Electrochemical Thiolation and Borylation of Arylazo Sulfones with Thiols and B2pin2

Article abstract of DOI:10.1002/adsc.202001518

An efficient electrochemical synthesis approach of various unsymmetrical thioethers and arylboronates has been developed. Bench stable arylazo sulfones were used as radical precursors for carbon-heteroatom bond formation under electrochemical conditions. Moreover, the scalability of this approach was evaluated by performing the electrochemical thiolation and borylation of arylazo sulfones with thiols and B₂pin₂ on a gram scale. This protocol not only avoided the use of stoichiometric oxidants, metal catalysts, activating agents and even added bases, but also exhibited favorable functional group tolerance. (Figure presented.).

Full text of DOI:10.1002/adsc.202001518

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DOI: 10.1002/adsc.202001518
Electrochemical Thiolation and Borylation of Arylazo Sulfones
with Thiols and B2pin2
Rongkang Wang,a Fangming Chen,a Lvqi Jiang,a,* and Wenbin Yia, b,*
a
School of Chemical Engineering, Nanjing University of Science and Technology
200 Xiao Ling Wei Street, Nanjing 210094, People’s Republic of China
E-mail: lvqi.jiang@njust.edu.cn; yiwb@njust.edu.cn
Key Laboratory of Organofluorine Chemistry, Shanghai Institute Organic Chemistry, Chinese Academy of Sciences, Shanghai
b
200032
Manuscript received: December 5, 2020; Revised manuscript received: January 20, 2021;
Version of record online: Februar 5, 2021
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.202001518
Abstract: An efficient electrochemical synthesis approach of various unsymmetrical thioethers and
arylboronates has been developed. Bench stable arylazo sulfones were used as radical precursors for carbon-
heteroatom bond formation under electrochemical conditions. Moreover, the scalability of this approach was
evaluated by performing the electrochemical thiolation and borylation of arylazo sulfones with thiols and
B2pin2 on a gram scale. This protocol not only avoided the use of stoichiometric oxidants, metal catalysts,
activating agents and even added bases, but also exhibited favorable functional group tolerance.
Keywords: Electrochemistry; Thiolation; Borylation; Arylazo sulfones; Radicals
Introduction
Organosulfides have received considerable attention
for their key importance in functional materials,
pharmaceuticals, synthetic chemistry, and food
science.[1] In particular, CÀ S bonds are important
structural motifs in various functional polymer materi-
als and bioactive compounds.[2] Thus, developing
efficient and mild methods to construct CÀ S bond
continue to be highly desirable. In the last few decades,
the transition-metal-catalyzed CÀ S bond cross-cou-
pling reactions as a powerful tool have attracted
significant attention (Figure 1a).[3] Among them,
palladium,[4] nickel,[5] copper,[6] iron,[7] and cobalt[8]
have been demonstrated as catalysts to promote these
transformations. Although these methods were great
breakthroughs for the synthesis of unsymmetrical
thioethers, the problem of catalyst poison can’t be
avoided for these transition-metal-catalyzed reactions.
Photochemical approach, which depends on the advan-
tages of the mild conditions and eco-sustainable
Figure 1. Synthesis of unsymmetrical thioethers.
required, has become another important tool for the
construction of CÀ S bond.[9] In the presence of weak
base, several reports that photoredox-catalyzed transi-
tion-metal-mediated thiolation of aryl halides under However, expensive photocatalysts or weak bases were
room temperature have been declared (Figure 1b).[10] needed. Mei and Pan described an electrochemically
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Table 1. Optimization of reaction conditions.[a]
promoted nickel-catalyzed thiolation of aryl halides,
respectively (Figure 1c).[11] There are still problems
with metal residues and increasing the cost of the final
products. Therefore, the development of a more
environmentally friendly and efficient approach is
desired.
Entry Variation from the standard conditions
Yield[b] (%)
Arylazo sulfones, easily prepared from commer-
cially available colorless anilines in a two-step
procedures,[12] can easily generate aryl radicals or
cations which are suitable precursors of chemical
intermediates upon visible-light irradiation.[13,14,15]
These colored thermally stable derivatives of aryl
diazonium salts, were applied in a series of photo-
chemical reactions by Protti and Fagnoni.[14] Recently,
the application of such sulfones was extended to the
construction of ArÀ B,[14g,15a] ArÀ S (to form aryl
sulphides[14g] or sulfoxides[15b]), ArÀ Sn[14h] and ArÀ P[14i]
bonds. However, the applications of arylazo sulfones
in electrochemistry have not been reported as far as we
know.
1
2
3
4
5
6
7
8
none
91(87)[c]
23
34
41
73
72
77
85
80
74
26
51
88
MeCN instead of MeCN/H2O
nBu4NClO4 instead of LiClO4
nBu4NPF6 instead of LiClO4
Et4NBF4 instead of LiClO4
Graphite rod as cathode
Ni plate as cathode
Pt plate as anode
9
5 mA, 4 h instead of 10 mA, 2 h
15 mA, 1.3 h instead of 10 mA, 2 h
2.0 V instead of 10 mA
2.5 V instead of 10 mA
under N2 atmosphere
10
11
12
13
14
15
No electric current
No electric current, under N2 atmosphere n.d.
trace
Organic electrochemistry has been recognized as a
highly efficient and environmentally friendly tool for
constructing new chemical bond and has received
considerable attention in the past few years.[16] In many
cases, the use of toxic bases, oxidants, reducing agents
or even catalysts could be avoided during the electro-
catalysis process, which meet with the requirement of
green and sustainable chemistry. Under constant
current conditions, thiol radicals generated from thiols
[a] Conditions: undivided cell, graphite rod anode (ϕ 3 mm), Pt
plate cathode (15×10×0.3 mm), constant current=10 mA,
1a (0.6 mmol), 2f (0.3 mmol), LiClO4 (0.8 mmol), MeCN/
H2O (7:1, 8.0 mL), rt, 2 h (2.49 FmolÀ 1).
[b] GC yields based on 2f.
[c] Isolated yield of 3f.
at the anode, which could undergo a rapid dimerization We speculated that water could effectively reduce the
to give disulfide.[17] However, reduction of arylazo resistance in the reaction system. The use of other
sulfones at the cathode remained undeveloped. Many supporting electrolytes such as nBu4NClO4, nBu4NPF6,
organic reactions have been transformed from photo- and Et4NBF4 didn’t lead to better results (Table 1,
redox catalytic methods to electrochemical processes entries 3–5). In addition, using graphite rod or Ni plate
due to the inherent similarity that both photoredox as cathode electrode resulted in a poorer yield (Table 1,
chemistry and organic electrochemistry use electrons entries 6 and 7). Replacing the graphite rod anode with
as reagents to activate substrates. Thus, we speculated a platinum plate furnished a lower yield (Table 1,
that arylazo sulfones might be reduced to form aryl entry 8). Considering the price of Pt, using graphite
radicals at the cathode. Herein, we develop an efficient rod as a cathode electrode would be more economic in
and facile electrochemical method for the synthesis of industrialization. Notably, either decreasing (5 mA) or
various unsymmetrical thioethers or arylboronates increasing (15 mA) the constant current led to a lower
from arylazo sulfones and thiols or B2pin2 under mild yield (Table 1, entries 9 and 10), and 4,4’-sulfinylbis
conditions for the first time (Figure 1d).
(methoxybenzene) was detected as by-product when
the reaction was carried out under 15 mA constant
current. Then we applied the constant potential instead
of constant current. And the yields of 3f were 26% and
Results and Discussion
We commenced our study by using 1-(4-meth- 51% when the constant potential were 2.0 V and 2.5 V,
oxyphenyl)-2-(methylsulfonyl)diazene 1a and 4-fluo- respectively (Table 1, entries 11 and 12). There was no
robenzenethiol 2f as model substrates to optimize the obvious difference when the reaction worked under a
reaction conditions. Utilizing acetonitrile (CH3CN) and nitrogen atmosphere (Table 1, entry 13). A trace
water (H2O) as the co-solvent, the desired product was amount of desired product was detected without
obtained in 91% yield under 10 mA constant current electricity (Table 1, entry 14). Finally, a nitrogen
for 2.0 hours (Table 1, entry 1). This result demon- protection experiment under no electricity conditions
strated that the reaction time was greatly reduced was performed and no desired product was detected
compared with the photocatalytic method using dis- (Table 1, entry 15).
ufides as S source.[14g] When water was removed, only
23% yield of product was obtained (Table 1, entry 2). investigated the scope of the electrochemical coupling
With the optimal reaction conditions in hand, we
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reaction with 1-(4-methoxyphenyl)-2-(methylsulfonyl)
Next, we tested the scope of arylazo sulfones as
diazene 1a and different thiols 2 in Scheme 1. shown in Scheme 2. Notably, both electron-rich and
Generally, thiophenols containing electron-withdraw- electron-deficient arylazo sulfones could also be
ing or electron-donating groups on the aryl rings were tolerated. The electrochemical condition possessed
all smoothly converted to the desired products (3a–i) excellent functional group compatibility, such as meth-
in good yields. Some functional groups, such as À NH2, yl (4a), phenyl (4b), acetyl (4c), cyano (4d), and
À F, À Cl, and À Br, were tolerated to give the ethoxycarbonyl (4e) group. Disubstituted arylazo
corresponding products, which can be applied in sulfones reacting with 4-methylbenzenethiol 2a con-
further transformation. However, 4-mercaptophenol, 4- verted to the desired products (4f–i) in good yields. In
mercaptobenzaldehyde and 4-mercaptobenzoic acid addition, the corresponding products (4j–l) could also
were not applicable in this transformation. Notably, be obtained when heteroarylazo sulfones used. Under
other aromatic skeletons including naphthalene, the same conditions, the reaction of benzeneselenol
pyridine, and pyrimidine were also examined, leading afforded several unsymmetrical selenides (4m–r) in
to the desired products (3l–o) being obtained. In 68–81% yield.
addition, heteroaromatic thiols (2p–t) were success-
Sulfoxides as the highly valuable building blocks
fully converted in good yields. Interestingly, benzo- have been widely employed in organocatalysis, orga-
thioic S-acid 2u and alkyl thiols (2v, 2w) were also nometallic, and chemistry materials.[18] As we men-
well compatible with this process, giving the desired tioned in Table 1, 4,4’-sulfinylbis(methoxybenzene) 5d
products in good yields (3u–w). Importantly, glucose was detected under 15 mA constant current. Thus, we
derived thiol 2x and L-cysteine 2y were also found to speculated that thioether and sulfoxide could be
be amenable substrates providing the corresponding selectively synthesized by only changing the current.
products 3x and 3y in 73% and 66% yields, To our delight, when the constant current increased to
respectively.
20 mA and the reaction time changed to 4 hours, 4,4’-
sulfinylbis(methoxybenzene) 5d could be detected in
Scheme 1. Substrate scope of thiols.
Scheme 2. Substrate scope of arylazo sulfones.
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88% yield (Scheme 3a). The electrolysis reaction of
Arylboronates play a significant role in chemical,
3d also gave 5d under the same conditions in 81% material, and medicinal areas.[19] Subsequently, we paid
yield (Scheme 3b). To gain more insight into this our attention to the reaction of arylazo sulfones and bis
oxidation, a reaction was conducted at nitrogen (pinacolato)diboron (B2pin2) under mild conditions.
atmosphere and only trace amount of sulfoxide was Delightedly, a variety of arylazo sulfones can be used
detected (Scheme 3c). Subsequently, we performed an regardless of their electronic nature and gave the
18
isotope labeling experiment in air by using H2 O. Very corresponding products (7a–h) as shown in Scheme 5.
few 18O products were detected, which showed that the The results demonstrate that electrochemical paired
oxygen atom of sulfoxide almost came from O2 in air electrolysis is a better alternative to the visible light
(Scheme 3d). These results indicated that higher photoredox-based oxidation quenching method owing
current (20 mA) not only helped to generate the to significantly reducing the reaction time.[15a] When 4-
thioethers but further over oxidized the products to methoxyphenyldiazonium tetrafluoroborate was ap-
sulfoxides in the presence of O2. As a comparison, plied in this electrochemical transformation, lower
even at air atmosphere, a suitable current (10 mA) yield (65%) of 7c was obtained, which indicated that
could control the product in thioethers stage with high arylazo sulfones had better reactivity.
selectivity. A preliminary study on substrate scope
To further explore the scalability of our method, we
were also investaged and several sulfoxides (5b, 5f, expanded this synthesis approach on a gram scale
5i, 5j) were successfully synthesized (Scheme 4).
(Scheme 6). With the same ratio of electric current
applied, the desired product 3m and 7c could be
obtained in 60% and 73% yield, respectively. The
result highlighted the potential of this electrochemical
reaction for application in actual industrial production.
To further study the reaction mechanism, several
control experiments were carried out (Scheme 7). The
Scheme 3. Study on selectively transformation of thioether and
sulfoxide.
Scheme 5. Borylation of Arylazo Sulfones with B2pin2.
Scheme 4. Synthesis of sulfoxides.
Scheme 6. Gram-scale synthesis.
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Scheme 7. Control experiments.
electrochemical coupling reaction was fully suppressed
when 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)
and 2,6-di-tert-butyl-4-methylphenol (BHT) were
added to the reaction system, which indicated a radical
process (Scheme 7a and 7b). When the reaction time
was changed to 0.5 h, 1,2-bis(4-fluorophenyl)disulfane
8f was detected by GC-MS with 37% GC yield
(Scheme 7c, see more details in SI). Then the reaction
of 1-(4-methoxyphenyl-2-(methylsulfonyl)diazene 1a
and 1,2-diphenyldisulfide 8a was carried out under
standard conditions and gave 52% yield of the desired
product 3a (Scheme 7d). Accordingly, we speculated
that 8a was the key intermediate in this reaction
system.
Figure 2. (a) CV curves 1 and 2 of 1a in MeCN and MeCN/
H2O, respectively. (b) CV curves 3 and 4 of 2f in MeCN and
MeCN/H2O, respectively. (c) CV curves 5 of 1a and 2f in
MeCN/H2O. (d) Reaction of 1a under optimal conditions. (e)
Reaction of 2f under optimized conditions.
“H” source like acetonitrile or water.[20] For 2f, only
Cyclic voltammograms (CV) experiments was oxidation was observed with or without water. We
carried out to study the redox potential of the speculated that a rapid formation of disulfide occurred
substrates 1a and 2f. 1-(4-methoxyphenyl)-2-(meth- instead of reduced at the other end of the electrode
ylsulfonyl)diazene 1a exhibited an obvious oxidation when 2f was oxidized to generate sulfur radical. We
peak at À 0.74 V and a reduction peak À 0.98 V vs Hg/ did observed trace amount of anisole as by-product in
HgCl2 (0.1 M in MeCN) while only a reduction peak at standard conditions, acetonitrile and water maybe the
À 0.95 V vs Hg/HgCl2 (0.1 M in MeCN/H2O) could be H source. However, based on the results that thioethers
observed (Figure 2a). The oxidation peak of 4-fluoro- were major products, it was obvious that phenyl radical
thiophenol 2f could also be observed at about 1.79 V is much easier to react with disulfide.
vs Hg/HgCl2 (0.1 M in MeCN) and 1.75 V vs Hg/
On the basis of previous reports[11a,14i] and obtained
HgCl2 (0.1 M in MeCN/H2O) (Figure 2b). The mixture experimental results, a plausible mechanism for the
of 1a and 2f was also conducted which showed a CÀ S formation process is presented in Figure 3.
reduction peak À 0.89 V vs Hg/HgCl2 (0.1 M in Single-electron-transfer (SET) oxidation of thiol 2 by
MeCN/H2O) and an oxidation peak at 1.61 V vs Hg/ the anode leads to the formation of sulfur radical I,
HgCl2 (0.1 M in MeCN/H2O) (Figure 2c). Next, we which generate the disulfide 8 by rapid dimerization.
conducted two reactions with 1a or 2f under optimal In the meantime, 1-(4-methoxyphenyl)-2-(methylsul-
conditions, respectively (Figure 2d and 2e). Anisole 9 fonyl)diazene 1a is reduced at the cathode to give the
and 1,2-bis(4-fluorophenyl)disulfane 8f were detected 4-methoxyphenyl radical II and methanesulfonyl anion
by GC-MS (details showed in the SI). These results III. The radical II is trapped by the disulfide 8 to
indicated that both reduction and oxidation of 1a deliver the desired product 3 with the release of thiol
occurred when only in MeCN while no oxidation radical I. The methanesulfonyl anion III is oxidated to
happened in MeCN/H2O. We speculated that 1a was furnish methanesulfonyl radical IV, trapped by 8 to
firstly reduced to generate phenyl radical, then formed give the by-product 10 which was detected by GC-MS
anisole 9 via hydrogen abstraction in the presence of (See SI for details). At the cathode, H2O is reduced to
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10 mm×0.3 mm). Cyclic voltammograms were obtained on a
CS310H potentiostat. Analytical thin-layer chromatography is
performed on glass plates precoated with silica gel impregnated
with a fluorescent indicator (254 nm), and the plates are
visualized by exposure to ultraviolet light. 1H, 13C and 19F NMR
spectra were recorded on a 500 MHz Bruker DRX 500.
Chemical shifts were reported in parts per million (ppm), and
the residual solvent peak was used as an internal reference:
proton (chloroform δ 7.26), carbon (chloroform δ 76.0). GC-
MS data was recorded on a ISQ LT Single Quadrupole Mass
Spectrometer, coupled with a Trace 1300 Gas Chromatograph
(Thermo Fisher Scientific). High resolution mass spectral data
were acquired on Waters Micromass GCT Premier spectrom-
eter.
General Procedure for the Synthesis of Thioethers
or Selenoethers from Arylazo Sulfones and Thiols
or Benzeneselenol
An undivided cell was equipped with graphite rod (ϕ 3 mm,
about 16 mm immersion depth in solution) as the anode and
platinum plate (15 mm×10 mm×0.3 mm) as the cathode. A
mixture of arylazo sulfone 1 (0.6 mmol), thiol or benzenesele-
nol 2 (0.3 mmol) and LiClO4 (0.8 mmol) in MeCN/H2O (7:1,
8.0 mL) were added to the undivided cell. The reaction mixture
was stirred and electrolyzed at a constant current of 10 mA at
room temperature for 2.0 h. After the reaction is over, EtOAc
(10.0 mL) was added, and the mixture was washed with water
(20×3 mL), dried with Na2SO4 and concentrated under vacuum
to give the crude product. Further column chromatography on
silica gel (ethyl acetate/petroleum ether) was needed to afford
the pure desired product.
Figure 3. Proposed reaction mechanism.
furnish H2 and HOÀ . As arylazo sulfones could
generate phenyl radical upon exposure to visible
(solar) light[14a] and thiols could form disulfide in
air,[15b] thus a trace amount of desired product could
also form without electricity (Table 1, entry 13).
General Procedure for the Synthesis of Arylboronic
Esters from Arylazo Sulfones and B2pin2
Conclusion
An undivided cell was equipped with graphite rod (ϕ 3 mm,
about 16 mm immersion depth in solution) as the anode and
platinum plate (15 mm×10 mm×0.3 mm) as the cathode. A
mixture of arylazo sulfone 1 (0.6 mmol), B2pin2 6 (0.9 mmol)
and LiClO4 (0.8 mmol) in MeCN/H2O (7:1, 8.0 mL) were added
to the undivided cell. The reaction mixture was stirred and
electrolyzed at a constant current of 10 mA at room temperature
for 2.0 h. After the reaction is over, EtOAc (10.0 mL) was
added, and the mixture was washed with water (20×3 mL),
dried with Na2SO4 and concentrated under vacuum to give the
crude product. Further column chromatography on silica gel
(ethyl acetate/petroleum ether) was needed to afford the pure
desired product.
In summary, we developed a mild and efficient electro-
chemical protocol to construct CÀ S and CÀ B bonds.
Various unsymmetrical thioethers and arylboronates
could be obtained in good to excellent yields from
readily available and simple starting materials. Nota-
bly, for this convenient and environmentally benign
electrochemical approach, neither exogenous-oxidants
nor metal catalysts were needed. Moreover, only by
changing the current, thioether and sulfoxide could be
selectively synthesized. We expect that these efforts
will guide the further development of synthetically
useful electrochemical organic transformations.
Experimental Section
Procedure for Gram Scale Synthesis of 3m and 7c
Aryldiazo sulfones were prepared according to the literature
procedure.[21] Other chemical reagents are obtained from
commercial suppliers and used without further purification. All
known compounds are identified by appropriate technique such
as 1H NMR, 13C NMR, 19F NMR and compared with previously
An undivided cell was equipped with graphite felt (30 mm×
20 mm×5 mm) as the anode and platinum plate (30 mm×
20 mm×0.3 mm) as the cathode. A mixture of 1-(4-meth-
oxyphenyl)-2-(methylsulfonyl)diazene 1a (6.0 mmol), pyridine-
4-thiol 2m (3.0 mmol) or (bis(pinacolato)diboron 6 (9.0 mmol),
and LiClO4 (8.0 mmol) in MeCN/H2O (7:1, 80.0 mL) were
added to the undivided cell. The reaction mixture was stirred
and electrolyzed at a constant current of 10 mA at room
1
reported data. All unknown compounds are characterized by H
NMR, 13C NMR, 19F NMR and HRMS. The anode electrode is
graphite rod and cathode electrode is platinum plate (15 mm×
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temperature for 20 h. After the reaction is over, EtOAc
(100.0 mL) was added, and the mixture was washed with water
(100×3 mL), dried with Na2SO4 and concentrated under
vacuum to give the crude product. Further column chromatog-
raphy on silica gel (ethyl acetate/petroleum ether) was needed
to afford the pure desired product.
Soc. Rev. 2015, 44, 291–314; d) C. C. Eichmann, J. P.
Stambuli, J. Org. Chem. 2009, 74, 4005–4008; e) M.
Arisawa, T. Tazawa, S. Tanii, K. Horiuchi, M. Yamagu-
chi, J. Org. Chem. 2017, 82, 804–810; f) P.-F. Wang, X.-
Q. Wang, J.-J. Dai, Y.-S. Feng, H.-J. Xu, Org. Lett. 2014,
16, 4586–4589; g) H. L. Li, Y. Kuninobu, M. Kanai,
Angew. Chem. 2017, 129, 1517–1521; Angew. Chem. Int.
Ed. 2017, 56, 1495–1499; h) M. Jiang, H. Li, H. Yang,
H. Fu, Angew. Chem. 2017, 129, 892–897; Angew. Chem.
Int. Ed. 2017, 56, 874–879.
Acknowledgements
We gratefully acknowledge the National Natural Science
Foundation of China (21776138, 22087161), Fundamental
Research Funds for the Central Universities (30920021124,
30918011314), Natural Science Foundation of Jiangsu Province
(BK20180476), the China Postdoctoral Science Foundation
Funded Project (No. 2019 M661848), Qing Lan and Six Talent
Peaks in Jiangsu Province and Priority Academic Program
Development of Jiangsu Higher Education Institutions for
financial support.
[4] a) M. A. Fernandez-Rodrıguez, Q. Shen, J. F. Hartwig, J.
Am. Chem. Soc. 2006, 128, 2180–2181; b) G. Y. Li,
Angew. Chem. 2001, 113, Nr. 8; Angew. Chem. Int. Ed.
2001, 40, 1513–1516; c) T. Itoh, T. Mase, Org. Lett.
2004, 6, 4587–4590; d) C. C. Eichman, J. P. Stambuli, J.
Org. Chem. 2009, 74, 4005–4008; e) P. Anbarasan, H.
Neumann, M. Beller, Chem. Commun. 2011, 47, 3233–
3235; f) M. Iwasaki, M. Iyanaga, Y. Tsuchiya, Y.
Nishimura, W. Li, Z. Li, Y. Nishihara, Chem. Eur. J.
2014, 20, 2459–2462; g) X. S. Zhang, G. Li, X. G.
Zhang, X. H. Zhang, Tetrahedron. 2015, 71, 5458–5464;
h) Z. Lian, B. N. Bhawal, P. Yu, B. Morandi, Science
2017, 356, 1059–1063.
[5] a) N. Taniguchi, J. Org. Chem. 2004, 69, 6904–6906;
b) Y. Zhang, K. C. Ngeow, J. Y. Ying, Org. Lett. 2007, 9,
3495–3498; c) K. Yang, Y. Wang, X. Chen, A. A. Kadi,
H.-K. Fun, H. Sun, Y. Zhang, H. Lu, Chem. Commun.
2015, 51, 3582–3585; d) F. Gao, W. Zhu, D. Zhang, S.
Li, J. Wang, H. Liu, J. Org. Chem. 2016, 81, 9122–9130;
e) M. S. Oderinde, M. Frenette, D. W. Robbins, B.
Aquila, J. W. Johannes, J. Am. Chem. Soc. 2016, 138,
1760–1763; f) N. Ichiishi, C. A. Malapit, Ł. Woźniak,
M. S. Sanford, Org. Lett. 2018, 20, 44–47.
[6] a) F. Y. Kwong, S. L. Buchwald, Org. Lett. 2002, 4,
3517–3520; b) P. Gandeepan, J. Koeller, L. Ackermann,
ACS Catal. 2017, 7, 1030–1034.
[7] a) Y. Y. Lin, Y. J. Wang, C. H. Lin, J. H. Cheng, C. F.
Lee, J. Org. Chem. 2012, 77, 6100–6106; b) A. Correa,
M. Carril, C. Bolm, Angew. Chem. 2008, 120, 2922–
2925; Angew. Chem. Int. Ed. 2008, 47, 2880–2883;
c) J. R. Wu, C. H. Lin, C. F. Lee, Chem. Commun. 2009,
4450–4452.
[8] a) Y. C. Wong, T. T. Jayanth, C. H. Cheng, Org. Lett.
2006, 8, 5613–5616; b) T. Gensch, F. J. R. Klauck, F.
Glorius, Angew. Chem. 2016, 128, 11457–11461; Angew.
Chem. Int. Ed. 2016, 55, 11287–11291.
[9] a) M. Jouffroy, C. B. Kelly, G. A. Molander, Org. Lett.
2016, 18, 876–879; b) H. Cui, W. Wei, D. Yang, Y.
Zhang, H. Zhao, L. Wang, H. Wang, Green Chem. 2017,
19, 3520–3524; c) W. Wei, H. Cui, D. Yang, Y. Zhang,
H. Yue, C. He, Y. Zhang, H. Wang, Green Chem. 2017,
19, 5608–5613; d) R. Rahaman, S. Das, P. Barman,
Green Chem. 2018, 20, 141–147.
References
[1] a) H. Liu, X. Jiang, Chem. Asian J. 2013, 8, 2546–2563;
b) T. Kondo, T. A. Mitsudo, Chem. Rev. 2000, 100,
3205–3220; c) F. Denes, M. Pichowicz, G. Povie, P.
Renaud, Chem. Rev. 2014, 114, 2587–2693; d) E. Block,
J. Sulfur, Chem. 2013, 34, 158–207; e) A. Correa, O.
Garcia Mancheno, C. Bolm, Chem. Soc. Rev. 2008, 37,
1108–1117; f) M. A. Vazquez-Prieto, R. M. Miatello,
Mol. Aspects Med. 2010, 31, 540–545; g) Y. Fang, T.
Rogge, L. Ackermann, S. Y. Wang, S. J. Ji, Nat.
Commun. 2018, 9, 2240; h) X. Ren, S. Tang, L. Li, J. Li,
H. Liang, G. Li, G. Yang, H. Li, B. Yuan, J. Org. Chem.
2019, 84, 8683–8690.
[2] a) G. Smith, G. Mikkelsen, J. Eskildsen, C. Bundgaard,
Bioorg. Med. Chem. Lett. 2006, 16, 3981–3984; b) J.
Dumas, D. Brittelli, J. Chen, B. Dixon, H. Hatoum-
Mokdad, G. Kçnig, R. Sibley, J. Witowsky, S. Wong,
Bioorg. Med. Chem. Lett. 1999, 9, 2531–2536; c) L.
Zhang, J. Fan, K. Vu, K. Hong, J.-Y. Le Brazidec, J. Shi,
M. Biamonte, D. J. Busch, R. E. Lough, R. Grecko, Y.
Ran, J. L. Sensintaffar, A. Kamal, K. Lundgren, F. J.
Burrows, R. Mans-field, G. A. Timony, E. H. Ulm, S. R.
Kasibhatla, M. F. Boehm, J. Med. Chem. 2006, 49,
5352–5362; d) G. La Regina, M. C. Edler, A. Brancale,
S. Kandil, A. Coluccia, F. Piscitelli, E. Hamel, G.
De Martino, R. Matesanz, J. F. Diaz, A. I. Scovassi, E.
Prosperi, A. Lavecchia, E. Novellino, M. Artico, R.
Silvestri, J. Med. Chem. 2007, 50, 2865–2874; e) M. C.
Bagley, T. Davis, M. C. Dix, V. Fusillo, M. Pigeaux,
M. J. Rokicki, D. Kipling, J. Org. Chem. 2009, 74,
8336–8342; f) P. Wang, S. Tang, P. Huang, A. Lei,
Angew. Chem. 2017, 129, 3055–3059; Angew. Chem. Int.
Ed. 2017, 56, 3009–3013.
[10] a) B. A. Vara, X. Li, S. Berritt, C. R. Walters, E. J.
Petersson, G. A. Molander, Chem. Sci. 2018, 9, 336–344;
b) M. S. Oderinde, M. Frenette, D. W. Robbins, B.
Aquila, J. W. Johannes, J. Am. Chem. Soc. 2016, 138,
1760–1763; c) M. Jiang, H. Li, H. Yang, H. Fu, Angew.
[3] a) C. F. Lee, Y. C. Liu, S. S. Badsara, Chem. Asian J.
2014, 9, 706–722; b) I. P. Beletskaya, V. P. Ananikov,
Chem. Rev. 2011, 111, 1596–1636; c) C. Shen, P. F.
Zhang, Q. Sun, S. Q. Bai, T. S. A. Hor, X. G. Liu, Chem.
Adv. Synth. Catal. 2021, 363, 1904–1911
1910
© 2021 Wiley-VCH GmbH

FULL PAPER
asc.wiley-vch.de
Chem. Int. Ed. 2017, 56, 874–879; Angew. Chem. 2017,
129, 892–897; d) M. W. Johnson, K. I. Hannoun, Y. Tan,
G. C. Fu, Chem. Sci. 2016, 7, 4091–4100; e) B. Liu, C.-
H. Lim, G. M. Miyake, J. Am. Chem. Soc. 2017, 139,
13616–13619.
2095; h) H.-B. Zhao, Z.-W. Hou, Z.-J. Liu, Z.-F. Zhou, J.
Song, H.-C. Xu, Angew. Chem. 2017, 129, 602–605;
Angew. Chem. Int. Ed. 2017, 56, 587–590; i) Q.-L. Yang,
Y.-Q. Li, C. Ma, P. Fang, X.-J. Zhang, T.-S. Mei, J. Am.
Chem. Soc. 2017, 139, 3293–3298; j) S. Tang, Y. Liu, A.
Lei, Chem 2018, 4, 27–45; k) K. D. Moeller, Chem. Rev.
2018, 118, 4817–4833; l) J. I. Yoshida, A. Shimizu, R.
Hayashi, Chem. Rev. 2018, 118, 4702–4730.
[11] a) D. Liu, H. X. Ma, P. Fang, T. S. Mei, Angew. Chem.
2019, 131, 5087–5091; Angew. Chem. Int. Ed. 2019, 58,
5033–5037; b) Y. Wang, L. L. Deng, X. C. Wang, Z. G.
Wu, Y. Wang, Y. Pan, ACS Catal. 2019, 9, 1630–1634.
[12] a) J. L. Kice, R. S. Gabrielsen, J. Org. Chem. 1970, 35,
1010–1015; b) G. Rosini, R. Ranza, J. Org. Chem. 1971,
36, 1915–1918.
[13] a) M. Kobayashi, S. Fujii, H. Minato, Bull. Chem. Soc.
Jpn. 1972, 45, 2039–2042; b) J. Eastoe, M. Sanchez-
Dominguez, H. Cumber, G. Burnett, P. Wyatt, R. K.
Heenan, Langmuir 2003, 19, 6579–6581.
[17] a) P. Huang, P. Wang, S. Tang, Z. Fu, A. Lei, Angew.
Chem. 2018, 130, 8247–8251; Angew. Chem. Int. Ed.
2018, 57, 8115–8119; b) Y. Li, Q. Yang, L. Yang, N. Lei,
K. Zheng, Chem. Commun. 2019, 55, 4981–4984; c) Z.-
Y. Mo, T. R. Swaroop, W. Tong, Y.-Z. Zhang, H.-T.
Tang, Y.-M. Pan, H.-B. Sun, Z.-F. Chen, Green Chem.
2018, 20, 4428–4432; d) D. Li, S. Li, C. Peng, L. Lu, S.
Wang, P. Wang, Y.-H. Chen, H. Cong, A. Lei, Chem. Sci.
2019, 10, 2791–27945.
[14] a) S. Crespi, S. Protti, M. Fagnoni, J. Org. Chem. 2016,
81, 9612–9619; b) A. Dossena, S. Sampaolesi, A. [18] a) I. Fernandez, N. Khiar, Chem. Rev. 2003, 103, 3651–
Palmieri, S. Protti, M. Fagnoni, J. Org. Chem. 2017, 82,
10687–10692; c) M. Malacarne, S. Protti, M. Fagnoni,
Adv. Synth. Catal. 2017, 359, 3826–3830; d) C. Sauer, Y.
Liu, A. De Nisi, S. Protti, M. Fagnoni, M. Bandini,
ChemCatChem 2017, 9, 4456–4459; e) P. E. da Silva Jú-
nior, H. I. M. Amin, A. M. Nauth, F. da Silva Emery, S.
Protti, T. Opatz, ChemPhotoChem 2018, 2, 878–883;
f) L. Onuigbo, C. Raviola, A. Di Fonzo, S. Protti, M.
3705; b) C. D. Jiang, J. Covell, A. F. Stepan, M. S.
Plummer, M. C. White, Org. Lett. 2012, 14, 1386–1389;
c) M. Mellah, A. Voituriez, E. Schulz, Chem. Rev. 2007,
107, 5133–5209; d) G. Sipos, E. E. Drinkela, R. Dorta,
Chem. Soc. Rev. 2015, 44, 3834–3860; e) V. V. Chaban,
Phys. Chem. Chem. Phys. 2016, 18, 10507–10515;
f) V. V. Chaban, Phys. Chem. Chem. Phys. 2018, 20,
23754–23761.
Fagnoni, Eur. J. Org. Chem. 2018, 5297–5303; g) L. [19] a) N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457–
Blank, M. Fagnoni, S. Protti, M. Rueping, Synthesis
2019, 51, 1243–1252; h) C. Lian, G. Yue, J. Mao, D.
Liu, Y. Ding, Z. Liu, D. Qiu, X. Zhao, K. Lu, M.
Fagnoni, S. Protti, Org. Lett. 2019, 21, 5187–5191; i) D.
Qiu, C. Lian, J. Mao, Y. Ding, Z. Liu, L. Wei, M.
Fagnoni, S. Protti, Adv. Synth. Catal. 2019, 361, 5239–
5244; j) D. Qiu, C. Lian, J. Mao, M. Fagnoni, S. Protti,
J. Org. Chem. 2020, 85, 12813–12822.
2483; b) R. L. Jarvest, J. M. Berge, M. J. Brown, P.
Brown, J. S. Elder, A. K. Forrest, C. S. V. Houge-
Frydrych, P. J. O’Hanlon, D. J. McNair, S. Rittenhouse,
R. J. Sheppard, Bioorg. Med. Chem. Lett. 2003, 13, 665–
668; c) X. Hui, S. J. Baker, R. C. Wester, S. Barbadillo,
A. K. Cashmore, V. Sanders, K. M. Hold, T. Akama,
Y. K. Zhang, J. J. Plattner, H. I. Maibach, J. Pharm. Sci.
2007, 96, 2622–2631; d) C. Shen, P. Zhang, Q. Sun, S.
Bai, T. S. A. Hor, X. Lui, Chem. Soc. Rev. 2015, 44,
291–314; e) W. L. Brooks, B. S. Sumerlin, Chem. Rev.
2016, 116, 1375–1397; f) H. S. Ban, H. Nakamura,
Chem. Rec. 2015, 15, 616–635; g) L. Xu, S. Zhang, P.
Li, Chem. Soc. Rev. 2015, 44, 8848–8858; h) A. J.
Lennox, G. C. Lloyd-Jones, Chem. Soc. Rev. 2014, 43,
412–443; i) D. Li, Y. Chen, Z. Liu, Chem. Soc. Rev.
2015, 44, 8097–8123.
[15] a) Y. Xu, X. Yang, H. Fang, J. Org. Chem. 2018, 83,
12831–12837; b) Q. Liu, L. Wang, H. Yue, J.-S. Li, Z.
Luo, W. Wei, Green Chem. 2019, 21, 1609–1613.
[16] a) J. B. Sperry, D. L. Wright, Chem. Soc. Rev. 2006, 35,
605–621; b) A. Jutand, Chem. Rev. 2008, 108, 2300–
2347; c) R. Francke, R. D. Little, Chem. Soc. Rev. 2014,
43, 2492–2521; d) E. J. Horn, B. R. Rosen, Y. Chen, J.
Tang, K. Chen, M. D. Eastgate, P. S. Baran, Nature 2016,
533, 77–81; e) A. Badalyan, S. S. Stahl, Nature 2016, [20] H. I. M. Amin, C. Raviola, A. A. Amin, B. Mannucci, S.
535, 406–410; f) A. Kirste, G. Schnakenburg, F. Stecker, Protti, M. Fagnoni, Molecules 2019, 24, 2164.
A. Fischer, S. R. Waldvogel, Angew. Chem. 2010, 122, [21] D. Y. Wang, X. Zhang, H. Liu, H. Chen, D. Huang, Org.
983; Angew. Chem. Int. Ed. 2010, 49, 971–975; g) P.
Wang, S. Tang, A. Lei, Green Chem. 2017, 19, 2092–
Chem. Front. 2017, 4, 31–36.
Adv. Synth. Catal. 2021, 363, 1904–1911
1911
© 2021 Wiley-VCH GmbH