Synthesis of Tetrasubstituted α,β-Unsaturated Aldehydes via Radical 1,4-Aryl Migration/Trifluoromethylthiolation Cascade Reaction of Aryl Propynyl Ethers

Article abstract of DOI:10.1002/adsc.201700534

A one-pot synthesis of tetrasubstituted acrylaldehydes via difunctionalization of aryl propynyl ethers has been achieved, which involves a trifluoromethylthiolation process and a radical 1,4-aryl migration from oxygen to carbon. The reaction shows excellent conversion of aryl propynyl ethers into trifluoromethyl-containing α,β-unsaturated aldehydes through a radical pathway. (Figure presented.).

Full text of DOI:10.1002/adsc.201700534

Title: Synthesis of Tetrasubstituted α,β-Unsaturated Aldehydes via
Radical 1,4-Aryl Migration/Trifluoromethylthiolation Cascade
Reaction of Aryl Propynyl Ethers
Authors: Chun-Huan Guo, Dao-Qian Chen, Si Chen, and Xue-yuan Liu
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700534
Link to VoR: http://dx.doi.org/10.1002/adsc.201700534

Advanced Synthesis & Catalysis
10.1002/adsc.201700534
COMMUNICATION
DOI: 10.1002/adsc.201
Synthesis of Tetrasubstituted α,β-Unsaturated Aldehydes via
Radical 1,4-Aryl Migration/Trifluoromethylthiolation Cascade
Reaction of Aryl Propynyl Ethers
a
b
a
a
Chun-Huan Guo, Dao-Qian Chen, Si Chen, and Xue-Yuan Liu*
a
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China.
E-mai:liuxuey@lzu.edu.cn
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, China.
b
Received:
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.
Abstract. An one-pot synthesis of tetrasubstituted carbon by using alkynoates as substrates.[8] However,
acrylaldehydes via difunctionalization of aryl propynyl these migration reactions are not only limited to
ethers
has
been
achieved,
which
involves putting alkynoates as substrates, but also restricted to
trifluoromethylthiolation process, radical 1,4-aryl migration acquiring trisubstituted alkenes. Actually carbon-
from oxygen to carbon. The reaction shows excellent carbon triple bonds can be easily converted into
[9]
3
conversion of aryl propynyl ethers into SCF -containing
tetrasubstituted alkenes by addition reactions. In
014, our group reported the synthesis of
α,β-unsaturated aldehydes through a radical pathway.
2
tetrasubstituted alkenes that involve copper-catalyzed
trifluoromethylation, radical 1,4-aryl migration from
carbon to carbon, and the formation of a carbonyl
Keywords: 1,4-aryl migration; trifluoromethylthiolation;
α,β-unsaturated aldehydes; radical reaction;
difunctionalization
[4c]
group. To the best of our knowledge, we realize
that the reaction involving radical 1,4-aryl migration
from oxygen to carbon and trifluoromethylthiolation
of aryl propynyl ethers has been not reported yet.
Radical aryl migration reactions represent a particular
interest to the chemical community due to their
intersection of both radical and rearrangement
Scheme 1. Summary of previous studies and our new
anticipation
[1]
reactions in radical chemistry and organic synthesis.
As a consequence, numerous versatile and fascinating
radical aryl migrations have been reported, such as
[2]
[3]
[4]
[5]
radical 1,2-, 1,3-, 1,4-, and 1,5- aryl migration.
Among these radical reactions, 1,4-migration
probably shows the most synthetically useful
transformation.[ For years, there have been a large
number of literatures involving radical 1,4-aryl
migrations from carbon to carbon and from sulfur
atom to carbon, but related reports of 1,4-migration
6]
[7]
between carbon and oxygen are rarely covered until
now. In 1993, Eun Lee and workmates first disclosed
radical 1,4-aryl translocation from oxygen to carbon
via intramolecular ipso substitution of aryl ethers, but
the corresponding products are observed as by-
It is well known that fluorine-containing
[7d]
product (Scheme 1a).
Subsequently, Prabhakar
compounds are widely used in agrochemicals,
group[ and Lobo group
4n]
[7b]
successively reported
[10]
pharmaceuticals,
and
materials.
In
the
S)
group not only holds a special position but also has a
that a series of benzyl phenyl ethers could be
converted to biaryl compounds in very low yields by
means of an analogous radical migration (Scheme 1b). great potential in the development of new
Therefore, one of the great challenges ahead is to
search new substrates to continue studying radical
organofluorine family, the trifluoromethylthio (CF
3
[11]
pharmaceutical and agrochemicals due to its strong
electron-withdrawing effects, extremely high
[12]
[13]
1
,4-aryl migration reactions from oxygen to carbon.
lipophilicity and good bioavailability. So far, a
variety of well-established methods about preparation
of trifluoromethylthiolated compounds have been
Very recently, several groups successfully studied
radical 1,4-aryl migration reactions from oxygen to
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201700534
realized,[14] and AgSCF
as an easily prepared and
screened, revealing that K
S
O was the best choice
3
2
2
8
stable trifluoromethylthiolation reagent has been
for the reaction (entries 2−4). A brief investigation of
solvents revealed that the highest yield was obtained
for the reaction conducted in DMSO, whereas no
desired product was detected in DCE, THF, and
toluene (entries 5−9). Subsequently, further study on
widely applied to the formation of the C-SCF bond
3
via a radical pathway.[ By taking into consideration
15]
our current interest in the synthesis of
trifluoromethylthio-containg compounds,
[14f, 15a]
as
well as the continued anticipation of innovative
methods to tetrasubstituted acrylaldehydes, we
disclose a novel route about the formation of
tetrasubstituted α,β-unsaturated aldehydes by using
aryl propynyl ethers as substrates, which combines
alkyne trifluoromethylthiolation, radical 1,4-aryl
migration from oxygen to carbon and formation of a
carbonyl moiety in a one-pot reaction (Scheme 1c).
Particularly, mild reaction conditions, low toxic and
experiment convenience are fully realized in our
reaction system.
the effect of bases indicated that K
3
PO was the most
4
suitable for this reaction and the yield could be
increased to 58% (entries 11-16). And yet, the yield
of the desired product was reduced to 34% in the
absence of base (entry 10).
A
subsequent
investigation on the effect of temperature showed that
this reaction was most efficiently conducted at 80 °C
(entries 16−18). Ultimately, the optimized reaction
conditions were confirmed by using 1a (0.2 mmol),
AgSCF
3
(1.5 equiv), K
2
2
S O
8
(3.0 equiv), and K
3
PO
4
(2.0 equiv) in DMSO at 80 °C for 8 h under argon.
Table 1. Optimization of the reaction conditionsa)
Scheme 2. Reaction scope of aryl 3-aryl-2-propynyl
ethers
a,b)
Yield
Entry Oxidant
Base (equiv) Solvent
b)
(
%)
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
K
2
S
2
O
8
HMPA(0.5)
HMPA(0.5)
HMPA(0.5)
HMPA(0.5)
HMPA(0.5)
HMPA(0.5)
HMPA(0.5)
HMPA(0.5)
HMPA(0.5)
-
CH
CH
CH
CH
DMSO
DCE
DMF
toluene
THF
DMSO
DMSO
3
3
3
3
CN
CN
CN
CN
20
0
16
Oxone
Na
PhI(OAc)
2
2
S O
8
2
0
c)
K
2
K
2
K
2
K
2
K
2
K
2
K
2
K
2
K
2
K
2
K
2
K
2
K
2
K
2
S
S
S
S
S
S
S
S
S
S
S
S
S
S
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
8
8
8
8
8
8
8
8
8
8
8
8
8
8
30 (27)
0
15
0
0
34
25
20
45
39
43
58
47
50
0
1
2
3
4
5
6
7
8
Et N(0.5)
3
t-BuOK(0.5) DMSO
Na CO (2.0) DMSO
CO (2.0) DMSO
CO (2.0) DMSO
2
3
Cs
2
3
Ag
2
3
3
K PO
3
K PO
3
K PO
4
4
4
(2.0)
(2.0)
(2.0)
DMSO
DMSO
DMSO
d)
e)
1
a)
Unless otherwise noted, all reactions were performed
(1.5 equiv), oxidant (3.0
with 1a (0.2 mmol), AgSCF
3
equiv) and base (2.0 equiv) in solvent (2.0 mL) at 80 °C
b)
under an argon atmosphere for 8 h. Yields are given for
c)
isolated products. 30 % of 3a was isolated in DMSO and
d)
2
7% in anhydrous DMSO, respectively. The temperature
e)
of reaction is 60 °C. The temperature of reaction is
1
00 °C.
At the beginning of this study, we investigated the
a)Reaction conditions: 1 (0.2 mmol), AgSCF
K S O (3.0 equiv) and K PO (2.0 equiv) in DMSO (2.0
2 2 8 3 4
3
(1.5 equiv),
reaction of (3-phenoxyprop-1-yn-1-yl)benzene 1a
with AgSCF
3
( 1.5 equive), K
S
2 2
O
8
(3.0 equive), and
b)
mL) at 80 °C under an argon atmosphere for 8 h. Isolated
HMPA (0.5 equive) in MeCN at 80 °C under an
argon atmosphere for 8 h. Much to our delight, the
anticipative product 3a was isolated in 20% yield
c)
yields. The olefin isomer E/Z ratios are assigned by
1
d)
integral area of H NMR spectra. The yield of scale-up
experiment of 1d (1.0 g)
(
Table 1, entry 1). Above all, various oxidants were
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201700534
With the optimized conditions in hand, then we
standard system (Scheme 3a). Next, the desired
transformation was also effectively inhibited when
we put 2.0 equiv of 2,6-di-tert-butyl-4-methylphenol
focused on exploring the substrate scope of aryl 3-
aryl-2-propynyl ethers. A wide variety of substitution
patterns and functional groups were tolerated. Aryl 3-
aryl-2-propynyl ethers bearing either the same
electron-donating or electron-withdrawing group in
the same position of two aryl rings were smoothly
converted into the desired products in moderate to
good yields (Scheme 2, 3a-3q). The reaction of 1b,
(
(
BHT) into the reaction under standard conditions
Scheme 3b). These results indicated that a radical
pathway could be possibly involved. And then, we
investigated the reaction of the isolated product 3w
(
(
3w’) under the standard conditions. The product 3w
3w’) was partly converted the other isomer 3w’ (3w),
1
3
c and 1d offered tetrasubstituted acrylaldehydes 3b,
c and 3d in 55%, 50% and 74% yields, respectively,
suggesting that electron-donating groups as ortho-
para directing group have a certain impact on
electronic distribution of aromatic ring, which could
also be deduced from the yield of products 3e, 3f and
g. Halogen substituents such as Cl and Br could be
tolerated to afford the corresponding products in 50-
0% yields (3l-3n) in this transformation, which may
provide an opportunity for trifluoromethylthio-
containing derivatizations via further cross-coupling
reaction. It was noteworthy that substrates with
which proved the fact that isomerization occurred
later on the product aldehydes. (Scheme 3c). In the
end, the substrate 1y with a benzyl group in the
substrate next to the O-atom only afforded product 3a
in 28% yield rather than 4y (Scheme 3d). This result
indicated that the alkoxyl radical was possibly the
intermediate in the transformation according to that
the benzyl radical fragmentation was faster than the
H-transfer.
3
7
Subsequently, A plausible mechanism is proposed
on the basis of our above experiments and previous
electron-withdrawing groups (NO
2
, CN, CO Me and
2
[
4, 6-9]
related literature
oxidized by K
could generate the trifluoromethylthio radical (·SCF
in Scheme 4. Firstly, AgSCF
3
is
CHO) worked smoothly and gave the desired
II
2
S
2
O
8
to produce Ag SCF
3
(A), which
products with yields ranging from 40% to 65% (3i-3k,
o, and 3p). In addition, aryl 3-aryl-2-propynyl ethers
3
)
3
[14g]
via single electron transfer . Secondly, the
regioselective addition of ·SCF onto the triple bond
bearing different groups were employed to examine
the stereoselectivity of the reaction, giving the mixed
E/Z isomers in 55-67% yields (3r-3w). Particularly,
the structure of tetrasubstituted α,β-unsaturated
aldehyde 3w’ was confirmed by single crystal X-ray
diffraction (see Supporting Information). Finally,
heteroarene substrate 1x could give the desired
product 3x with 54% yield. Although the yields were
moderate, no identifiable byproducts were observed.
3
of substrate 1w gives vinyl radical intermediate B.
Next, spiro-intermediate C is formed with the
intramolecular radical ipso-cyclization of B, followed
by radical 1,4-aryl migration of C to gain
intermediate D. Ultimately, the desired products 3w
and 3w’ are obtained via hydrogen atom abstraction
(
HAT) of radical intermediate species D.
Scheme 4. Proposed reaction mechanism.
Scheme 3. Control experiments for mechanistic insights.
In summary, we have developed a unprecedented
one-pot reaction of aryl 3-aryl-2-propynyl ethers that
involves the trifluoromethylthiolation of alkynes,
radical 1,4-aryl migration from oxygen to carbon, and
formation of a carbonyl group. And during the
substrate expansion, a series of 3, 3-diaryl-2-
(
(trifluoromethyl)thio)acrylaldehyde derivatives have
been gained in moderate to good yield under mild
reaction conditions, which may show vast potential in
radical chemistry and synthesis of tetrasubstituted
α,β-unsaturated aldehydes.
Finally, to gain insight into the reaction mechanism,
additional mechanistic studies have been conducted.
First of all, the reaction was completely suppressed
when 2.0 equiv of 2,2,6,6,-tetramethylpiperidinooxy
(
TEMPO) as free-radical scavenger was added to
Experimental Section
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201700534
General Procedure for the synthesis of 3
7
763; Angew. Chem. Int. Ed. 2014, 53, 7629-7633; d)
W. Kong, E. Merino, C. Nevado, Angew. Chem. Int. Ed.
1
(0.2 mmol), AgSCF
3 2 2 8
(0.3 mmol), K S O (3.0 equiv),
2
014, 53, 5078-5082; Angew. Chem. 2014, 126, 5178-
K
3
PO (2.0 equiv) were added to an over-dried tube. The
4
5
182; e) W. Kong, M. Casimiro, E. b. Merino, C.
tube was evacuated and backfilled with argon (repeated
three times). And then DMSO (2 mL) was added via
syringe. The resulting mixture was stirred at 80 °C for 8 h.
After cooling to room temperature, the mixture was
extracted with ethyl ether (3 × 10 mL), washed with a
saturated aqueous brine solution, dried over anhydrous
Nevado, J. Am. Chem. Soc. 2013, 135, 14480-14483; f)
W. Kong, M. Casimiro, N. Fuentes, E. Merino, C.
Nevado, Angew. Chem. Int. Ed. 2013, 52, 13086-13090;
Angew. Chem. 2013, 125, 13324-13328; g) J.
Sandoval-Lira, J. M. Hernández-Pérez, F. Sartillo-
Piscil, Tetrahedron Lett. 2012, 53, 6689-6693; h) M.
Pudlo, I. Allart-Simon, B. Tinant, S. Gerard, J. Sapi,
Chem. Commun. 2012, 48, 2442-2444; i) V. Rey, A. B.
Pierini, A. B. Peñéñory, J. Org. Chem. 2009, 74, 1223-
2 4
Na SO , and evaporated under reduced pressure. The
residue was further purified by chromatography on silica
gel (petroleum ether/ethyl acetate: 20:1) to afford product
3
.
Acknowledgements
1
230; j) J. Robertson, M. J. Palframan, S. A. Shea, K.
Tchabanenko, W. P. Unsworth, C. Winters,
Tetrahedron 2008, 64, 11896-11907; k) M. J.
Palframan, K. Tchabanenko, J. Robertson, Tetrahedron
Lett. 2006, 47, 8423-8425; l) A. Gheorghe, B. Quiclet-
Sire, X. Vila, S. Z. Zard, Org. Lett. 2005, 7, 1653-1656;
m) K. Wakabayashi, H. Yorimitsu, H. Shinokubo, K.
Oshima, Org. Lett. 2000, 2, 1899-1901; n) W. R.
Bowman, E. Mann, J. Parr, J. Chem. Soc., Perkin Trans.
We are grateful to the National Science Foundation
(NSF21472074) for financial support.
References
[
[
1] a) Z.-M. Chen, X.-M. Zhang, Y.-Q. Tu, Chem. Soc.
Rev. 2015, 44, 5220-5245; b) A. J. Clark, S. R. Coles,
A. Collis, D. R. Fullaway, N. P. Murphy, P. Wilson,
Tetrahedron Lett. 2009, 50, 6311-6314; c) A. Gheorghe,
B. Quiclet-Sire, X. Vila, S. Z. Zard, Org. Lett. 2005, 7,
1
. 2000, 2991-2999; o) E. Lee, H. S. Whang, C. K.
Chung, Tetrahedron Lett. 1995, 36, 913-914.
[5] a) B. Schulte, R. Fröhlich, A. Studer, Tetrahedron 2008,
64, 11852-11859; b) M. Bossart, R. Fässler, J.
Schoenberger, A. Studer, Eur. J. Org. Chem. 2002,
1
2
653-1656; d) A. Studer, M. Bossart, Tetrahedron
001, 57, 9649-9667.
2
002, 2742-2757; c) R. Leardini, H. McNab, M.
Minozzi, D. Nanni, J. Chem. Soc., Perkin Trans. 1.
001, 1072-1078; d) A. Studer, M. Bossart, T. Vasella,
2] a) J. Zhao, H. Fang, R. Song, J. Zhou, J. Han, Y. Pan,
Chem. Commun. 2015, 51, 599-602; b) R.-J. Song, Y.-
Q. Tu, D.-Y. Zhu, F.-M. Zhang, S.-H. Wang, Chem.
Commun. 2015, 51, 749-752; c) Y. Li, B. Liu, H.-B. Li,
Q. Wang, J.-H. Li, Chem. Commun. 2015, 51, 1024-
2
Org. Lett. 2000, 2, 985-988; e) D. L. J. Clive, S. Kang,
Tetrahedron Lett. 2000, 41, 1315-1319; f) S. Amrein,
M. Bossart, T. Vasella, A. Studer, J. Org. Chem. 2000,
1
026; d) X. Mi, C. Wang, M. Huang, Y. Wu, Y. Wu,
6
5, 4281-4288; g) A. Studer, M. Bossart, Chem.
Org. Biomol. Chem. 2014, 12, 8394-8397; e) X.-Q.
Chu, Y. Zi, H. Meng, X.-P. Xu, S.-J. Ji, Chem.
Commun. 2014, 50, 7642-7645; f) X. Liu, F. Xiong, X.
Huang, L. Xu, P. Li, X. Wu, Angew. Chem. 2013, 125,
Commun. 1998, 2127-2128; h) G. Calestani, R.
Leardini, H. McNab, D. Nanni, G. Zanardi, J. Chem.
Soc., Perkin Trans. 1. 1998, 1813-1824; i) B. Alcaide,
A. Rodríguez-Vicente, Tetrahedron Lett. 1998, 39,
7
6
100-7104; Angew. Chem. Int. Ed. 2013, 52, 6962-
966; g) Z.-M. Chen, W. Bai, S.-H. Wang, B.-M. Yang,
6
589-6592.
Y.-Q. Tu, F.-M. Zhang, Angew. Chem. 2013, 125,
[
[
6] a) A. J. Clark, D. R. Fullaway, N. P. Murphy, H.
Parekh, Synlett 2010, 2010, 610-614; b) A. Gheorghe,
B. Quiclet-Sire, X. Vila, S. Z. Zard, Tetrahedron 2007,
63, 7187-7212.
9
9
963-9967; Angew. Chem. Int. Ed. 2013, 52, 9781-
785; h) M. Bietti, A. Calcagni, D. O. Cicero, R.
Martella, M. Salamone, Tetrahedron Lett. 2010, 51,
129-4131; i) B. Quiclet-Sire, G. Revol, S. Z. Zard,
4
7] a) D. Crich, J.-T. Hwang, J. Org. Chem. 1998, 63,
Org. Lett. 2009, 11, 2832-2835; j) M. Bietti, S.
Fiorentini, I. P. Pato, M. Salamone, J. Org. Chem. 2006,
2
765-2770; b) A. M. Rosa, A. M. Lobo, P. S. Branco, P.
Sundaresan, Tetrahedron 1997, 53, 285-298; c) L. Eun,
L. Chulbom, S. T. Jin, S. W. Ho, S. L. Kap,
Tetrahedron Lett. 1993, 34, 2343-2346; d) M. D. Bachi,
E. Bosch, D. Denenmark, D. Girsh, J. Org. Chem. 1992,
57, 6803-6810; e) W. H. Starnes, J. Am. Chem. Soc.
1963, 85, 3708-3709; f) J. W. Wilt, D. D. Oathoudt, J.
Am. Chem. Soc. 1958, 23, 218-224.
7
2
1, 3167-3175; k) L. Grossi, S. Strazzari, J. Org. Chem.
000, 65, 2748-2754.
[
[
3] a) Y.-R. Chen, W.-L. Duan, J. Am. Chem. Soc. 2013,
35, 16754-16757; b) E. Bacqué, M. El Qacemi, S. Z.
1
Zard, Org. Lett. 2005, 7, 3817-3820.
4] a) W. Kong, N. Fuentes, A. García-Domínguez, E.
Merino, C. Nevado, Angew. Chem. Int. Ed. 2015, 54,
[
8] a) C. Pan, H. Zhang, C. Zhu, Tetrahedron Lett. 2016,
2
487-2491; Angew. Chem. 2015, 127, 2517-2521; b) W.
5
7, 595-598; b) C. Pan, Y. Chen, S. Song, L. Li, J.-T.
Thaharn, D. Soorukram, C. Kuhakarn, P. Tuchinda, V.
Reutrakul, M. Pohmakotr, Angew. Chem. 2014, 126,
Yu, J. Org. Chem. 2016, 81, 12065-12069; c) S. Ni, L.
Zhang, W. Zhang, H. Mei, J. Han, Y. Pan, J. Org.
Chem. 2016, 81, 9470-9475; d) T. Miao, D. Xia, Y. Li,
P. Li, L. Wang, Chem. Commun. 2016, 52, 3175-3178;
e) D.-L. Kong, L. Cheng, H.-R. Wu, Y.-X. Li, D. Wang,
L. Liu, Org. Biomol. Chem. 2016, 14, 2210-2217; f) S.
2
2
244-2247; Angew. Chem. Int. Ed. 2014, 53, 2212-
215; c) P. Gao, Y.-W. Shen, R. Fang, X.-H. Hao, Z.-H.
Qiu, F. Yang, X.-B. Yan, Q. Wang, X.-J. Gong, X.-Y.
Liu, Y.-M. Liang, Angew. Chem. 2014, 126, 7759-
4
This article is protected by copyright. All rights reserved.

Advanced Synthesis & Catalysis
10.1002/adsc.201700534
Ni, Y. Zhang, C. Xie, H. Mei, J. Han, Y. Pan, Org. Lett.
015, 17, 5524-5527.
Chem. Int. Ed. 2015, 54, 4065-4069; e) N. Fuentes, W.
Kong, L. Fernández-Sánchez, E. Merino, C. Nevado, J.
Am. Chem. Soc. 2015, 137, 964-973; f) M. Hu, J. Rong,
W. Miao, C. Ni, Y. Han, J. Hu, Org. Lett. 2014, 16,
2
[
9] a) T. Koike, M. Akita, Acc. Chem. Res. 2016, 49, 1937-
1
4
945; b) M. Gao, B. Xu, Org. Lett. 2016, 18, 4746-
749; c) A. Ferry, T. Billard, B. R. Langlois, E. Bacqué,
2
030-2033.
Angew. Chem. 2009, 121, 8703-8707; Angew. Chem.
Int. Ed. 2009, 48, 8551-8555; d) H. Prokopcová, J.
Ramírez, E. Fernández, C. O. Kappe, Tetrahedron Lett.
2
008, 49, 4831-4835; e) P. Conte, B. Panunzi, M.
Tingoli, Tetrahedron Lett. 2006, 47, 273-276; f) C.
Zhou, R. C. Larock, J. Org. Chem. 2005, 70, 3765-
3
1
3
777; g) D. J. Burton, V. Jairaj, J. Flu. Chem. 2005,
26, 797-801; h) D. Dolenc, B. ket, Synlett, 1995, 1995,
27-328; i) C. Saluzzo, G. Alvernhe, D. Anker, G.
Haufe, Tetrahedron Lett. 1990, 31, 2127-2130.
[
[
[
10] a) F. Yin, X.-S. Wang, Org. Lett. 2014, 16, 1128-
1
131; b) S. Purser, P. R. Moore, S. Swallow, V.
Gouverneur, Chem. Soc. Rev. 2008, 37, 320-330; c) D.
O'Hagan, H. S. Rzepa, Chem. Commun. 1997, 645-652.
11] a) X.-H. Xu, K. Matsuzaki, N. Shibata, Chem. Rev.
2
015, 115, 731-764; b) A. Tlili, T. Billard, Angew.
Chem. 2013, 125, 6952-6954; Angew. Chem. Int. Ed.
013, 52, 6818-6819.
2
12] a) L. Jiang, J. Qian, W. Yi, G. Lu, C. Cai, W. Zhang,
Angew. Chem. 2015, 127, 15178-15182; Angew. Chem.
Int. Ed. 2015, 54, 14965-14969; b) J. Wang, M.
Sánchez-Roselló, J. L. Aceña, C. del Pozo, A. E.
Sorochinsky, S. Fustero, V. A. Soloshonok, H. Liu,
Chem. Rev. 2014, 114, 2432-2506.
[
13] a) B. Manteau, S. Pazenok, J.-P. Vors, F. R. Leroux, J.
Flu. Chem. 2010, 131, 140-158; b) F. Leroux, P.
Jeschke, M. Schlosser, Chem. Rev. 2005, 105, 827-856;
c) C. Hansch, A. Leo, R. W. Taft, Chem. Rev. 1991, 91,
1
65-195.
[
14] a) K. Liu, Q. Jin, S. Chen, P. N. Liu, RSC Adv., 2017,
7
, 1546-1552; b) M.-T. Chen, X.-Y. Tang, M. Shi, Org.
Chem. Front. 2017, 4, 86-90; c) W. Wu, W. Dai, X. Ji,
S. Cao, Org. Lett. 2016, 18, 2918-2921; d) T. Liu, G.
Qiu, Q. Ding, J. Wu, Tetrahedron 2016, 72, 1472-1476;
e) Y.-K. Song, P.-C. Qian, F. Chen, C.-L. Deng, X.-G.
Zhang, Tetrahedron, 2016, 72, 7589-7593; f) Y.-F. Qiu,
X.-R. Song, M. Li, X.-Y. Zhu, A.-Q. Wang, F. Yang,
Y.-P. Han, H.-R. Zhang, D.-P. Jin, Y.-X. Li, Y.-M.
Liang, Org. Lett. 2016, 18, 1514-1517; g) Y.-F. Zeng,
D.-H. Tan, Y. Chen, W.-X. Lv, X.-G. Liu, Q. Li, H.
Wang, Org. Chem. Front. 2015, 2, 1511-1515; h) H.
Wu, Z. Xiao, J. Wu, Y. Guo, J.-C. Xiao, C. Liu, Q.-Y.
Chen, Angew. Chem. 2015, 127, 4142-4146; Angew.
Chem. Int. Ed. 2015, 54, 4070-4074; i) F. Yin, X.-S.
Wang, Org. Lett. 2014, 16, 1128-1131.
[
15] a) D.-P. Jin, P. Gao, D.-Q. Chen, S. Chen, J. Wang,
X.-Y. Liu, Y.-M. Liang, Org. Lett. 2016, 18, 3486-
3
489; b) H. Wu, Z. Xiao, J. Wu, Y. Guo, J.-C. Xiao, C.
Liu, Q.-Y. Chen, Angew. Chem. Int. Ed. 2015, 54,
070-4074; Angew. Chem. 2015, 127, 4142-4146; c) Y.-
4
F. Qiu, X.-Y. Zhu, Y.-X. Li, Y.-T. He, F. Yang, J. Wang, H.-L.
Hua, L. Zheng, L.-C. Wang, X.-Y. Liu, Y.-M. Liang, Organic
Letters 2015, 17, 3694-3697; d) S. Guo, X. Zhang, P.
Tang, Angew. Chem. 2015, 127, 4137-4141; Angew.
5
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