the heterocyclic (5-bromothienyl, methyl
4-carboxylate-5-methylthienyl, ethyl 5-carboxylate-2-meth-
ylthienyl, thieno[3,2-b]thiophenyl, and methyl 5-carboxylate 1-
tosyl-1H-indolyl) arenes were also effective for this transforma-
tion and furnished the corresponding products 3an–3ar in
moderate to good yields (61–72%).
Having demonstrated the generality of arenes, we next
moved on to examine the scope of α-aryl-α-diazoesters. As
illustrated in Table 3, the arylation reaction of mono-substituted
ChemCatChem 2021, 13, 1–6
www.chemcatchem.org
3
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

Communications
doi.org/10.1002/cctc.202100271
ChemCatChem
extrudes N2. This mechanism is different compared with
Burtoloso’s work,[20] in which the quinone type intermediate
from methoxy substituted α-aryl-α-diazoesters by H2SO4À SiO2
underwent the Friedel-Crafts alkylation reaction with a phe-
nolic-based nucleophile.
In summary, we have developed an efficient time-econom-
ical TfOH-catalyzed CÀ H activation of α-aryl-α-diazoesters with
arenes under mild conditions, offering a way to construct
various diarylacetate derivatives. The significant feature of this
process is tolerated a range of functional groups with good
yields. Further applications of this strategy for the synthesis of
biological and pharmaceutical compounds are ongoing in our
laboratory.
Scheme 2. Gram-Up Reaction and Synthetic Application.
To understand the reaction mechanism, the control experi- Experimental Section
ment was performed (Scheme 3). In this deuterium experiment,
General Method: All reactions were carried out in Schlenk tubes.
Flash column chromatography was performed over a silica gel. H
1
TfOH and deuterated benzene (D6-2b) acted as proton sources
during the anhydrous solvent reaction as the hydrogen and
deuterium were incorporated in the final product D6-3ab
(determined by NMR spectroscopy; see the Supporting Informa-
tion for details).
nuclear magnetic resonance (NMR) spectra were recorded using a
Bruker AM400 spectrometer; chemical shifts (in ppm) were referred
to CDCl3 (δ=7.26 ppm). The 13C NMR spectrum was obtained using
the same NMR spectrometer and was calibrated with CDCl3
(δ =77.0 ppm). The following abbreviations are used to illuminate
the diversities: δ=chemical shifts, J=coupling constant, s=singlet,
d=doublet, t=triplet, q=quartet, and m=multiplet. High-resolu-
tion mass spectrometry (HRMS) was performed using a Bruker
micrOTOF spectrometer (ESI). All of the solvents were distilled. The
heat source is an oil bath. All chemicals were obtained from
commercial suppliers unless otherwise stated. PE=petroleum ether
and EA=ethyl acetate.
Based on our previous mechanistic studies,[22] literature
precedence,[24] and control experiment, we proposed a plausible
reaction mechanism outlined in Scheme 4. The diazonium ion
intermediate A could be generated from methyl α-(p-tolyl)-α-
diazoacetate (1a) in the presence of TfOH catalyst. Then, the
diazonium ion A, which would undergo a nucleophilic addition
reaction with p-xylene (2a), provides the desired product
diarylacetate 3aa after the intermolecular CÀ H functionalization
Acknowledgments
This work was supported by Fudan University (JIH1615060).
Conflict of Interest
The authors declare no conflict of interest.
Scheme 3. Control Experiment.
Keywords: TfOH · arylation · α-aryl-α-diazoesters · arenes ·
diarylacetates
[1] a) M. A. Farajzadeh, A. S. Hojghan, M. R. A. Mogaddam, J. Food Compos.
Anal. 2018, 66, 90–97; b) S. Faruqi, C. Wright, R. Thompson, A. H. Morice,
Br. J. Clin. Pharmacol. 2014, 78, 1272–1280; c) T. Minagawa, M. Gotoh, O.
Yokoyama, K. Sugaya, T. Yamanishi, K. Kawahara, K. Kaga, T. Kikuchi, O.
Nishizawa, F. s. group, Int. J. Urol. 2018, 25, 486–491; d) S. Murgas, D.
Adolf, Research and Reports in Urology 2019, 11, 9–13; e) S. Nishijima,
K. K. Sugaya, K. Ashitomi, T. Ueda, H. Yamaoto, Biomedical Research
(Tokyo) 2019, 40, 145–152; f) Z. Tavsan, H. A. Kayalı, Process Biochemistry
2014, 49, 745–750.
[2] G. Spitzmaul, F. Gumilar, J. P. Dilger, C. Bouzat, Br. J. Pharmacol. 2009,
157, 804–817.
[3] S. Yokoyama, Y. Fujino, Y. Kawamoto, A. Kaneko, T. Fujie, Chem. Pharm.
Bull. 1994, 42, 1351–1353.
[4] a) Y. F. Chen, H. Y. Tsai, K. J. Wu, L. R. Siao, W. G. Wood, PLoS One 2013,
8, e75654; b) M. M. Lee, Y. Y. Chen, P. Y. Liu, S. Hsu, M. J. Sheu, Chem.-
Biol. Interact. 2015, 236, 19–30; c) M. J. Sheu, P. Y. Chou, C. S. Huang, I. C.
Scheme 4. Proposed Reaction Mechanism.
ChemCatChem 2021, 13, 1–6
www.chemcatchem.org
4
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

Communications
doi.org/10.1002/cctc.202100271
ChemCatChem
Tsai, Y. C. Chien, S. Y. Lin, H. Y. Tsai, H. C. Cheng, C. H. Wu, Clin. Exp.
Pharmacol. Physiol. 2010, 37, 605–612.
[16] a) E. Tayama, T. Yanaki, H. Iwamoto, E. Hasegawa, Eur. J. Org. Chem.
2010, 2010, 6719–6721; b) E. Tayama, M. Ishikawa, H. Iwamoto, E.
Hasegawa, Tetrahedron Lett. 2012, 53, 5159–5161.
[5] a) M. Camilleri, Neurogastroenterol Motil 2008, 20, 971–979; b) L. A.
Szarka, M. Camilleri, D. Burton, J. C. Fox, S. McKinzie, T. Stanislav, J.
Simonson, N. Sullivan, A. R. Zinsmeister, Clin. Gastroenterol. Hepatol.
2007, 5, 1268–1275.
[6] a) G. B. Leslie, G. E. Conway, Pharmacol. Res. Commun. 1970, 2, 201–204;
b) M. G. Palfreyman, E. S. C. Palfreyman, M. S. G., Eur. J. Pharmacol. 1974,
28, 379–383.
[7] a) W. A. Moradi, S. L. Buchwald, J. Am. Chem. Soc. 2001, 123, 7996–8002;
b) B. Song, T. Himmler, L. J. Gooßen, Adv. Synth. Catal. 2011, 353, 1688–
1694.
[8] a) Y. Kim, Y. S. Choi, S. K. Hong, Y. S. Park, Org. Biomol. Chem. 2019, 17,
4554–4563; b) P.-S. Lai, J. A. Dubland, M. G. Sarwar, M. G. Chudzinski,
M. S. Taylor, Tetrahedron 2011, 67, 7586–7592.
[17] a) Y. Xi, Y. Su, Z. Yu, B. Dong, E. J. McClain, Y. Lan, X. Shi, Angew. Chem.
Int. Ed. 2014, 53, 9817–9821; Angew. Chem. 2014, 126, 9975–9979; b) Z.
Yu, B. Ma, M. Chen, H. H. Wu, L. Liu, J. Zhang, J. Am. Chem. Soc. 2014,
136, 6904–6907; c) B. Ma, Z. Chu, B. Huang, Z. Liu, L. Liu, J. Zhang,
Angew. Chem. Int. Ed. 2017, 56, 2749–2753; Angew. Chem. 2017, 129,
2793–2797; d) B. Ma, J. Wu, L. Liu, J. Zhang, Chem. Commun. 2017, 53,
10164–10167; e) W. Zhang, G. Xu, L. Qiu, J. Sun, Org. Biomol. Chem.
2018, 16, 3889–3892; f) L. Carreras, A. Franconetti, A. Grabulosa, A.
Frontera, A. Vidal-Ferran, Org. Chem. Front. 2020, 7, 1626–1634.
[18] a) A. F. da Silva, M. A. S. Afonso, R. A. Cormanich, I. D. Jurberg, Chem.
Eur. J. 2020, 26, 5648–5653; b) C. Peng, W. Zhang, G. Yan, J. Wang, Org.
Lett. 2009, 11, 1667–1670.
[9] Q. Xu, B. Li, Y. Ma, F. Sun, Y. Gao, N. Ye, Org. Biomol. Chem. 2020, 18,
666–670.
[10] R. B. Kothapalli, R. Niddana, R. Balamurugan, Org. Lett. 2014, 16, 1278–
[19] Z. Yu, Y. Li, J. Shi, B. Ma, L. Liu, J. Zhang, Angew. Chem. Int. Ed. 2016, 55,
14807–14811; Angew. Chem. 2016, 128, 15027–15031.
[20] R. D. C. Gallo, P. B. Momo, D. P. Day, A. C. B. Burtoloso, Org. Lett. 2020,
22, 2339–2343.
1281.
[11] a) Y. Zhang, J. Wang, Chem. Commun. 2009, 5350–5361; b) J. N.
Johnston, H. Muchalski, T. L. Troyer, Angew. Chem. Int. Ed. 2010, 49,
2290–2298; Angew. Chem. 2010, 122, 2340–2349; c) S. F. Zhu, Q. L. Zhou,
Acc. Chem. Res. 2012, 45, 1365–1377; d) X. Guo, W. Hu, Acc. Chem. Res.
2013, 46, 2427–2440; e) H. Keipour, V. Carreras, T. Ollevier, Org. Biomol.
Chem. 2017, 15, 5441–5456; f) L. W. Ciszewski, K. Rybicka-Jasinska, D.
Gryko, Org. Biomol. Chem. 2019, 17, 432–448.
[12] a) J. M. Yang, Y. Cai, S. F. Zhu, Q. L. Zhou, Org. Biomol. Chem. 2016, 14,
5516–5519; b) B. Wang, I. G. Howard, J. W. Pope, E. D. Conte, Y. Deng,
Chem. Sci. 2019, 10, 7958–7963.
[21] S. Hu, J. Wu, Z. Lu, J. Wang, Y. Tao, M. Jiang, F. Chen, J. Org. Chem. 2020.
DOI: 10.1021/acs.joc.0c02588.
[22] S. Hu, Z. Lu, M. Liu, H. Xu, J. Wu, F. Chen, J. Org. Chem. 2020, 85, 14916–
14925.
[23] M. He, Y. Chen, Y. Luo, J. Li, R. Lai, Z. Yang, Y. Wang, Y. Wu, Green Synth.
Catal. 2020, 1, 180–182.
[24] C. Zhai, D. Xing, C. Jing, J. Zhou, C. Wang, D. Wang, W. Hu, Org. Lett.
2014, 16, 2934–2937.
[13] a) J. Ghorai, P. Anbarasan, J. Org. Chem. 2015, 80, 3455–3461; b) Y. Xia,
Z. Liu, S. Feng, F. Ye, Y. Zhang, J. Wang, Org. Lett. 2015, 17, 956–959;
c) B. Xu, M. L. Li, X. D. Zuo, S. F. Zhu, Q. L. Zhou, J. Am. Chem. Soc. 2015,
137, 8700–8703.
[14] C. P. Owens, A. Varela-Álvarez, V. Boyarskikh, D. G. Musaev, H. M. L.
Davies, S. B. Blakey, Chem. Sci. 2013, 4, 2590–2596.
Manuscript received: February 19, 2021
Revised manuscript received: March 8, 2021
Accepted manuscript online: March 18, 2021
Version of record online: ■■■, ■■■■
[15] S. M. Golitsin, I. P. Beletskaya, I. D. Titanyuk, Synthesis 2020, 52, 775–780.
ChemCatChem 2021, 13, 1–6
www.chemcatchem.org
5
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

COMMUNICATIONS
Dr. S. Hu, Dr. J. Wu, Z. Lu, Dr. J.
Wang, Dr. Y. Tao, Dr. M. Jiang*,
Prof. F. Chen*
1 – 6
Time-Economical Synthesis of Dia-
rylacetates Enabled by TfOH-
Catalyzed Arylation of α-Aryl-α-
Diazoesters with Arenes
Tick-tock: A time-economical
cetates in good yields with broad
substrate scope, excellent functional
group compatibility, and mild
reaction conditions.
synthesis of diarylacetates by TfOH-
catalyzed arylation of α-aryl-α-diazo-
esters with arenes is described. This
protocol provides a variety of diaryla-