Electrochemical Alkynyl/Alkenyl Migration for the Radical Difunctionalization of Alkenes

Article abstract of DOI:10.1002/chem.201804157

An efficient electrochemical 1,2-sulfonylation/alkynylation of alkenes via radical 1,4-alkynyl migration of alkynyl-substituted tertiary alcohols is described, which used sodium sulfinates as sulfonyl sources affording the corresponding α-sulfonyl-β-alkynylated products in moderate to excellent yields. This electrochemical reaction proceeds smoothly without the use of any metal catalyst, additive and oxidant and thus represents a new and eco-friendly strategy for the difunctionalization of unactive olefins, and also the first example of the electrochemical distal radical migration reaction.

Full text of DOI:10.1002/chem.201804157

A Journal of
Accepted Article
Title: Electrochemical Alkynyl/Alkenyl Migration for the Radical
Difunctionalization of Alkenes
Authors: Jianlin Han, Yongyuan Gao, Haibo Mei, and Yi Pan
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201804157
Link to VoR: http://dx.doi.org/10.1002/chem.201804157
Supported by

Chemistry - A European Journal
10.1002/chem.201804157
COMMUNICATION
Electrochemical Alkynyl/Alkenyl Migration for the Radical
Difunctionalization of Alkenes
[
a]
[a]
[a,b]
[a,b]
Yongyuan Gao, Haibo Mei, Jianlin Han,*
and Yi Pan*
Dedication ((optional))
[
16]
Abstract: An efficient electrochemical 1,2-sulfonylation/alkynylation
of alkenes via radical 1,4-alkynyl migration of alkynyl-substituted
tertiary alcohols has been described, which used sodium sulfinates
as sulfonyl sources affording the corresponding α-sulfonyl-β-
alkynylated products in moderate to excellent yields. This
electrochemical reaction proceeded smoothly without the use of any
metal-catalyst, additive and oxidant, which represents a new and
eco-friendly strategy for the difunctionalization of unactive olefins,
and also the first example of the electrochemical distal radical
migration reaction.
reaction
have been achieved through electrochemical
oxidation. Since electrochemistry represents one of the most
intimate ways of interacting with molecules, the development of
new electrochemical organic transformations becomes very
urgent. Inspired by the above elegant works,
that whether the distal radical migration transformation can be
achieved under electrochemical oxidative conditions.
[
12-16]
we envisioned
Herein, we provide concrete support for this hypothesis. The
first example of the electrochemical radical migration
transformation is described (Scheme 1), which proceeds through
tandem radical sulfonylation and alkynyl/alkenyl migration. This
reaction used sodium benzene sulfinate as the sulfonyl
Distal radical migration strategy represents a particular type of
organic transformations in the field of organic synthesis due to
its potential application in the construction of complex
[17]
source, and was carried out under mild conditions, without the
use of any catalyst or oxidant, to realize α-sulfonyl-β-
alkynylation/alkenylation of alkenes. This protocol represents a
new example of mild and green radical migration reaction and
may provide new opportunities in the fields of electrochemical
organic synthesis and alkene difunctionalization.
[
1]
compounds in an efficient way. Subsequently, the need for
advanced approaches and new reagents is at an all-time high.
Specifically, the intramolecular radical functional group migration
reaction proceeds through the formation of a cyclic intermediate
or transition state, which provides an effective strategy for the
[
2,3]
O
difunctionalization of C-C double bond in a proper position.
In
O
HO
O
C (+) C (-), 2 mA/cm2
CH CN/H O (1:1), rt
S
O
the past few years, the elegant works on the vicinal
+
R
S
[
4]
R
ONa
Ar
3
2
difunctionalization of alkenyl moiety via intramolecular formyl,
undevided cell
[
5]
[6]
[7]
[8]
Ar
aryl, cyano, and heteroaryl migration has been developed.
catalyst-free, oxidant-free,
additive-free, mild conditions
unknown: electrochemical radical migration
Very recently, the Zhu group reported a photoredox-catalyzed
radical trifluoromethylative alkynylation of unactivated alkenes
[
9]
via distal alkynyl migration. The Studer group has developed a
difunctionalization of alkynyl-substituted tertiary alcohol via 1,4-
Scheme 1. Electrochemical radical migration.
[
10]
alkenyl migration.
These radical migration reactions mainly
focused on the light initiation and metal catalysis, which usually
need transition-metal, photocatalyst or additives.
Initially, the electrochemical oxidation reaction was carried out
with 3-methyl-1-phenylhept-6-en-1-yn-3-ol 1a and para-
methylbenzenesulfinate 2a as model substrates with the use of
In recent years, electrochemical synthesis has attracted
widespread attention in the field of organic synthesis, as
electroorganic transformation is considered as one of the green
and sustainable synthetic strategies. Electrochemical reaction
uses electron as an oxidant, and thus avoids the use of metal-
platinum-plate anode and cathode, and NH
reaction can occur at a constant current density of 2 mA/cm in
1,4-dioxane/H O (1:1) at room temperature for 12 h, affording
the desired product 3a in 36% yield (entry 1, Table 1).
Subsequently, other additives, such as NH Br and TBAB, were
4
I as an additive. The
2
2
[
11]
catalysts and a large number of oxidants. In the past years,
several types of reactions, such as dehydrogenative cross-
4
screened in this electrochemical system, and no obvious
improvement on the chemical yield was obtained (entries 2−3).
To our surprise, the reaction also proceeded smoothly without
the addition of any additives, and the same level of yield was
found (46% yield, entry 4). Next, several types of electrodes,
including platinum-plate, nickel-plate, iron-plate and graphite
plate were investigated for this reaction (entries 5−8). We found
that when the graphite electrode was used for both the cathode
and the anode, the reaction proceeded very well, and the
corresponding product was obtained in 66% yield (entry 8). Then,
a series of regular solvents were tested to further improve the
reaction efficiency (entries 9−14). We found that the mixture of
[
12]
[13]
coupling,
difunctionalization
difunctionalization of alkenes,
dehydrogenative homo-coupling,
electrochemical
electrochemical
[
14]
of
alkynes,
[
15]
and cascade cyclization
[
a]
b]
Y. Y. Gao, Dr. H. B. Mei, Dr. J. L. Han, Dr. Y. Pan
School of Chemistry and Chemical Engineering, State Key
Laboratory of Coordination Chemistry
Nanjing University, Nanjing, 210093, China
E-mail: hanjl@nju.edu.cn
[
Jiangsu Key Laboratory of Advanced Organic Materials
Nanjing University, Nanjing, 210093, China
CH
further increased to 78% (entry 10). In sharp contrast, when
CH CN was used as the sole solvent, only 12% yield of the
corresponding product was obtained (entry 14). Finally, the
3 2
CN and H O (1:1) was the best choice, and the yield was
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
3
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201804157
COMMUNICATION
variation on the current density and reaction time was not
meta-Me, meta-Cl, ortho-OMe substituted phenyl ring were used
successful, and no improvement on the reaction yield was found. in the reaction, good chemical yields were obtained in 76%, 82%,
[
a]
Table 1. Optimization of reaction conditions.
and 85%, respectively (3i, 3j and 3k). Moreover, the reaction of
a 2-thienyl reactant with para-methylbenzenesulfinate 2a also
proceeded smoothly and gave the product in 61% yield (3m). It
is worth noting the reaction did not proceed when the cyclohexyl
alkynyl-substituted tertiary alcohol 1n was used as the substrate
mainly because that the radical adjacent to the aliphatic
cyclohexyl group is not stable. Fortunately, 1,6-diphenyl-4-
(tosylmethyl)hex-5-yn-1-one was also a suitable substrate and
afforded the desired product 3o in 84% yield. The substrate 1p
bearing substituted C-C double bond was suitable, however only
Entry
anode/
cathode
additive
(equiv)
electrolyte
Yield
[e]
(%)
36
41
43
46
48
43
52
66
72
78
21
62
68
12
74
32
75
1
2
3
4
5
6
7
8
9
Pt/Pt
Pt/Pt
Pt/Pt
Pt/Pt
C/Pt
C/Fe
C/Ni
C/C
C/C
C/C
C/C
C/C
C/C
C/C
C/C
C/C
C/C
NH
4
4
I (0.5)
1,4-dioxane/H
1,4-dioxane/H
1,4-dioxane/H
1,4-dioxane/H
1,4-dioxane/H
1,4-dioxane/H
1,4-dioxane/H
1,4-dioxane/H
2
2
2
2
2
2
2
2
O (1;1)
O (1;1)
O (1;1)
O (1;1)
O (1;1)
O (1;1)
O (1;1)
O (1;1)
47% of chemical yield was obtained mainly due to steric
NH
Br (0.5)
hinderance.
TBAB (0.5)
O
-
-
-
-
-
-
-
-
-
-
-
-
-
-
HO
O
S
O
S
C (+) C (-) : 2 mA/cm2
+
ONa
O
CH3CN/H2O (1:1), rt, 12 h
CCE, undivided cell
R
R
1
a-1p
2a
3a-3p
O
O
O
O
O
S
O
S
O
S
O
S
O
O
O
O
acetone / H
CH CN/ H O (1:1)
THF/ H O (1:1)
2
O (1:1)
10
11
12
13
14
15
16
17
3
2
F
Cl
3
a, 78% yield
3b, 72% yield
3c, 83% yield
3d, 77% yield
O
O
O
O
O
O
O
O
2
O
S
O
O
S
O
S
O
O
S
O
CH
CH
CH
CH
CH
CH
3
3
3
3
3
3
OH/ H
2
O (1:1)
O
CN/ H
2
O (1:2)
CN
CN
CF3
Br
3
h, 84% yield
3
e, 75% yield
3f, 68% yield
3g, 76% yield
[
[
[
b]
c]
d]
O
O
CN/ H
CN/ H
CN/ H
2
2
2
O (1:1)
O (1:1)
O (1:1)
O
S
O
O
S
O
S
O
O
S
O
O
O
Cl
Ph
3
i, 76% yield
3j, 82% yield
3k, 85% yield
3l, 41% yield
[
a] Reaction conditions: graphite plate anode (1 cm×1 cm×0.3 cm), graphite
plate cathode (1 cm×1 cm×0.3 cm), 1a (0.3 mmol), 2a (0.9 mmol), additive
0.5 equiv) and solvent (6 mL) were carried out in a undivided cell under an
argon atmosphere conducted at a constant current 2 mA/cm for 12 h (3.0 F).
b] 4 mA/cm . [c] 1 mA/cm . [d] 18 h. [e] Isolated yield.
O
O
O
S
O
S
O
S
O
S
(
Ph
2
O
O
O
O
2
2
[
S
With the optimal conditions in hand, we next examined the
3
m, 61% yield
3n, trace
3o, 84% yield
3p, 47% yield
substrate scope of various alkynyl-substituted tertiary alcohols
by reacting with para-methylbenzenesulfinate 2a (Scheme 2). As
presented in Scheme 2, this new electrochemical radical 1,4-
alkynyl migration reaction was found to be of a considerable
degree of structural generality. Introduction of substituents at the
para-position of the aromatic ring did not influence the reaction
outcome. The substrates bearing the electron-donating groups
Scheme 2. Substrate scope of tertiary alcohols. (Reaction conditions: 1 (0.3
mmol), 2a (0.9 mmol), CH CN/H O (6 mL), in an undivided cell under an argon
atmosphere at a constant current (2 mA/cm ) for 12 h (3.0 F). Isolated yields.)
3
2
2
Then, the reaction scope with regard to the sodium sulfinates
was explored by reacting with 3-methyl-1-phenylhept-6-en-1-yn-
3-ol 1a. As shown in Scheme 3, most of the examined aryl
sulfinates were suitable substrates, affording the desired product
(
(
tert-butyl, methyl, 3b,3h), and electron-withdrawing groups
fluorine, chlorine, bromine, trifluoromethyl, and cyano, 3c-3g)
worked very well in the reaction, affording the products in good
yields (68-84%). In the case of no substituent on the phenyl ring,
also good chemical yield was obtained (3a, 78%). The position
of the substituent on the aromatic ring showed no effect on the
reaction efficiency. For example, when the substrates containing
in
good
chemical
yields
(55-85%).
For
example,
benzenesulfinate and halogenated benzenesulfinates worked
very well, and the corresponding products, 3q, 3r, 3s, and 3t
were generated in 85%, 78%, 75% and 55% yields, respectively.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201804157
COMMUNICATION
Scheme 4. Reaction of 3-methyl-1-phenylhepta-1,6-dien-3-ol 4 with sulfinates.
It is worth noting that sodium para-nitrophenylsulfinate was not
compliant with the reaction, and no desired product 3u was
obtained, which is mainly because that the existence of strong
electron-withdrawing group makes the sulfonyl radical unstable.
Finally, the alkyl-substituted sodium sulfinates were also found
to be suitable substrates for this electrochemical radical reaction,
and the excellent yields were obtained (86%-92%, 3w-3y).
Especially, in the case of methyl sodium sulfinate, the highest
chemical yield was obtained (3w, 92 % yield).
(
Reaction conditions: 4 (0.3 mmol), 2 (0.9 mmol), CH
undivided cell under an argon atmosphere at a constant current (2 mA/cm ) for
2 h. Isolated yields.)
3 2
CN/H O (6 mL), in an
2
1
The
scalability
of
this
electrochemical
1,2-
sulfonylation/alkynylation of alkene via radical alkynyl migration
was then evaluated by performing 5 mmol scale reaction, which
was conducted using inexpensive graphite plate. The reaction
2
can proceed smoothly under a current density of 4 mA/m for 36
O
hours with a yield of 58% (Scheme 5).
O
HO
O
S
C (+) C (-) : 2 mA/cm2
S
R
O
+
R
ONa
CH3CN/H2O (1:1), rt, 12 h
CCE, undivided cell
1
a
2
3q-3y
O
O
O
O
O
S
O
S
O
S
O
S
O
O
O
O
F
Cl
Br
Scheme 5. Large-scale synthesis of reaction conditions: 1a (5 mmol), 2a (15
3 2
mmol), CH CN/H O (100 mL), graphite plate anode (5 cm×5 cm×0.5 cm),
3
q, 85% yield
3r, 78% yield
O
3s, 75% yield
O
3t, 55% yield
graphite plate cathode (5 cm×5 cm×0.5 cm), in an undivided cell under an
O
O
O
S
O
O
O
S
O
S
O
argon atmosphere at a constant current (4 mA/ cm ) for 36 h (27.0 F). Isolated
2
S
yields.
O
O
NO2
[
18]
We also investigated the follow-up chemistry of this reaction
by using 3a as the starting material (Scheme 6). The cyclization
of 3a in the presence of TfOH afforded the α,β-unsaturated
ketone 6 in 73% isolated yield.
3
u, trace
3v, 63% yield
3w, 92% yield
3x, 87% yield
O
O
S
O
3
y, 86% yield
Scheme 3. Substrate scope of sodium sulfinates (Reaction conditions: 1h (0.3
mmol), 2 (0.9 mmol), CH CN/H O (6 mL), in an undivided cell under an argon
3
2
2
atmosphere at a constant current (2 mA/ cm ) for 12 h (3.0 F). Isolated yields.)
To further extend the scope of the electrochemical radical
migration reaction, we tried to investigate the possibility of the
alkenyl migration in this system. To our delight, When (E)-3-
methyl-1-phenylhepta-1,6-dien-3-ol was used as a substrate to
react with sodium sulfinates, the reaction can also proceed
smoothly via 1,4-migration, which gave the corresponding
products in excellent yields (72-85%, 5a-5c).
Scheme 6. Follow-up chemistry.
Finally, two control experiments were carried out to get insight
into the reaction mechanism. We found that the reaction was
totally inhibited when a radical inhibitor TEMPO (3 equiv) was
added to the system under standard reaction conditions
(
Scheme 7a). When 1,1 diphenylethylene was added into the
reaction under standard conditions, the adduct of (2-tosylethene-
,1-diyl)dibenzene 8 was isolated in yield 62% (Scheme 7b).
1
These results indicate that the sulfonyl radical is involved in this
reaction.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201804157
COMMUNICATION
We gratefully acknowledge the financial support from the
National Natural Science Foundation of China (Nos. 21472082,
21772085 and 21761132021).
Keywords:
electrochemistry
•
radical
migration
•
difunctionalization of alkenes • sulfonylation • green method
[
1]
2]
For selected reviews, see: a) W. Li, W. Xu, J. Xie, S. Yu, C. Zhu, Chem.
Soc. Rev. 2018, 47, 654-667; b) X. Wu, S. Wu, C. Zhu, Tetrahedron
Lett. 2018, 59, 1328-1336.
[
For selected reviews, see: a) Z. Chen, X. Zhang, Y. Tu, Chem. Soc.
Rev. 2015, 44, 5220-5245; b) A. Studer, M. Bossart, Tetrahedron 2001,
Scheme 7. Control experiments.
57, 9649-9667; c) Y. Zeng, C. Ni, J. Hu, Chem. Eur. J. 2016, 22,
3210−3223.
Based on the above experimental results and previous
[3]
For selected examples, see: a) Y. Li, B. Liu, H. B. Li , Q. Wang, J. H. Li,
Chem. Commun. 2015, 51, 1024-1026; b) H. L. Huang, H. Yan, C.
Yang, W. Xia, Chem. Commun. 2015, 51, 4910-4913; c) J. C. Zhao, H.
Fang, R. Song, J. Zhou, J. L. Han, Y. Pan, Chem. Commun. 2015, 51,
[
9,10,15]
reports,
a plausible mechanism for this electrochemical
radical migration reaction was proposed in Scheme 8. First
sodium sulfinate 2 is oxidized at the anode to give the oxygen-
centered radical A. The oxygen-centered radical A resonates to
the more stable sulfonyl radical B. Then, the sulfonyl radical B
adds to the terminal position of the alkene 1 to give the radical C.
Subsequently, 1,5-radical cyclization of C leads to the vinyl
radical D, which further undergoes the regioselective C–C bond
cleavage to generate the radical E. Then, dehydrogenation of E
will produce the ketyl radical intermediate F, which is oxidized at
anode to afford the final product 3. It should be mentioned that
the catalytic cycle may also proceed via the reduction of
intermediate C at cathode to form the anion, which then
undergoes the Michael addition to alkyne, intramolecular
liberation of alkyne, and oxidation to form the final product 3.
599-602; d) L. Zheng, C. Yang, Z. Z. Xu, F. Gao, W. Xia, J. Org. Chem.
2015, 80, 5730–5736; e) W. Thaharn, D. Soorukram, C. Kuhakarn, P.
Tuchinda, V. Reutrakul, M. Pohmakotr, Angew. Chem. Int. Ed. 2014, 53,
212−2215; f) W. Kong, M. Casimiro, E. Merino, C. Nevado, J. Am.
2
Chem. Soc. 2013, 135, 14480−14483; g) W. Kong, E. Merino, C.
Nevado, Angew. Chem. Int. Ed. 2014, 53, 5078−5082.
[
[
4]
5]
Z.-L. Li, X.-H. Li, N. Wang, N.-Y. Yang, X.-Y. Liu, Angew. Chem. Int. Ed.
2016, 55, 15100–15104.
L. Li, Z.-Z. Li, F.-L. Wang, Z. Guo, Y.-F. Cheng, N. Wang, X.-W. Dong,
C. Fang, J. Liu, C. Hou, B. Tan, X.-Y. Liu, Nat. Commun. 2016, 7,
13852.
[
6]
R. Ren, Z. Wu, L. Huan, C. Zhu, Adv. Synth. Catal. 2017, 359, 3052–
3056.
[7]
a) N.-Y. Yang, Z.-L. Li, B. Tan, X.-Y. Liu, Chem. Commun. 2016, 52,
052–9055; b) Z. Wu, D. Wang, Y. Liu, L. Huan, C. Zhu, J. Am. Chem.
9
Soc. 2017, 139, 1388–1391; c) J. Yu, D. Wang, Y. Xu, Z. Wu, C. Zhu,
Adv. Synth. Catal. 2018, 360, 744-750.
OH
O
S
O
S
A
O
S
R
1
HO
R
O
R
O
O
O
[
8]
a) L. Li, Q. S. Gu, N. Wang, P. Song, Z. L. Li , X. H. Li , F. L. Wang, X.
Y. Liu, Chem. Commun. 2017, 53, 4038-4041; b) P. Gao, Y. W. Shen,
R. Fang, X. H. Hao, Z. H. Qiu, F. Yong, X. B. Yan, Q. wang, X. J. Gong,
X. Y. Liu, Y. M. Liang, Angew. Chem. Int. Ed. 2014, 53, 7629-7633.
Y. Xu, Z. Wu, J. Jiang, Z. Ke, C. Zhu, Angew. Chem. Int. Ed. 2017, 56,
Ar
Ar
S
B
C
R
SET
D
O
O
R
S
2
ONa
O
O
S
O
OH
O
[9]
R
S
O
R
1/2 H2
4545–4548.
F
Ar
E
[10] a) X. Tang, A. Studer, Angew. Chem. Int. Ed. 2018, 57, 814-817; b) X.
Tang, A. Studer, Chem. Sci. 2017, 8, 6888-6892.
Ar
Anode
O
Cathode
H+
O
S
R
O
[11]
For selected reviews, see: a) J. i. Yoshida, K. Kataoka, R. Horcajada
and A. Nagaki, Chem. Rev. 2008, 108, 2265-2299; b) K. D. Moeller,
Tetrahedron 2000, 56, 9527-9554; c) J. B. Sperry, D. L. Wright, Chem.
Soc. Rev. 2006, 35, 605-621; d) M. Yan, Y. Kawamata, P.S. Baran,
Chem. Rev. 2017, 117, 13230-13319; f) J. i. Yoshida, A. Shimizu, R.
Hayashi, Chem. Rev. 2018, 118, 4702–4730; g) Y. Jiang, K. Xu, C.
Zeng, Chem. Rev. 2018, 118, 4485–4540; h) R. Feng, J. A. Smith, K. D.
Moeller, Acc. Chem. Res. 2017, 50, 2346−2352; i) J. B. Sperry, D. L.
Wright, Chem. Soc. Rev. 2006, 35, 605–621; j) S. Tang, Y. Liu, A. Lei,
Chem 2018, 4, 27-45; k) M. Yan, Y. Kawamata, P. S. Baran, Angew.
Chem. Int. Ed. 2018, 57, 4149–4155; l) A. Wiebe, T. Gieshoff, S. Möhle,
E. Rodrigo, M. Zirbes, S. R. Waldvogel, Angew. Chem. Int. Ed. 2018,
3
Ar
Scheme 8. Proposed mechanism.
In summary, a novel electrochemical radical migration reaction
alkynyl-substituted tertiary alcohols has been developed, which
proceeded through sulfonylation of alkenes and alkynyl/alkenyl
migration. The reaction used sodium sulfinates as sulfonyl
sources, without the use of any metal-catalyst, additive, and
oxidant, affording the corresponding α-sulfonyl-β-alkynylation
product in good yields. The reaction represents a new and green
strategy for the difunctionalization of unactive olefins and also
the first electrochemical distal radical migration reaction.
57, 5594–5619; m) K. D. Moeller, Chem. Rev. 2018, 118, 4817–4833;
[
12]
For selected examples, see: a) X. Gao, P. Wang, L. Zeng, S. Tang, A.
Lei, J. Am. Chem. Soc. 2018, 140, 4195–4199; b) S. Tang, D. Wang, Y.
Liu, L. Zeng, A. Lei, Nature Comm. 2018, 9, 798; c) P. Wang, S. Tang,
P. F. Huang, A. Lei, Angew. Chem. Int. Ed. 2017, 56, 3009-3013; d) C.
Li, Y. Kawamata, H. Nakamura, J. C. Vantourout, Z. Liu, Q. Hou, D.
Bao, J. T. Starr, J. Chen, M. Yan, P. S. Baran, Angew. Chem. Int. Ed.
2
017, 56, 13088; e) Z. J. Wu, H. C. Xu, Angew. Chem. Int. Ed. 2017, 56,
Acknowledgements ((optional))
4
734-4738; f) R. Hayashi, A. Shimizu, Y. Song, Y. Ashikari, T. Nokami,
J. Yoshida, Chem. Eur. J. 2017, 23, 61-64; g) R. Hayashi, A. Shimizu, J.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201804157
COMMUNICATION
Yoshida, J. Am. Chem. Soc. 2016', 138, 8400-8403; h) T. Morofuji, A.
Shimizu, J. Yoshida, J. Am. Chem. Soc. 2015, 137, 9816–9819; i) T.
Morofuji, A. Shimizu, J. Yoshida, J. Am. Chem. Soc. 2014, 136, 4496–
[15] a) G. S. Sauer, S. Lin, ACS Catal. 2018, 8, 5175-5187; b) K. Ye, G.
Pombar, N. Fu, G. S. Sauer, I. Keresztes, S. Lin, J. Am. Chem. Soc.
2018, 140, 2438–2441; c) N. Fu, G. S. Sauer, S. Lin, J. Am. Chem.
Soc. 2017, 139, 15548-15553; d) N. Fu, G. S. Sauer, A. Saha, A. Loo,
S. Lin, Science 2017, 357, 575-579; e) P. Xiong, H. H. Xu, H. C. Xu, J.
Am. Chem. Soc. 2017, 139, 2956–2959; f) Y. Ashikari, A. Shimizu, T.
Nokami, J. Yoshida, J. Am. Chem. Soc. 2013, 135, 16070–16073.
4499; j) T. Morofuji, A. Shimizu, J. Yoshida, J. Am. Chem. Soc. 2013,
135, 5000–5003; k) S. Lips, B. A. Frontana-Uribe, M. Dörr, D.
Schollmeyer, R. Franke, S. R. Waldvogel, Chem. Eur. J. 2018, 24,
057–6061; l) A. Wiebe, S. Lips, D. Schollmeyer, R. Franke, S. R.
6
Waldvogel, Angew. Chem. Int. Ed. 2017, 56, 14727–14731; m) T.
Gieshoff, A. Kehl, D. Schollmeyer, K. D. Moeller, S. R. Waldvogel,
Chem. Commun. 2017, 53, 2974–2977; n) J. Tian, K. Maurer, E. Tesfu,
K. D. Moeller, J. Am. Chem. Soc. 2005, 127, 1392–1393.
[16]
a) K. Liu, S. Tang, P. Huang, A. Lei, Nature Commun. 2017, 8, 775; b)
P. Wang, S. Tang, A. Lei, Green Chem. 2017,19, 2092-2095; c) Z. J.
Wu, S. R. Li, H. Long, H. C. Xu, Chem. Commun. 2018, 54, 4601-4604;
d) Z. W. Hou, Z. Y. Mao, Y. Y. Melcamu, X. Lu, H. C. Xu, Angew. Chem.
Int. Ed. 2018, 57, 1636; f) H. B. Zhao, Z. J. Liu, J. Song, H. C. Xu,
Angew. Chem. Int. Ed. 2017, 56, 12732; g) S. Zhang, L. Li, H. Wang, Q.
Li, W. Liu, K. Xu, C. Zeng, Org. Lett. 2018, 20, 252–255; h) Z. W. Hou,
Z. Y. Mao, J. Song, H. C. Xu, ACS Catal. 2017, 7, 5810-5813; i) X. Y.
Qian, S. Q. Li, J. Song, H. C. Xu, ACS Catal. 2017, 7, 2730–2734; j) L.
J. Wesenberg, S. Herold, A. Shimizu, J. Yoshida, S. R. Waldvogel,
Chem. Eur. J. 2017, 23, 12096–12099; k) A. Redden, K. D. Moeller,
Org. Lett. 2011, 13, 1678–1681; l) F. Tang, K. D. Moeller, J. Am. Chem.
Soc. 2007, 129, 12414–12415.
[
13] a) A. Kehl, T. Gieshoff, D. Schollmeyer, S. R. Waldvogel, Chem. - Eur. J.
2018, 24, 590–593; b) S. B. Beil, T. Müller, S. B. Sillart, P. Franzmann,
A. Bomm, M. Holtkamp, U. Karst, W. Schade, S. R. Waldvogel, Angew.
Chem. Int. Ed. 2018, 57, 2450–2454; c) T. Yamamoto, B. Riehl, K.
Naba, K. Nakahara, A. Wiebe, T. Saitoh, S. R. Waldvogel, Y. Einaga,
Chem. Commun. 2018, 54, 2771–2773; d) T. Gieshoff, A. Kehl, D.
Schollmeyer, K. Moeller, S. R. Waldvogel, J. Am. Chem. Soc. 2017,
1
39, 12317–12324; e) L. Schulz, M. Enders, B. Elsler, D. Schollmeyer,
K. M. Dyballa, R. Franke, S. R. Waldvogel, Angew. Chem. Int. Ed. 2017,
6, 4877–4881; f) T. Gieshoff, D. Schollmeyer, S. R. Waldvogel,
5
[17]
[18]
a) X. Zhao, E. Dimitrijevic, V. M. Dong, J. Am. Chem. Soc. 2009, 131,
3466; b) O. Saidi, J. Marafie, A. E. W. Ledger, P. M. Liu, M. F. Mahon,
G. Kociok-Kohn, J. Am. Chem. Soc. 2011, 133, 19298; c) F. Xiao, S.
Chen, Y. Chen, H. Huang, G. Deng, Chem. Commun. 2015, 51, 652; d)
P. Qian, Y. Deng, H. Mei, J. Han, J. Zhou, Y. Pan, Org. Lett. 2017, 19,
4798–4801.
Angew. Chem. Int. Ed. 2016, 55, 9437–9440; g) A. Wiebe, D.
Schollmeyer, K. M. Dyballa, R. Franke, S. R. Waldvogel, Angew. Chem.
Int. Ed. 2016, 55, 11801–11805; h) C. Gütz, M. Selt, M. Bänziger, C.
Bucher, C. Römelt, N. Hecken, F. Gallou, T. R. Galvão, S. R.
Waldvogel, Chem. - Eur. J. 2015, 21, 13878–13882; i) Y. Gao, Y. Wang,
J. Zhou, H. Mei, J. Han, Green Chem. 2018, 20, 583-587.
T. Jin, F. Yang, C. Liu, Y. Yamamoto, Chem. Commun. 2009, 3533–
3535.
[
14]
a) F. Xu, Y. J. Li, C. Huang, H. C. Xu, ACS Catal. 2018, 8, 3820–3824;
b) P. Xiong, H. H. Xu, J. Song, H. C. Xu, J. Am. Chem. Soc. 2018, 140,
2460–2464; c) Z. W. Hou, Z. Y. Mao, H. B. Zhao, Y. Y. Melcamu, X. Lu,
J. Song, H. C. Xu, Angew. Chem. Int. Ed. 2016, 55, 9168-9172;
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201804157
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
COMMUNICATION
Yongyuan Gao, Haibo Mei, Jianlin Han,*
Yi Pan*
Page No. – Page No.
Electrochemical Alkynyl/Alkenyl
Migration for the Radical
Difunctionalization of Alkenes
The first example of electrochemical alkynyl migration has been described, which
used sodium sulfinates as sulfonyl sources affording the corresponding α-sulfonyl-
β-alkynylation product in good yields. The reaction does not need any catalyst,
additive, or oxidant, which represents
difunctionalization of unactive olefins.
a new and green strategy for the
This article is protected by copyright. All rights reserved.