Facile synthesis of 1,2-thiobenzonitriles: Via Cu-catalyzed denitrogenative radical coupling reaction

Article abstract of DOI:10.1039/c9cc05099j

A Cu-catalyzed synthesis of 1,2-thiobenzonitriles via oxidative C-N cleavage of 3-aminoindazoles followed by radical coupling with thiols is developed. A diverse array of 1,2-thiobenzonitriles were obtained in good yields with wide substrate scope. Notably, this is the first example of denitrogenative radical coupling with 3-aminoindazoles.

Full text of DOI:10.1039/c9cc05099j

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DOI: 10.1039/C9CC05099J
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Facile Synthesis of 1,2-Thiobenzonitriles via Cu-Catalyzed
Denitrogenative Radical Coupling Reaction
Yao Zhoua, Ya Wanga, Yixian Loub and Qiuling Song*a,b,c
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Me
A Cu-catalyzed synthesis of 1,2-thiobenzonitriles via oxidative C-N
cleavage of 3-aminoindazoles followed by radical coupling with
thiols is developed. A diverse array of 1,2-thiobenzonitriles were
obtained in good yields with wide substrate scope. Notably, this is
the first example for denitrogenative radical coupling with 3-
aminoindazoles.
AcO
OAc
N
S
N
HO
NH2
AcHN
S
H
S
S
H
R
N
R
OH
R = Cl, 403U76
R = I, IDAM
R = I, ADAM
R = F, F-ADAM
KPR-203
McN 5652
Figure 2. Representative examples of bioactive aromatic sulfides
Aryl sulfides are ubiquitous structural motifs in pharmaceutical
industry and materials science.7 A myriad of natural products and
bioactive compounds are aryl thioether-derived molecules (Figure
2).8 Therefore, a plethora of synthetic methods have been explored
for incorporation of sulfur atoms into targeted molecules to afford
the aryl sulfides.9 One of the most powerful tools is the cross-
coupling of thiols or their surrogates with aryl halides, pseudo
halides, Grignard reagents, diazonium salts, boronic acids, triflates,
etc.9a,9c,10 Since direct arythiation of C-H bonds is more economical
and practical, in recent years, direct C-H functionalization of arenes
with sulfenylating reagents has emerged as an intriguing platform
to access these valuable aryl sulfides.11 In addition to these vigoroso
processes, it’s desirable to form the C-S bond concomitant with the
introduction of additional functionalities under one set conditions,
which could be further transformed for expanding molecule
complicacy. In this regard, recently, Werz and coworkers reported a
novel access towards 1,2-thiobenzonitriles via Pd-catalyzed
activation of aryl thiocyanates followed by aryne insertion (Scheme
1a).12 As part of our ongoing interest for developing new reactions
of 3-aminoindazoles,13 herein, we disclose a facile approach to
streamline the synthesis of 1,2-thiobenzonitriles via Cu-catalyzed C-
N bonds activation of 3-aminoindazoles followed by radical coupling
with mercaptans (Scheme 1b).
The formation and transformation of C-N bonds have
demonstrably emerged as promising topic in organic chemistry,
organometallic chemistry as well as biochemistry.1 Compared with
cleavage of activated C-N bonds, for instance, ammonium salts,2
diazonium salts,3 pyridinium salts,4 triazoles5 and strained
azaheterocycles,6 the cleavage of unactivated C-N bonds has
loomed as challenge in organic chemistry, due to the high C-N bond
dissociation energy. Although transition-metal-catalyzed selective
C-N bond activation has become flourishing in the past decades, up
to now, rare strategies have been successfully developed for the
cleavage of multiple C-N bonds in one molecule under one set of
conditions. Especially, the direct transformation of relatively stable
five-membered heterocycles through selective cleavage of two C-N
bonds in one step is still far from being replenished.
activated C-N bonds
unactivated C-N bonds
NH2
R1
N
N
N
N
R3
-
+
-
+
R
Ar
N
N
Ar NR3X
X
n
N+ X-
N
R
R1
R2
N
R2
R
H
Figure 1. Different Types of C-N bonds.
a) previous work:
N
OTf
S
aInstitute of Next Generation Matter Transformation, College of Chemical
Ar
CN
Pd
Ar
+
Ar
Ar
Engineering and College of Materials Science Engineering at Huaqiao University,
668 Jimei Blvd, Xiamen, Fujian, 361021, P. R. China
S
TMS
bCollaborative Innovation Center of Yangtze River Delta Region Green
Pharmaceuticals, Zhejiang University of Technology, Hangzhou, Zhejiang, 310000
(P. R. China)
b) This work:
NH2
N
cKey Laboratory of Molecule Synthesis and Function Discovery, Fujian Province
University College of Chemistry at Fuzhou University, Fuzhou, Fujian, China, 350108
Email: qsong@hqu.edu.cn; fax:86-592-6162990;
Ar
N
Ar
RSH
Cu
+
R
N
S
H
Scheme 1. Transition-metal-catalyzed Synthesis of 1,2-
Thiobenzonitriles
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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To experimentally confirm our hypothesis, we selected the Subsequently, the scope with respect to various 3-aminoindazoles
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commercially available 3-amino-1H-indazole (1a) as model was also assessed. As shown in Scheme 2, DaObIa: 1tt0e.1r0y3o9/fCs9uCbCs0ti5tu09te9dJ
substrate for the coupling of phenthiol (2a). To our delight, the ring- 3-aminoindazoles were proved to be good donors for producing the
opening product 3aa was indeed obtained in 53% yield when the expectant 1,2-thiobenzonitriles via Cu-catalyzed denitrogenative
reaction was conducted in presence of 20 mol% Cu(OAc)2 and DTBP ring-opening. The desired thioether products 3bd-3hd could be
at 60 oC for 18 h. The model reaction was subsequently subjected to achieved in moderate to excellent yields under the optimal
a range of oxidants to test the effect of the oxidants (Table S1, conditions.
Scheme 2. Scope for synthesis of 1,2-thiobenzonitriles
entries 2-7). Among the oxidants investigated, TBHP displayed the
best choice (Table S1, entry 3). We also screened the effect of
reaction temperature on the reaction yield (Table S1, entry 8-9). As
a result, when the reaction proceeded at 40 oC, the yield of 3aa was
slightly increased to 78%. As a following-up optimization, a set of
solvents were assessed. However, only marginal improvements
were obtained when other solvents, such as DCM, EtOH, Dioxane,
THF, DMF and EtOAc were used instead of CH3CN (Table S1, entries
10-15). We also tested the loading of the catalyst. However, inferior
results were obtained when 10 mol% or 5 mol% of Cu(OAc)2 was
utilized (Table S1, entries 16-17). Stagnant reaction was observed
when the reaction was performed in the absence of Cu(OAc)2 or
TBHP (Table S1, entries 18-19)., which suggested that Cu salt and
oxidant were all indispensable for this transformation. Since
diarylsulfone derivatives are also momentous frameworks which
have been widely applied in the pharmaceutical and polymer
industries. We were inquisitive that if the diarylsulfones could be
obtained by oxidizing the thioether in-situ under this oxidative
system. However, to our disappointment, no diarylsulfone was
detected even 6 equivalents TBHP was added to the reaction (eq 1).
NH2
N
Cu(OAc)2
R1
R1
N
+
RSH
2
aq.TBHP, CH3CN
40 oC, air
N
SR
H
1
3
N
N
N
S
R
S
R
S
R
3aa, R = H, 78%
3aj, R = OMe, 79%
3ak, R = NH2, 76%
X-ray of 3ad
3ab, R = Me, 84%
3ac, R = iPr, 81%
3al, R = Me, 71%
3am, R = OH, 56%
3an, R = NH2, 90%
3ao, R = F, 60%
3ap, R = Cl, 53%
3aq, R = Br, 49%
N
N
F
3ad, R = OMe, 87%
3ae, R = OH, 70%
3af, R = F, 68%
S
F
F
S
Cl
Cl
F
3ag, R = Br, 57%
3ah, R = CF3, 59%
3ai, R = NHAc, 77%
F
3ar, 57%a
3as, 52%a
N
N
N
N
S
S
S
S
N
S
S
N
3at, 64%
N
3au, 76%
3av, 73%
S
3aw, 64%a
N
N
N
S
S
S
11
OMe
3ax, 72%
N
3ay, 60%
N
3az, 88%
3bd, 82%
Me
N
NH2
N
Cu(OAc)2 (20 mol%)
TBHP (6 equiv)
O
O
SH
S
S
N
+
S
S
(eq 1)
N
CH3CN, air
H
OMe
MeO
OMe
Br
OMe
OMe
1a
2a
Ph
3A
3cd, 70%
3dd, 84%
N
3ed, 62%
N
Having identified the optimum reaction conditions, the scope of
this Cu-catalyzed denitrogenative radical coupling reaction for
synthesis of 1,2-thiobenzonitriles was evaluated (Scheme 2).
Gratifyingly, a range of para-substituted phenthiols which bear
electron-donating (Me, iPr, OMe, OH) or either electron-
withdrawing (Br, CF3, NHAc) groups on the benzene ring were well
compatible under the standard conditions, delivering the desired
1,2-thiobenzonitriles in moderate to high yields (3ab-3ai). The
structure of 3ad was unambiguously affirmed by X-ray
crystallographic analysis.14 In addition to para-substituted
phenthiols, meta- and ortho-substituted phenthiols could work
smoothly in this transformation as well, providing the targeted
products 3aj-3aq in decent yields. Of note, functional groups such
as free hydroxyl and amino groups (2e, 2k, 2m, 2n) were well
tolerated in this Cu-catalyzed radical coupling reaction. Compared
with the monohalo-substituted phenthiols, the dihalo-substituted
phenthiol 2r and electron deficient pentafluorothiophenol 2s were
also amenable to transformation, furnishing the corresponding 3ar
and 3as in modest yields. The treatment of 2-naphthalenethiol with
3-aminoindazole 1a was also successful and the desired product 3at
could be isolated with 64% yield. To our delight, heteroaromatic
thiols, such as 2u and 2v were also good candidates for the
construction of C-S bond and rendered the expected products 3au
and 3av in 76% and 73% yields, respectively. In addition to aromatic
thiols, the aliphatic mercaptans could be efficiently converted into
the targeted thioethers 3ax-3az in 60%-88% yields as well.
N
S
S
S
F
F
O
F
OMe
F
OMe
O
3fd, 72%
3gd, 60%
3hd, 54%
1
2
Reaction conditions: (0.3 mmol), (0.2 mmol), Cu(OAc)2 (20 mol%), aq.TBHP (0.4 mmol),
MeCN, 40 oC, air, 18 h.
a 1
2
(0.2 mmol), (0.3 mmol),
Inspired by the success for synthesis of various aromatic
sulfides form 3-aminoindazoles, we attempted to construct
selenides via this Cu-catalyzed C-N bonds activation of 3-
aminoindazoles. As shown in Scheme 3, diphenyl, dimethyl and
dibenzyl diselenides were good coupling partners in this
transformation, enabling the generation of the selenides 5a-5c in
81%, 69% and 72% yields, respectively.
NH2
N
Cu(OAc)2, TBHP
CH3CN, air
N
+
RSe-SeR
4
N
SeR
H
5a, R = Ph, 81%
5b, R = Me, 69%
5c, R = Bn, 72%
1a
Scheme 3. Synthesis of Selenides
Peptidomimetic S-arylcysteines are significant pharmacophores
and have been present in a suite of drug agentias, such as nelfinavir
which is an inhibitor of HIV protease.15 The synthetic utility of this
method was demonstrated by the functionalization of cysteine-
containing molecules to construct S-arylcysteine derivative. When
dipeptide 6 was submitted to this transformation, the reaction
2 | J. Name., 2012, 00, 1-3
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could produce the S-arylcysteine derivative 7 in 62% yield (Scheme
Based on the above experiments,
a
possVibielweArtriceleaOctniloinne
DOI: 10.1039/C9CC05099J
4a). The product 3im could also be effectively converted into 2- mechanism for this Cu-catalyzed denitrogenative radical coupling
chlorodibenzo[b,f][1,4]thiazepin-11-amine 8 in 76% yield (Scheme reaction is delineated in Scheme 6. Firstly, compound A is
4b), which is an analogue of clothiapine16 (an atypical neuroleptic or generated by the oxidation of 3-aminoindazole 1. Subsequently, the
antipsychotic). Moreover, the bromo-substituted product 3jd could Cu(II) species is reduced to Cu(I) species via Single Electron Transfer
undergo the Pd-catalyzed intramolecular C-H arylation to afford the (SET) from compound A, which further goes through extrusion of
benzothiophene 9 in decent yield (Scheme 4c).
one molecular nitrogen and deprotonation to engender the radical
intermediate B. Simultaneously, the thiyl radical C could be
produced from thiol 2 with the help of t-BuO• or t-BuOO• radicals,
which further coordinates with the Cu(I) species to form the
complex D.17,18 Since the transient thiyl radical C was stabilized by
the coordination with Cu(I) species, the C-S bond can be selectively
formed through the coupling of radical intermediate B and complex
D, delivering the desired product 3. At the same time, Cu(I) species
is released and will be oxidized under this oxidative conditions to
NH2
N
SH
S
O
Cu(OAc)2, TBHP
(a)
aa1
H
N
+
O
O
N
O
37 oC, CH3CN, air
N
H
N
H
N
H
O
O
O
OH
6
1a
7, 62%
H2N
Cl
Cl
1) Cu(OAc)2, TBHP,
CH3CN, 40 o
NH2
N
N
SH
C
(b)
(c)
+
+
S
2) t-BuONa, THF
N
NH2
H
1i
2m
8, 76%
N
regenerate Cu(II) species for the next catalytic cycle.
NH2
1) Cu(OAc)2, TBHP,
S
SH
N
CH3CN, 40 o
C
N
N
MeO
H
2) PdCl2(PPh3)2
CsOPiv, DMA
N
Br
OMe
SR
1j
2d
9, 74%
NH2
CuI
3


Scheme 4. Synthetic Applications and Transformations
As following study, several control experiments were
S
N
R
E
a
N
H
1
CuI
RSH
tBuOO

conducted to shed light on the reaction mechanism. When 1a was
exposed under the standard conditions in absence of thiols, trace
amount of benzonitrile (10) and [1,1'-biphenyl]-2,2'-dicarbonitrile
(11) were detected by GC-MS (Scheme 5a). When 2,2,6,6-
tetramethyl-1-piperidinyloxy (TEMPO) and 2,6-di-tert-butyl-4-
methylphenol (BHT) were utilized as radical probes to react with 1a
and 2a under the optimal conditions, the S-arylation reaction was
entirely inhibited (Scheme 5b). Compound 12 and compound 13
were also detected by GC-MS when 1,1-diphenylethylene was
added to the reaction. These results indicated that a radical process
was involved in this Cu-catalyzed denitrogenative reaction. To verify
the essential conditions for the generation of these two radicals,
several control experiments were further carried out. The outcomes
in Scheme 5d and 5e manifested that the combination of Cu salt
and TBHP was crucial for producing the benzonitrile radical and
or tBuO
RS

R
C
[O]
2
tBuOOH
S
or tBuOH
CuI
D
CuII
CuI
..
NH
NH
NH
N
tBuOOH
SET
N

N
N
H
tBuOH, H2O
A
B
H+, N2
1''
Scheme 6. Proposed Reaction Mechanism
In conclusion, we have disclosed a novel Cu-catalyzed synthesis
of 1,2-thiobenzonitriles from 3-aminoindazoles and thiols under
mild conditions. In analogy of the reaction, a radical process is
involved in this Cu-catalyzed denitrogenative ring-opening of 3-
aminoindazoles and the transformations proceed via a radical cross-
coupling pathway to deliver a fund of 1,2-thiobenzonitriles in good
to excellent yields with a wide substrate scope. In addition to 1,2-
thiobenzonitriles, 1,2-selanylbenzonitriles could be easily achieved
in good yields as well. Functionalization of cysteine-containing
molecules to access S-arylcysteine derivatives is also successful in
this Cu-catalyzed denitrogenation of 3-aminoindazoles.
thiyl radical could be readily gained with the assistance of TBHP.
CN
CN
NH2
Cu(OAc)2, TBHP
CH3CN, 40 oC, air
(a)
N
+
N
NC
H
10
11
1a
CN
NH2
Cu(OAc)2, TBHP
CH3CN, 40 oC, air
S
SH
(b)
N
This research was financially supported by the National Natural
Science Foundation (21772046) and the Natural Science Foundation
of Fujian Province (2016J01064). We also thank the Instrumental
Analysis Center of Huaqiao University for analysis support.
+
+
radical scavengers
N
H
TEMPO, 3, 0%
BHT, 3, trace
2a
1a
NH2
Ph
N
Ph
Cu(OAc)2, TBHP
CH3CN, 40 oC, air
SH
N
Ph
(c)
(d)
+
Ph
S
N
1,1-diphenylethylene
H
2a
1a
13
12
N
Conflicts of interest
The authors declare no competing financial interest.
Ph
Ph
NH2
Conditions
N
+
CH3CN, 40 o
C
N
Ph
Ph
H
1a
12
12
Conditions: Only Cu(OAc)2,
12
(not observed)
Only TBHP,
(not observed)
Notes and references
12 (42%)
Cu(OAc)2 and TBHP,
Ph
1
For some reviews on transition-metal-catalyzed C-N
activation: (a) K. Ouyang, W. Hao, W.-X. Zhang and Z. Xi,
Chem. Rev., 2015, 115, 12045; (b) Q. Wang, Y. Su, L. Li and H.
Huang, Chem. Soc. Rev., 2016, 45, 1257; (c) G. Meng, S. Shi
SH
TBHP
(e)
+
Ph
Ph
CH3CN, 40 o
C
+
PhSSPh
Ph
S
2a
13, 29%
Scheme 5. Control Experiments
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