Cobalt(II)-catalyzed bis-isocyanide insertion reactions with sulfonyl azides via nitrene radicals: Chemoselective synthesis of sulfonylamidyl amide and 3-imine indole derivatives

Article abstract of DOI:10.1039/c7cc06531k

A chemoselective Co(ii)-catalyzed effective synthesis of sulfonylamidyl amide and 3-imine indole derivatives by using isocyanides and sulfonyl azides has been developed. This protocol provides a new, environmentally friendly and simple strategy for the efficient synthesis of the sulfonylamidyl amide and 3-imine indole derivatives with a wide range of substrates in the absence of any oxidants and additives.

Full text of DOI:10.1039/c7cc06531k

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Z. Gu, J. Li, S.
Wang and S. Ji, Chem. Commun., 2017, DOI: 10.1039/C7CC06531K.
This is an Accepted Manuscript, which has been through the
Volume 52 Number
1 4 January 2016 Pages 1–216
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Accepted Manuscripts are published online shortly after
Chemical Communications
www.rsc.org/chemcomm
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
first methanofullerene derivatives of Sc N@D5h-C80
=
3
rsc.li/chemcomm

ChemComm
Page 1 of 5Journal Name
Dynamic Article Links ►
View Article Online
DOI: 10.1039/C7CC06531K
Cite this: DOI: 10.1039/c0xx00000x
www.rsc.org/xxxxxx
ARTICLE TYPE
Cobalt(II)-Catalyzed Bis-isocyanides Insertion Reactions with
Sulfonyl Azides via Nitrene Radical：Chemoselective Synthesis
of The Sulfonylamidyl amide and 3-Imine Indole Derivatives
Zheng-Yang Gu, Jing-Hao Li, Shun-Yi Wang,* and Shun-Jun Ji*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
a) Classical reactions of nitrenes
A chemoselective Co(II)-catalyzed effective synthesis of
R
C
C
sulfonylamidyl amide and 3-imine indole derivatives by using
isocyanides and sulfonyl azides has been developed. This
protocol provides a new, environment-friendly and simple
strategy for the efficient synthesis of the sulfonylamidyl amide
and 3-imine indole derivatives with a wide range of substrates
in the absence of any oxidants and additives.
N
C
C
Aziridination
or
N
N
R
C-H Amination
R
C
R
N
C
H
H
Metals: Cu, Rh, Ru, Mn, Fe, Ag, Co...
Nitrenes, normally regarded as highly reactive species
analogous to like their carbenes cousins, have recently emerged
as useful tools for selective introduction of nitrogen atom in
organic molecules. Practical transition metalꢀcatalyzed nitrene
radical protocols have attracted considerable attention in various
nitrogen transfer reactions such as addition reactions, radical
coupling reactions, as well as CꢀH activation reactions (Scheme
1, a).1 Furthermore, transition metalꢀcoordinated nitrogenꢀ
centered radicals are generally more stable than nitrogenꢀcentered
free radicals, which are highly reactive but poorly discriminating
species. Over the last decade, the ability of transition metal
complexes to catalyze nitrene transfers opened new avenues for
the potential catalytic applications.2 For example, Zhang’s group
have made great contributions in the Co(II)ꢀbased metalloradical
reactions, such as radical CꢀH alkylation,3 radical CꢀH
amination,4 radical olefin cyclopropanation5 and radical
aziridination.6 Moreover, the computational studies of the
Co(III)ꢀnitrene radical species and their application in organic
synthesis also suggested that formation of the metallanitrenes was
the key step in these reactions.7 However, the preꢀprepared metal
complex catalysts are expensive and seldom applied in industrial
processes. Therefore, it is more desirable to develop these
significant but simple and economical transition metalꢀcatalyzed
nitrene transfer reactions.
b) Reaction characteristics of isocyanides
electrophlic
nucleophlic
Nu-, E+
Nu
E
R
N
C
R
N C
R
N C
c) Our previous work: cobalt-catalyzed nitrene radical coupling
R2
R2
N
C
R2
N
R1 SO2N3
+
R2 NC
C
Nu
N
O
S
R1
O
Co
amine or alcohol
CoIII
L
N
N
Nu
L
H
O
S
O
R1
d) This work: new application of cobalt-catalyzed nitrene radical coupling
reaction 2
R2 NC
R2 = aryl
reaction 1
R'
R2
O
R2 NC, H2O
Co
+
HN
N
O
O
R1
O
R1
O
H
S
N
R2 = alkyl
S
N
R2
N
R1 SO2N3
H
N
R2
Low Catalyst Loading
Oxidant Free
yield up to 97%
yield up to 88%
Additive Free Green Solvent
Scheme 1. New cobaltꢀcatalyzed nitrene radical strategy for
organic synthesis.
alcohols (Scheme 1, c).11 In order to further verify this new
cobaltꢀcatalyzed nitrene reaction strategy, herein we describe a
chemoselective Co(II)ꢀcatalyzed effective synthesis of
sulfonylamidyl amide and 3ꢀimine indole derivatives with bisꢀ
isocyanides using sulfonyl azides as nitrene source (Scheme 1, d).
This protocol provides a new, environmentꢀfriendly and simple
strategy to effective synthesis of the sulfonylamidyl amide and 3ꢀ
imine indole derivatives with a wide range of substrates without
any oxidants and additives.
Isocyanides are considered to be important organic synthons,
which can be used as either electrophilic or nucleophilic reagents
to construct various nitrogenꢀcontaining compounds in
multicomponent reactions (Scheme 1, b).8 Recently, isocyanides
have been extensively studied in transition metalꢀcatalyzed
insertion reactions.9 Our group devoted to developing the
insertion reactions of isocyanides,10 and we have reported Co(II)ꢀ
catalyzed synthesis of sulfonyl guanidines or sulfonyl isoureas
via nitrene radical coupling with isonitriles and amines or
Initially, we tried the reaction of sulfonyl azide 1a with
isocyanide 2a catalyzed by 5 mol % CoC2O4 (cobalt oxalate) in
MeCN and H2O (50 uL) at 80 °C for 4h. Gratifyingly, the desired
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 1

ChemComm
Page 2 of 5
View Article Online
DOI: 10.1039/C7CC06531K
Table 2. Synthesis of sulfonylamidyl amide 3a,b
.
product
(Z)ꢀNꢀ(tertꢀbutyl)ꢀ2ꢀ(tertꢀbutylamino)ꢀ2ꢀ
R
O
(tosylimino)acetamide 3aa was observed in 25% LCꢀyield (Table
1, entry 1). Structure of 3aa was confirmed by Xꢀray diffraction
analysis. When the reaction time was further extended to 8 h, the
starting material 1a disappeared and furnished the product 3aa in
78% LCꢀyield (Table 1, entry 5). However, the reaction did not
occur in the absence of the Co catalyst (Table 1, entry 2). Varying
the reaction temperature indicated that the yield of 3aa was
significantly reduced when the reaction temperature decreased
(Table 1, entries 3ꢀ5). Further optimization study of the amount
of H2O showed that the desired product 3aa could be obtained in
92% LCꢀyield when 40 uL H2O was added to this reaction (Table
1, entries 6ꢀ9). As expected, control experiments in the absence
O
S
CoC2O4 (5 mol %)
HN
O
S
H
R'
H2O
R'
N3
N
+
R
NC
N
R
MeCN, 80 o
C
O
O
3
1
2
MeO
O
O
S
O
HN
O
H
R'
F
S
S
S
N
N
N
N
N
O
O
O
O
O
3aa
3ba
3ca, 5
6%
, 50%
, 63%
3
Cl
Br
I
O
O
O
S
O
S
S
S
N
N
N
O
N
O
O
O
3da
3ea
, 86%
, 72%
3fa, 88%
3ga
, 83%
O
H
of water did not take place (Table 1, entry 10).
Table 1. Optimization of reaction conditions for the synthesis of
sulfonylamidyl amide 3a
N
O
O
N
O
S
O
N
S
S
S
O
N
N
O
3ka
3ab
N
O
O
3ia
, 63%
3ha
, 71%
, 61%
3ja
, 41%
R
O
O
HN
R= Cyclohexyl,
R= Adamantyl,
, 42%
, 48%
H
S
S
O
N
N
Ts
N
O
N
R
3ac
Entry Cat. (5 mol %) H2O (uL) T (oC)
Yield (%)b
O
3la
3ma
, 75%
, 74%
3
1
2
3
4
5
6
7
8
9
CoC2O4
ꢀꢀꢀꢀ
50
50
50
50
50
40
30
20
10
ꢀꢀꢀꢀ
80
r.t.
40
60
80
80
80
80
80
80
25c
ꢀꢀꢀꢀ
aReaction conditions: 1 (0.5 mmol), 2 (1.2 mmol), CoC2O4 (5
mol%), H2O (40 uL), MeCN (3 mL), 8 h, under air atmosphere.
bIsolated yield.
CoC2O4
CoC2O4
CoC2O4
CoC2O4
CoC2O4
CoC2O4
CoC2O4
CoC2O4
11
36
78
92 (50)d
87
70
61
trace
10
Scheme 2. Cobaltꢀcatalyzed nitrene radical coupling and CꢀH
functionalization.
aReaction conditions: 1a (0.5 mmol), 2a (1.2 mmol), catalyst (5
b
mol %), MeCN (3 mL), 8 h under air atmosphere. The yields
To our surprise, the reaction involving orthoꢀdisubstituted aryl
isocyanides produced the sulfonylguanidine derivatives 4 instead
of the sulfonylamidyl amide products 3 under the identical
reaction conditions (Detials see Supporting Inormation, Table
S1). When further investigating the scope of aryl isocyanides
under the optimal conditions, we found that the orthoꢀ
were determined by LC analysis using diphenyl as an internal
standard. cReaction time：4 h. dIsolated yield.
Under the optimized reaction conditions, we first investigated
the scope of various sulfonyl azides 1 (Table 2). It was found that
benzenesulfonyl azides with electronꢀdonating groups (Me, H,
OMe) showed a moderate reactivity, leading to the desired
products 3aaꢀca in 50ꢀ63% yields. Generally, the halogenꢀ
substituted benzenesulfonyl azides (F, Cl, Br, I) displayed a better
reactivity than electronꢀdonating groups, and the desired product
could be obtained in relatively excellent yields (3da-ga, 72ꢀ88%).
The reaction of 4ꢀacetamidobenzenesulfonyl azide and
naphthaleneꢀ2ꢀsulfonyl azide also worked well, delivering the
products 3ha and 3ia in 61% and 63% yields, respectively. The
heterocyclic 3ꢀpyridylsulfonyl azide showed a lower reactivity
and the product 3ja could be obtained in 41% yield. Besides
arylsulfonyl azides, alkylsulfonyl azides, such as butaneꢀ1ꢀ
sulfonyl azide, propaneꢀ1ꢀsulfonyl azide and ethanesulfonyl
azide, also exhibited a good reactivity in this transformation,
producing the target products 3ka-ma in 71ꢀ75% yields. We next
investigated the scope of isocyanides under the optimal
conditions and found that the isocyanocyclohexane and 1ꢀ
adamantyl isocyanide were proven to be suitable substrates for
this reactions (3ab-ac, 42ꢀ48%).
unsubstituted
aryl
isocyanide,
such
as
3,5ꢀ
dimethylphenylisocyanide, could produce the CꢀH functionalized
3ꢀimine indole derivative 5a in 83% yield (Scheme 2).
Analogously, structure of 5a was confirmed by Xꢀray diffraction
analysis. Base on the above results, we speculated that the
reaction of 1a and 2g showed different pathway, thus further
optimization studies were carried out to improve the yield of 3ꢀ
imine indole derivative 5ag (Detials see Supporting Inormation,
Table S2).
With the optimized conditions in hand, we investigated the
scope of various sulfonyl azides 1 (Table 3). It was gratifying to
observe that paraꢀsubstituted sulfonyl azides bearing all kinds of
electronꢀdonating groups (Me, H, OMe), and halogen atoms (F,
Cl, Br, I) exhibited a very high reactivity under this wellꢀ
established reaction conditions (5agꢀgg, 81ꢀ97%). Moreover, the
4ꢀacetamidobenzenesulfonyl azide and naphthaleneꢀ2ꢀsulfonyl
azide also exhibited a good reactivity in this transformation,
generating the products 5hg and 5ig in 96% and 94% yields,
respectively. The heterocyclic 3ꢀpyridylsulfonyl azide worked
2
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 3 of 5
ChemComm
View Article Online
DOI: 10.1039/C7CC06531K
equally well, and the product 5jg could be isolated in 93% yield.
Furthermore, alkylsulfonyl azides, such as butaneꢀ1ꢀsulfonyl
azide, propaneꢀ1ꢀsulfonyl azide and ethanesulfonyl azide, were
amenable to in this transformation, producing the anticipated
products 5kg-mg in 65ꢀ88% yields. Then, the scope of
isocyanides were investigated under the standard conditions. The
use of paraꢀsubstituted aryl isocyanides containing electronꢀ
donating groups (Me, OMe) led to the products 5ah and 5ai in
87% and 92% yields, respectively. However, aryl isocyanides
with electronꢀwithdrawing groups displayed a lower reactivity
than electronꢀdonating groups, and only a trace amount of
product 5aj could be detected when 1ꢀisocyanoꢀ4ꢀnitrobenzene
was emplyed in this reaction. Moreover, the reaction using ethyl
4ꢀisocyanobenzoate as substrate only furnished the desired
product 5ak in 21% yield. Then, some halogenꢀsubstituted aryl
isocyanides were also tested and the desired product 5al-am
could be isolated in 51% and 25% yields, respectively. Notably,
when 2ꢀphenylphenyl isocyanide was used in this reaction, the
corresponding product 5an instead of phenanthrene derivative
could be obtained in 78% yield.
isolated in 51% yield, which could be confirmed by HRMS (eq. 1,
18O[M+Na]+ 378.1713; found 378.1723). In addition, we tried the
reaction of pꢀtoluenesulfonyl tertꢀbutylcarbodiimide 6 (0.5 mmol)
with 2a (0.6 mmol) under similar conditions, the product 3aa
could be obtained in 63% LCꢀyield (eq. 2), and the reactions
could not proceed in the absence of cobalt catalyst (eq. 3). These
results implied that the Co(II)ꢀcarbodiimide complexes, rather
than carbodiimide 6, could be the intermediate of the two
reactions. Unfortunately, we were unable to synthesize pꢀ
toluenesulfonyl 3,5ꢀdimethylphenylcarbodiimide to examine the
CꢀH functionalization reaction. Besides, more detailed
experiments for investigating the formation of sulfonylguanidine
4 were shown in the Supporting Information (Scheme S1).
Table 3. Synthesis of 3ꢀimine indole 5a,b
.
Scheme 3. Control reactions.
MeCN
CoC2O4
[CoC2O4(MeCN)2
]
A
R
C
R
O
N
C
O
HN
proton
transfer
O
S
N
C
proton
transfer
O
N
R'
H
O
R'
R'
S
R'
N
S
N
R-NC
S
N
R
R
C
H
N
N
O
N
N
O
O
O
O
H
N
H
R
I
3
L
R
H
5
[CoC2O4(R-NC)2]
R-NC
R-NC
B
2
2
R
N
R'SO2N3
N
C
N
LnColl
LnColl
O2S
R'
C
C
N
R
N
S
H
N
N
O
S
O
C
R
N
O
O
H
O
R'
N
R'
H
CollLn
K
H
C
H2O
N2
R
R
N
R
N
C
N
C
N
C
LnColl
C
LnColl
O
N
S
R'
C
CoIII
N
S
C
L
N
R
N
O
O
O
R
N
L
J
O
R'
S
R'
G
O
R
D
R-NC
R = aryl
CollLn
CollLn
R-NC
R = alkyl
R
R
R
N
C
O
O
N C N
N
C N
2
S
S
2
N
R'
O
R'
O
F
C
F
CoIII
L
reaction 1
N
reaction 2
L
O
S
O
R'
E
Scheme 4. Plausible mechanism.
According to the literatures and experimental results12, a
possible mechanism was summarized in Scheme 4. The fourꢀ
coordinated CoC2O4 reacted with two MeCN solvent molecules
as ligands to form intermediate A. Subsequently, A undergoes
ligand exchange with two isocyanide molecules and one sulfonyl
azide to afford sixꢀcoordinated intermediate C. The dissociation
of N2 from the intermediate C generate the Co(III)ꢀnitrene
intermediate D, which undergoes coupling reaction between the
nitrene moiety with the coordinated isocyanide ligand to produce
intermediate F. For reaction 1, another alkyl isocyanide serves as
nuclephile to attack the central carbon of F, leading to the G
intermediate, and G is further quenched by H2O to generate
aReaction conditions: 1 (0.5 mmol), 2 (1.2 mmol), CoC2O4 (1
mol%), MeCN (3 mL), 6 h, under air atmosphere. bIsolated yield.
Our previous reports and computational studies indicated that
the catalytic role of Co(II) catalyst might attribute to the
dissociation of N2 from the sulfonyl azide to generate the Co(III)ꢀ
nitrene intermediate, which could be detected by EPR
spectroscopy.11a To further understand the mechanism of this
reactions, several control reactions were performed as shown in
Scheme 3. In order to verify the oxygen atom of carbonyl coming
from H2O, we carried out the reaction under standard conditions
using H218O instead of H2O and the desired product 3aa’ could be
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3

ChemComm
Page 4 of 5
View Article Online
DOI: 10.1039/C7CC06531K
P. T. G. Rabet, S. Boyd, M. F. Greaney, Angew. Chem. Int. Ed.
2015, 54, 11481. (c) F. Xie, Z.ꢀS. Qi, X.ꢀW. Li, Angew. Chem. Int.
Ed. 2013, 52, 11862. (d) I. T. Alt, B. Plietker, Angew. Chem. Int. Ed.
2016, 55, 1519. (e) Y. M. Badiei, A. Dinescu, X.ꢀL. Dai, R. M.
Palomino, F. W. Heinemann, T. R. Cundari, T. H. Warren, Angew.
Chem. Int. Ed. 2008, 47, 9961. (f) N. Jung, S. Brase, Angew. Chem.
Int. Ed. 2012, 51, 5538. (g) S. Wiese, M. J. B. Aguila, E. Kogut, T.
H. Warren, Organometallics 2013, 32, 2300.
intermediate H. The formed H intermediate dissociates from the
Co(II) center after the ligand exchange with the isocyanide to
yield intermediate I, which further undergo proton transfer to
form the product 3. For reaction 2, another aryl isocyanide
attacks the central carbon of F giving rise to intermediate J, and J
further undergoes the electrophilic ring addition reaction to
furnish the intermediate K. Finally, intermediate K dissociates
from the Co(II) center after the ligand exchange with the
isocyanide to generate intermediate L, which further undergoes
proton transfer to form the product 5. In addition, the plausible
mechanism for the synthesis of sulfonylguanidine 4 was shown in
the Supporting Information (Scheme S2).
3. X. Cui, X. Xu, L.ꢀM. Jin, L. Wojtas, X. P. Zhang, Chem. Sci. 2015, 6,
1219.
4. (a) H.ꢀJ. Lu, V. Subbarayan, J.ꢀR. Tao, X. P. Zhang, Organometallics
2010, 29, 389. (b) H.ꢀJ. Lu, H.ꢀL. Jiang, L. Wojtas, X. P. Zhang,
Angew. Chem. Int. Ed. 2010, 49, 10192. (c) H.ꢀJ. Lu, C.ꢀQ. Li, H.ꢀL.
Jiang, C. L. Lizardi, X. P. Zhang, Angew. Chem. Int. Ed. 2014, 53,
7028.
In summary, we have developed a chemoselective Co(II)ꢀ
catalyzed effective synthesis of sulfonylamidyl amide and 3ꢀ
imine indole derivatives by reacting isocyanides with organic
azides. This protocol provides a new, environmentꢀfriendly and
simple strategy for the effective synthesis of the sulfonylamidyl
amide and 3ꢀimine indole derivatives with a wide range of
substrates in the absence of any oxidants and additives. The
reaction shows that the formation of sulfonylamidino amide
derivatives requires the participation of water and the oxygen
atom of carbonyl comes from H2O. When different molecular
structure of aryl isocyanide are used, such as 2,6ꢀdimethyl phenyl
isocyanide and 3,5ꢀdimethyl phenyl isocyanide, the former
generates sulfonyl guanidine derivatives, and the latter produces
sulfonyl imide indole derivatives. Therefore, different reaction
environments and different substrate structures could furnish
different products, which provides a new strategy for precise
organic synthesis. Further investigations of the Co(II)ꢀcatalyzed
nitrene reactions are currently underway in our laboratory.
We gratefully acknowledge the National Natural Science
Foundation of China (21772137, 21672157, 21372174), the
Major Basic Research Project of the Natural Science Foundation
of the Jiangsu Higher Education Institutions (No. 16KJA150002),
PAPD, and Soochow University for financial support, and State
and Local Joint Engineering Laboratory for Novel Functional
Polymeric Materials.
5. (a) S.ꢀF. Zhu, X. Xu, J. A. Perman, X. P. Zhang, J. Am. Chem. Soc.
2010, 132, 12796. (b) X. Xu, H.ꢀJ. Lu, J. V. Ruppel, X. Cui, S. L. de
Mesa, L. Wojtas, X. P. Zhang, J. Am. Chem. Soc. 2011, 133, 15292.
6. (a) G.ꢀY. Gao, J. E. Jones, R. Vyas, J. D. Harden, X. P. Zhang, J. Org.
Chem. 2006, 71, 6655. (b) J. V. Ruppel, J. E. Jones, C. A. Huff, R. M.
Kamble, Y. Chen, X. P. Zhang, Org. Lett. 2008, 10, 1995. (c) L.ꢀM.
Jin, X. Xu, H. Lu, X. Cui, L. Wojtas, X. P. Zhang, Angew. Chem. Int.
Ed. 2013, 52, 5309.
7. (a) M. Goswami, V. Lyaskovskyy, S. R. Domingos, W. J. Buma, S.
Woutersen, O. Troeppner, I. IvanovićꢀBurmazović, H.ꢀJ. Lu, X. Cui,
X. P. Zhang, E. J. Reijerse, S. DeBeer, M. M. van Schooneveld, F. F.
Pfaff, K. Ray, B. de Bruin, J. Am. Chem. Soc. 2015, 137, 5468. (b) N.
D. Paul, S. Mandal, M. Otte, X. Cui, X. P. Zhang, B. de Bruin, J. Am.
Chem. Soc. 2014, 136, 1090.
8. For recent reviews, see: (a) A. Domling, Chem. Rev. 2006, 106, 17.
(b) L. El Kaim, L. Grimaud, Tetrahedron 2009, 65, 2153. (c) L.
Banfi, R. Riva, A. Basso, Synlett 2010, 23. (d) A. V. Lygin, A. de
Meijere, Angew. Chem. 2010, 122, 9280. (e) M. Tobisu, N. Chatani,
Chem. Lett. 2011, 40, 330.
9. For recent reviews, see: (a) G. Qiu, Q.ꢀP. Ding, J. Wu, Chem. Soc.
Rev. 2013, 42, 5257. (b) A. V. Gulevich, A. G. Zhdanko, R. V. A.
Orru, V. G. Nenajdenko, Chem. Rev. 2010, 110, 5235. (c) T. Vlaar, E.
Ruijter, B. U. W. Maes, R. V. A. Orru, Angew. Chem. Int. Ed. 2013,
52, 7084. For select literatures, see: (d) T. Vlaar, R. C. Cioc, P.
Mampuys, B. U. W. Maes, R. V. A. Orru, E. Ruijter, Angew. Chem.
Int. Ed. 2012, 51, 13058. (e) V. Estévez, G. V. Baelen, B. H.
Lentferink, T. Vlaar, E. Janssen, B. U. W. Maes, R. V. A. Orru, E.
Ruijter, ACS Catal. 2014, 4, 40. (f) J.ꢀY. Liao, P.ꢀL. Shao, Y. Zhao, J.
Am. Chem. Soc. 2015, 137, 628. (g) Y. Kobiki, S. Kawaguchi, A.
Ogawa, Org. Lett. 2015, 17, 3490. (h) Z. Zhang, Z.ꢀY. Li, B. Fu, Z.ꢀ
H. Zhang, Chem. Commun. 2015, 51, 16312. (i) Z. Zhang, B.ꢀL.
Huang, G.ꢀY. Qiao, L. Zhu, F. Xiao, F. Chen, B. Fu, Z.ꢀH. Zhang,
Angew. Chem. Int. Ed. 2017, 56, 4320.
10. T.ꢀH. Zhu, S.ꢀY. Wang, G.ꢀN. Wang, S.ꢀJ. Ji, Chem. Eur. J. 2013, 19,
5850. (b) T.ꢀH. Zhu, X.ꢀP. Xu, J.ꢀJ. Cao, T.ꢀQ. Wei, S.ꢀY. Wang, S.ꢀJ.
Ji, Adv. Synth. Catal. 2014, 356, 509. (c) T.ꢀH. Zhu, S.ꢀY. Wang, T.ꢀ
Q. Wei, S.ꢀJ. Ji, Adv. Synth. Catal. 2015, 357, 823. (d) T.ꢀH. Zhu, S.ꢀ
Y. Wang, Y.ꢀQ. Tao, S.ꢀJ. Ji, Org. Lett. 2015, 17, 1974. (e) T.ꢀH. Zhu,
S.ꢀY. Wang, Y.ꢀQ. Tao, T.ꢀQ. Wei, S.ꢀJ. Ji, Org. Lett. 2014, 16, 1260.
(f) Z.ꢀY. Gu, T.ꢀH. Zhu, J.ꢀJ. Cao, X.ꢀP. Xu, S.ꢀY. Wang, S.ꢀJ. Ji,
ACS Catal. 2014, 4, 49. (g) Z.ꢀY. Gu, X. Wang, J.ꢀJ. Cao, S.ꢀY.
Wang, S.ꢀJ. Ji, Eur. J. Org. Chem. 2015, 4699. (h) Z.ꢀY. Gu, C.ꢀG.
Liu, S.ꢀY. Wang, S.ꢀJ. Ji, J. Org. Chem. 2017, 82, 2223.
11. (a) Z.ꢀY. Gu, Y. Liu, F. Wang, X.ꢀG. Bao, S.ꢀY. Wang, S.ꢀJ. Ji, ACS
Catal. 2017, 7, 3893. (b) T. Jiang, Z.ꢀY. Gu, L. Yin, S.ꢀY. Wang, S.ꢀJ.
Ji, J. Org. Chem., DOI: 10.1021/acs.joc.7b01127.
12. Y. Issa, G. D. Majid, N. Manijeh, Tetrahedron Letts. 2015, 56, 2416.
13. CCDC (1563708) (3aa), CCDC (1555517) (4ad) and CCDC
(1551700) (5ag) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The
Notes and references
a Key Laboratory of Organic Synthesis of Jiangsu Province, College of
Chemistry, Chemical Engineering and Materials Science & Collaborative
Innovation Center of Suzhou Nano Science and Technology, Soochow
University, Suzhou 215123, China; E-mail: shunjun@suda.edu.cn;
shunyi@suda.edu.cn.
† Electronic Supplementary Information (CI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/b000000x/
1. (a) G. Dequirez, V. Pons, P. Dauban, Angew. Chem. Int. Ed. 2012,
51, 7384. (b) S. O. Scholz, E. P. Farney, S. Kim, D. M. Bates, T. P.
Yoon, Angew. Chem. Int. Ed. 2016, 55, 2239. (c) K. Sun, S. Liu, P.
M. Bec, T. G. Driver, Angew. Chem. Int. Ed. 2011, 50, 1702. (d) Q.
Nguyen, K. Sun, T. G. Driver, J. Am. Chem. Soc. 2012, 134, 7262.
(e) M.ꢀH. Shen, B. E. Leslie, T. G. Driver, Angew. Chem. Int. Ed.
2008, 47, 5056. (f) A. Takaoka, M.ꢀE. Moret, J. C. Peters, J. Am.
Chem. Soc. 2012, 134, 6695.
Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
2. (a) A. I. O. Suarez, V. Lyaskovskyy, J. N. H. Reek, J. I. der Vlugt, B.
de Bruin, Angew. Chem. Int. Ed. 2013, 52, 12510. (b) G. Fumagalli,
4
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/C7CC06531K
Cobalt(II)-Catalyzed Bis-isocyanides Insertion Reactions
with Sulfonyl Azides via Nitrene Radical: Chemoselective
Synthesis of The Sulfonylamidyl amide and 3-Imine Indole
Derivatives
Zheng-Yang Gu,a Jing-Hao Li,a Shun-Yi Wang,*a and Shun-Jun Ji*a
A chemoselective Co(II)-catalyzed effective synthesis of sulfonylamidyl amide and 3-imine indole
derivatives by using isocyanides and sulfonyl azides has been developed.