Ni-Catalyzed C-H Cyanation of (Hetero)arenes with 2-Cyanoisothiazolidine 1,1-Dioxide as a Cyanation Reagent

Article abstract of DOI:10.1021/acs.orglett.1c00468

A nickel-catalyzed C-H cyanation reaction of arenes has been developed using 2-cyanoisothiazolidine 1,1-dioxide as an electrophilic cyanation reagent. Many different directing groups can be used in this cyanation to obtain a series of cyanation products with good yields. Adopting this strategy to introduce a cyano group, natural alkaloid menisporphine was successfully synthesized through cyano group conversion that further proved the practicality of this cyanation method.

Full text of DOI:10.1021/acs.orglett.1c00468

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Letter
Ni-Catalyzed C−H Cyanation of (Hetero)arenes with
2‑Cyanoisothiazolidine 1,1-Dioxide as a Cyanation Reagent
Junjie Ma, Hao Liu, Xin He, Zhicheng Chen, Yue Liu, Chuanfu Hou, Zhizhong Sun, and Wenyi Chu*
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ABSTRACT: A nickel-catalyzed C−H cyanation reaction of arenes has been developed using 2-cyanoisothiazolidine 1,1-dioxide as
an electrophilic cyanation reagent. Many different directing groups can be used in this cyanation to obtain a series of cyanation
products with good yields. Adopting this strategy to introduce a cyano group, natural alkaloid menisporphine was successfully
synthesized through cyano group conversion that further proved the practicality of this cyanation method.
romatic nitriles as important skeleton structures are
widely used in drugs, dyes, agrochemicals, materials, and
cyanation reaction and electrophilic cyanation reaction of the
direct C−H bond which is catalyzed by transition metals have
attracted extensive attention. Among them, the nucleophilic
cyanation reaction has been extensively developed by using
various nucleophilic cyanation reagents (Scheme 1a).10
Although these methods are effective, these cyanation reagents
A
natural products, such as the drugs neratinib1 and rilpivirine.2
Meanwhile, they are vital intermediates for synthesizing
carboxylic acids,3 amines,4 tetrazoles,5 and amides6 by
conversion of the nitrile group, for example, synthesis of
natural product menisporphine7 and perspicamides A and B8
(Figure 1). In addition to the Rosenmund−von Braun
Scheme 1. Strategies for the Synthesis Aryl Nitriles
Figure 1. Representative cyano- and cyanide-converted drug
molecules.
reaction, the Sandmeyer reaction is another traditional method
for obtaining aromatic nitriles from aryl halides or aryl
diazonium salts with opper cyanation salt.9 However, these
methods require preactivated aromatic compounds as sub-
strates and have low atom utilization. To solve the above
issues, transition-metal-catalyzed direct C−H bond cyanation
reactions have attracted a lot of attention for use in
synthesizing the aromatic cyanides. At present, the nucleophilic
Received: February 8, 2021
Published: March 31, 2021
https://doi.org/10.1021/acs.orglett.1c00468
© 2021 American Chemical Society
Org. Lett. 2021, 23, 2868−2872
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a
limit their practical application due to the toxic and severe
reaction conditions; for example, heating needs to exceed 100
°C. Therefore, there is an urgent demand for a safe, mild, and
efficient strategy for promoting the cyanidation in organic
synthesis.
Table 1. Optimization of Reaction Conditions
In recent years, it has been common that they were a wide
use of a variety of electrophilic cyanation reagents, such as 4-
toluenesulfonyl cyanide (TsCN),11 N-cyano-N-phenyl-p-tolue-
nesulfonamide (NCTS),12 N-cyanosuccinimide,13 and N-
cyanophthalimide14 as the cyanide sources. These cyanation
reagents exhibit unique advantages of low toxicity and simple
postprocessing. For example, electrophilic C−H cyanation
catalyzed by Rh and Ru has been developed by using NCTS as
cyanation reagent (Scheme 1b).15 However, large-scale
application of these methods is limited due to the high cost
and low conversion of cyanation reagents. Therefore, it is
desirable to find high conversion and low cost alternatives to
NCTS and develop catalytic systems using inexpensive
transition metals as the catalysts.
Based on this idea and inspired by previous work, we
envisioned using cheap nickel16 as the catalyst instead of noble
metal catalysts and NCITD as a high conversion rate cyanation
reagent, wherein NCITD has the advantages of simple
preparation, safety, and stability. Herein, a Ni(acac)2-catalyzed
C(sp2)−H electrophilic cyanation strategy was described by
applying NCITD as the cyanide source (Scheme 1c).
“CN”
b
entry
source
catalyst
ligand
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
1,10-Phen
Pcy3
DPEphos
solvent
yield (%)
1
2
3
4
5
6
7
8
NCTS
TSCN
NCP
NNS
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Pd(OAc)2
Cu(OAc)2
Co(OAc)2
Ni(OAc)2
NiCl2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
toluene
CCl4
MeOH
DMF
56
35
28
31
c
d
NCITD
NCITD
NCITD
NCITD
NCITD
NCITD
NCITD
NCITD
NCITD
NCITD
NCITD
NCITD
NCITD
NCITD
65 ; 72; 72
71
trace
25
36
42
9
10
11
12
13
14
15
16
17
18
60
63
e
f
76 ; 85; 84
15
67
70
51
36
DPEphos
DPEphos
DPEphos
DPEphos
In order to obtain optimal reaction conditions, we applied 2-
phenylpyridine (1a) as a model substrate. The experimental
results obtained were shown in Table 1. Initially, NCTS was
used as electrophilic cyanation reagent when we adopted the
Ni(acac)2 as catalyst, PPh3 as ligand, AgOAc as additive, and
Et3N as base in dichloroethane (DCE) under a temperature of
80 °C for a period of 12 h. In the reaction, as desired, there was
product 2a generated with a 56% yield (Table 1, entry 1).
According to the results, the Ni-catalyzed C−H bond
electrophilic cyanation reaction is feasible. We tried to find
other similar electrophilic cyanation reagents to replace NCTS
due to it is complicated to prepare and expensive
commercially. TSCN, NNS, and NCP were used as the
cyanation reagents to obtain the yields of 2a were obtained
(28−35%) (Table 1, entries 2−4). To our delight, NCITD was
chosen as the electrophilic cyanation reagent, in which case
there was the product 2a generated in a yield reaching 72%
(Table 1, entry 5). According to the results, NCITD was more
compatible with this nickel-catalyzed process than the
commonly used cyanation reagents such as NCTS and
TsCN. Next, the catalyst was evaluated as a crucial factor in
the reaction by using some common transition metal as the
catalysts. Pd(OAc)2 was used as the catalyst to give a slightly
decreased yield (Table 1, entry 6). Cu(OAc)2 was use as the
catalyst without the corresponding product 2a obtained (Table
1, entry 7). Co(OAc)2 as the catalyst only produced the
product 2a in 26% yield (Table 1, entry 8). The yields of NiCl2
and Ni(OAc)2 instead of Ni(acac)2 were 36% and 42%,
respectively (Table 1, entries 9 and 10). According to the
above experimental results, Ni(acac)2 was an effective catalyst.
Then the ligands as another factor of the reaction were also
investigated. In the case of use of the 1,10-Phen and
tricyclohexylphosphan (Pcy3) as the ligands, there were a
decrease in the yields of the product 2a to respective
percentages of 60% and 63%. (Table 1, entries 11 and 12).
However, in the event of application of bis[2-
(diphenylphosphino)phenyl] ether (DPEphos) as the ligand,
a
Reaction conditions: 2-phenylpyridine (1a, 0.10 mmol), “CN”
source (0.20 mmol), catalyst (10 mol %), ligand (15 mol %), AgOAc
(0.20 mmol), Et3N (0.025 mmol), in solvent (1.0 mL), refluxing for
12 h. Yield by rapid column chromatography.
NCITD (0.15 and 0.25 mmol, respectively). Catalyst Ni(acac)2 (5
and 15 mol %, respectively).
b
c,d
“CN” source
e,f
there was an increase in yielding 2a to 85% (Table 1, entry
13). We found that no ligand was added, and the yield
decreased significantly to 15% (Table 1, entry 14).
Finally, an investigation on the reaction solvents was
performed. As per the results, the toluene and CCl4 were
adopted as the solvents to afford the yields in 67% and 70%,
respectively (Table 1, entries 15 and 16). Methanol (MeOH)
and N,N-dimethylformamide (DMF) as the solvents gave
lower yields in 51% and 36%, respectively (Table 1, entries 17
and 18). Moreover, the yield of the product did not change
with the increase of the amount of NCITD (Table 1, entries 5c
and 5d). The yield of the product changed little with the
increase of the amount of Ni(acac)2 (Table 1, entries 13e and
f
13 ).
Under the optimized reaction conditions, we conducted an
exploration of substrate scope and this reaction’s limitations as
shown in Scheme 2. For 2-pyridyl as the direct group, we first
studied the effect of the substituent −R in the aryl moiety. As
mentioned earlier, 2-phenylpyridine (1a) as the substrate
afforded a yield of 85%. For the substituent at para position,
electron-donating group −CH3 gave the product 2b in 87%
yield, while electron-withdrawing group −F gave a reduced
yield of the product 2c to 70%. The −CH3 at the meta position
also afforded the product 2d in 83% yield. For ortho
substituents, the −CH3 gave cyanide product in a dropped
yield to 70% (2e), while the yield of the −F was only 50% (2f).
Next, we evaluated the effect of the substituents in pyridine
moiety. The electron-donating groups −CH3 and −OCH3
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para position of the benzene ring, the products were generated
in a good yield ranging from 70% to 83% (2x−2ab), while the
substituents in ortho position only gave the products with
yields of 53−60% because of the steric hindrance (2ac−2ad).
Via the substituent (−OCH3) in the isoquinoline moiety, the
products were also generated in yields of 75−81% (2ae and
2af). In addition, the cyanation of 3-thienyl group instead of
phenyl group could be carried out smoothly, and the yield was
73% (2ag). Finally, when 2-benzimidazolyl group was used as
the direct group, it was also smooth to convert the cyanation
reaction for obtaining the desired products with good yields
(2ah and 2ai).
Scheme 2. Substrates Scope for Nickel-Catalyzed C−H
a
Cyanation
A conversion of the cyano group into other important
functional groups could be conducted to synthesize some
important compounds. For example, the obtained product 2af
can be employed as a vital intermediate to synthesize the
natural alkaloid menisporphine, which is an alkaloid from
Menispermum dauricum DC (Menispermaceae) and has
exhibited activities against cancer cells. According to literature
reports,17 a multistep reaction was performed to synthesize
menisporphine by using 8-bromo-6,7-dimethoxyisoquinoline
as a starting material with low yield and harsh reaction
conditions. Herein, a new synthetic route was carried out
through the cyanation reaction, hydrolysis, and cyclization to
obtain menisporphine (Scheme 3). Compared with the
literature, the new method features simple operation, mild
conditions for reaction, high yield, and other advantages.
a
Reaction conditions: 1 (0.10 mmol), NCITD (0.20 mmol),
Ni(acac)2 (10 mol %), DPEphos (15 mol %), AgOAc (0.20 mmol),
Et3N (0.025 mmol), in solvent (2.0 mL), refluxing for 12 h.
Scheme 3. Synthesis of Natural Alkaloid Menisporphine
gave the corresponding product (2g−2h) with good yields of
82% and 80%, respectively. However, the electron-withdrawing
group (−NO2) caused a decrease in the yields of the products,
especially the aryl moiety with the electron-withdrawing group
(−F) (2i−2j). Furthermore, naphthalene and thiophene
groups were used as the aryl moiety also gave the desired
products with yields of 78−81% (2k−2m). The foregoing
experimental results indicated the superiority of the electron-
donating groups to the electron-withdrawing groups in terms
of the reaction effect. In addition, the ortho substituents could
cause the yields of the reaction to decrease because of the
steric hindrance.
These initial findings encouraged us to give a further
definition of this reaction in its scope. A study was performed
on the feasibility to adopt other N-heteroaryl including
(iso)quinoline and benzimidazole as the direct groups in the
cyanation process. Under the optimal reaction conditions, 2-
arylquinoline derivatives, 1-arylisoquinoline derivatives and 2-
arylbenzimidazole derivatives were used to explore the scope of
the substrate expansion. First, 2-phenylquinoline as the
substrate obtained the product with a good yield of 78%
(2n). It was found that the different substituents in the para or
meta position of the benzene ring could give the corresponding
products with good yields of 73−79% (2o−2s). However,
-substituents caused the yield of the product to decrease to
50−55% due to steric hindrance (2t−2u). Here, we also found
that the yields of the products containing the electron-
withdrawing groups were lower than those of the electron-
donating groups. The substituent (−CH3) in the quinoline
moiety also afforded the product 2v with a good yield of 77%.
Next, 1-isoquinolinyl group was used as the direct group to
explore the scope of the substrates. 1-Phenylisoquinoline was
used as the substrate to afford the product 2w successfully with
a yield of 80%. Similarly, due to the substituents in the meta or
We performed certain control experiments for the purpose
of defining the potential pathway of this reaction (Scheme 4).
According to the results, the addition of the radical scavenger
2,2,6,6-tetramethyl-1- piperidinyloxy (TEMPO) in the reaction
mixture still gave a yield of product 2a reaching 79%. This
showed a possible involvement of a nonradical pathway in the
reaction (Scheme 4a). Under the standard conditions, in the
case of using the biphenyl as a substrate, there were no
Scheme 4. Control Experiments
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products observed in the reaction (Scheme 4b), which
indicated that the reaction was a C−H activation reaction
but not a substitution reaction.18 Furthermore, to compare the
substrates in terms of electronic effects, via NCITD, we
processed an equimolar amount of 2-phenylpyridine with an
electron-donating group (1b) and electron-withdrawing group
(1c) under the standard conditions (Scheme 4c), from which
we obtained the corresponding cyanation products 2b and 2c
which were generated in yields of 50% and 26%, respectively.
As per the intermolecular competition experiments, the
electron-donating groups contained substrates had more
contributions to the ortho-C(sp2)−H cyanation reaction.
Because of the electron-donating effect, the benzene ring had
a bigger electron density, making the reation easier to proceed.
This indicated it was an electrophilic cyanylation reaction, and
NCITD is an electrophilic cyanylation reagent.19
moderate to good yields by employing the NCITD as a
electrophilic cyanation reagent. In addition, the natural alkaloid
menisporphine was successfully synthesized by using this
strategy and cyano conversion. The scheme and the cyanation
reagent will be more important in medicinal chemistry and
material sciences. Further applications of the cyanation
reagents are still being carried out in our laboratory.
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.1c00468.
Experimental procedures, NMR spectra of target
compounds (PDF)
As per the foregoing results and also the previous related
studies,20−24 we offer a description as to a possible mechanism
for this C−H cyanation in Scheme 5. First, as observed, there
AUTHOR INFORMATION
Corresponding Author
■
Wenyi Chu − School of Chemistry and Materials Science,
Heilongjiang University, Harbin 150080, P.R. China;
orcid.org/0000-0002-4926-4475; Phone: +86-451-
86609135; Email: wenyichu@hlju.edu.cn; Fax: +86-451-
86609135
Scheme 5. Proposed Mechanism
Authors
Junjie Ma − School of Chemistry and Materials Science,
Heilongjiang University, Harbin 150080, P.R. China
Hao Liu − School of Chemistry and Materials Science,
Heilongjiang University, Harbin 150080, P.R. China
Xin He − School of Chemistry and Materials Science,
Heilongjiang University, Harbin 150080, P.R. China
Zhicheng Chen − School of Chemistry and Materials Science,
Heilongjiang University, Harbin 150080, P.R. China
Yue Liu − School of Chemistry and Materials Science,
Heilongjiang University, Harbin 150080, P.R. China
Chuanfu Hou − School of Chemistry and Materials Science,
Heilongjiang University, Harbin 150080, P.R. China
Zhizhong Sun − School of Chemistry and Materials Science,
Heilongjiang University, Harbin 150080, P.R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.1c00468
Author Contributions
is a generation of a cationic Ni(II) species A in situ from
Ni(acac)2 and DPEphos when the AgOAc is added. The
coordination of the compound 1a with the species A generates
a cationic five-membered cyclonickel intermediate B by ortho-
C−H bond activation. The cyanide reagent NCITD with
nickel center of the intermediate B chelates to form
intermediate C. Et3N as a base can increase the electrophilicity
of NCITD, which leads to easy generation of −CN cations,
and the cyano group (CN) is transferred to the metal ring to
form the key imino intermediate D. Then C−C(N) bond of
the intermediate D is cleaved to produce the product 2a and
generate to isothiazolidine 1,1-dioxide nickel complex E.
Finally, there was a conversion of the complex E to the
species A with catalytic activity, accompanied by the release of
isothiazolidine 1,1-dioxide.
J.M., H.L., X.H., Z.C., Y.L., C.H., and Z.S. conducted the
experiments; W.C. designed the experiments and wrote the
paper.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful for financial support from Project Supported
by the Foundation for Engineering Technology Talent
Training from Ministry of Education of China (Grant No.
19JDGC005) and the Research Project of the Natural Science
Foundation of Heilongjiang Province of China (No.
B2018012).
In summary, a nickel-catalyzed C(sp2)−H bond electrophilic
cyanation strategy was developed for aryl compounds with
nitrogen-containing heterocycles as the direct group under
mild conditions. A range of cyanides were prepared in
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