Domino Reactions Initiated by Copper-Catalyzed Aryl-I Bond Thiolation For the Switchable Synthesis of 2,3-Dihydrobenzothiazinones and Benzoisothiazolones

Article abstract of DOI:10.1002/adsc.201801221

The three-component reactions of o-iodobenzamides, elemental sulfur and dichloromethane (DCM) providing 2,3-dihydro-4H-benzo[e][1,3]thiazin-4-ones (2,3-dihydrobenzothiazinones) are accomplished via copper-catalyzed aryl C?I thiolation and subsequent N-, S-hetero ring formation. In addition, the in situ aryl C?I bond thiolation is also employed for the switchable synthesis of benzo[d]isothiazol-3(2H)-ones (benzoisothiazolones) by subjecting o-iodobenzamides, elemental sulfur to the copper-catalyzed condition with microwave irradiation. (Figure presented.).

Full text of DOI:10.1002/adsc.201801221

Title: Domino Reactions Initiated by Copper-Catalyzed Aryl-
I Bond Thiolation For the Switchable Synthesis of 2,3-
Dihydrobenzothiazinones and Benzoisothiazolones
Authors: Jin Xiong, Guofeng Zhong, and Yunyun Liu
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: Adv. Synth. Catal. 10.1002/adsc.201801221
Link to VoR: http://dx.doi.org/10.1002/adsc.201801221

10.1002/adsc.201801221
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Domino Reactions Initiated by Copper-Catalyzed Aryl-I Bond
Thiolation For the Switchable Synthesis of 2,3-
Dihydrobenzothiazinones and Benzoisothiazolones
Jin Xiong,a Guofeng Zhonga and Yunyun Liua*
a
College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, P. R. China
Fax: +86 791 8812 0380
Email: chemliuyunyun@jxnu.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. The three-component reactions of o- benzo[d]isothiazol-3(2H)-ones (benzoisothiazolones) by
iodobenzamides, elemental sulfur and dichloromethane subjecting o-iodobenzamides, elemental sulfur to the
(DCM) providing 2,3-dihydro-4H-benzo[e][1,3]thiazin-4- copper-catalyzed condition with microwave irradiation.
ones (2,3-dihydrobenzothiazinones) are accomplished via
copper-catalyzed aryl C-I thiolation and subsequent N-, S-
hetero ring formation. In addition, the in situ aryl C-I bond
thiolation is also employed for the switchable synthesis of
Keywords: Ullmann C-I thiolation; domino reaction;
switchable; 2,3-dihydrobenzothiazinone;
benzoisothiazolone
and o-aminothiphenols via tandem C-N and C-S
coupling.[6] Wen and Li et al have developed the
domino reactions of o-bromo-arylisothiocyanates and
Introduction
The copper-catalyzed Ullmann-type cross coupling
reactions between aryl/vinyl halides and
aroylhydrazides
benzo[4,5]thiazolo[2,3-c][1,2,4]triazoles.[7]
Furthermore, the synthesis of
benzo[b][1,4]thiazin-3(4H)-ones,[8]
benzothiophenes,[9]
benzisothiazol-3(2H)-ones,[11]
as
synthetic
route
to
a
nucleophile represent a classical and reliable strategy
in constructing C-C and C-heteroatom (N, O, S etc)
bonds. Owing to its general applicability in forging
new C(sp2)-C/heteroatom bond as well as the low
cost and toxicity of the copper catalyst, the Ullmann
cross coupling remains as one of the irreplaceable
synthetic tools in both industrial and laboratory
synthesis.[1] As an representative application mode,
designing domino reactions by making use of the
Ullmann cross coupling as the key transformation has
in the past decade gained huge success in the
synthesis of a massive number of organic products
with different structures.[2] For example, by
employing the Ullmann C-S coupling as a key
transformation, a number of elegant domino reactions
showing high efficiency in the synthesis of sulfur
containing compounds have been realized. Ma and
co-wokers have reported a facile method on
benzothiazole synthesis via copper-catalyzed
reactions of N-acyl o-haloanilines and sulfide salts.[3]
In addition, the C-S coupling-based domino reactions
between o-haloanilines and carbon disulfide giving
benzothiaozles are also achieved.[4] Bao and co-
workers developed the synthetic method toward 2-
iminobenzo-1,3-oxathioles via the assemblies of o-
iodophenols and isothiocyanates.[5] Zeng et al have
identified the copper-catalyzed one-pot synthesis of
phenothiazines via the reactions of aryl o-dihalides
2H-
2-aminobenzothiazoles,[10]
2-
(arylthio)arylcyanamides,[12] as well as thiazino[2,3,4-
hi]indoles[13] have also been reported. In these known
reports on domino reactions initiated by the Ullmann
C-S coupling, various sulfur sources such as
thiophenols, sulfide salts, and isothiocyanates etc
have been utilized. Amazingly, as the simplest,
cheapest and most abundant sulfur source, the
elemental sulfur has not yet been applied to design
such type of domino reactions regardless its
widespread application on many other C-S bond
forming reactions[14] and direct thiolation reactions of
aryl halides.[15] In this context, developing Ullmann
C-S coupling-based domino reactions using elemental
sulfur as the source of sulfur atom is of high merits
because of the incomparable atom economy
associated with elemental sulfur.
Due to the privileged relevance of sulfur
containing molecules with drug discovery and
clinical pharmaceuticals, the synthesis of structurally
diversified
attracting
sulfur-containing
products
The
keeps
2,3-
extensive
interests.[16]
dihydrobenzothiazinone is a typical sulfur containing
heterocycle motif with well-known application in
discovering biologically active lead compounds and
1
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801221
Advanced Synthesis & Catalysis
the synthesis of other useful sulfur-based
heterocycles.[17] Over the past decades, several
different methodologies have been devised for the
synthesis of 2,3-dihydrobenzothiazinones. For
example, the annulation reactions of 2-
mercaptobenzoic acid with imines,[18] the annulation
of thioureas with perfluorobenzoyl chlorides or
methyl o-iodobenzoate,[19] the condensation of 2-
mercaptobenzamides with aldehydes,[20] and the
cyclization of 2-mercaptobenzamides with alkyl
propiolates[21] are predominantly utilized methods.
While the employment of the odour smelling
thiophenol derivative or sensitive acyl chloride as
substrate remains as restriction in the known
approaches, developing new synthetic protocols
reaction at both higher and lower temperature (entries
23-24, Table 1). A control entry without using base
additive provided 4a with trace amount, suggesting
the important role of base in the reaction (entry 25,
Table 1). In additional control experiments, no
expected reaction takes place when N-phenyl o-
bromobenzamide or N-phenyl o-chlorobenzamide
was used as alternative substrate of 1a, respectively.
Table 1 The optimization on reaction conditiona
entry catalyst
base
ligand solvent yield
[%]b
allowing
the
synthesis
of
2,3-
dihydrobenzothiazinones without using sensitive of
odour chemical is of high urgency. Based on our
research interest in developing synthetic methods via
Ullmann coupling-based domino reactions and
organic reactions employing gem-dihaloakane as
building block,[22] we report herein the first domino
reaction of o-iodobenzamide, elemental sulfur and
dichloromethane (DCM) for the synthesis of 2-
unsubstituted 2,3-dihydrobenzothiazinones via the
sequential transformations of Ullmann-type Ar-I
bond thiolation and N-/S-double heteroannulation
based on DCM. In addition, modification on the
reaction conditions in the absence of DCM allowed
1
2
3
4
CuBr
CuI
CuCl
CuBr2
Et3N
Et3N
Et3N
Et3N
no
no
no
no
no
no
no
no
no
DMSO 23
DMSO 16
DMSO 18
DMSO 48
DMSO 25
DMSO 15
DMSO 23
DMSO 25
DMSO 12
DMSO 23
DMSO 27
DMSO 25
DMSO 40
DMSO 38
DMSO 69
DMSO 40
DMSO 36
DMSO 52
5
Cu(OAc)2 Et3N
6
CuCl2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
Et3N
Et3N
Et3N
KOH
7c
8d
9
10
11
12
13e
14f
15
16
17
18
19
20
21
22
23g
24h
25
NaHCO3 no
Cs2CO3
K3PO4
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
-
no
no
no
no
the
switchable
and
rapid
synthesis
of
benzoisothiazolones via domino Ar-I thiolation and
L1
L2
L3
L4
L1
L1
L1
L1
L1
L1
L1
dehydrogenative N-S bond formation.[23]
Results and Discussion
DMF
NMP
nr
nr
At the beginning, the reaction of N-benzyl o-
iodobenzamide 1a, elemental sulfur 2 and DCM 3
was tentatively employed in the presence of CuBr
DMAC nr
xylene nr
DMSO 59
DMSO 62
DMSO trace
o
and Et3N, by heating at 120 C in DMSO, the target
product 4a was observed with 23% yield (entry 1,
Table 1). The subsequent screening to different Cu(I)
and Cu(II) catalysts led to the observation that CuBr2
was a much better catalyst (entries 2-6, Table 1).
Variation on the CuBr2 loading revealed that 25 mol%
catalyst was proper (entries 7-8, Table 1). Later on, a
series of different base additives such as KOH,
NaHCO3, Cs2CO3, K3PO4 were compared for the
reaction, and Et3N remained as the most favourable
base additive (entries 9-12, Table 1). Increasing or
reducing the loading of Et3N was both negative to the
formation of 4a (entries 13-14, Table 1). In addition,
attempts in employing a ligand turned out to be
helpful to improve the yield of 4a, and 1,10-
phenanthroline displayed the best effect (entries 15-
18, Table 1). Notably, the parallel reaction conducted
in reaction media of different polarity such as DMF,
DMAC (N,N-dimethylacetamide), NMP and xylene
gave 4a with very low or no yield, suggesting the
dependence of this reaction on DMSO (entries 19-22,
Table 1). Finally, the reaction temperature was also
optimized, but the drop on product yield was found in
aThe reaction conditions: 1a (0.2 mmol), 2 (1.0 mmol), 3
(0.5 mL), copper catalyst (0.05 mmol), base (0.8 mmol),
ligand (0.06 mmol) in 2 mL solvent, heated at 120 C
(sealed tube) for 12 h under air atmosphere. Yield of
o
b
c
isolated product based on 1a. The loading of CuBr2 was
d
e
20 mol%. The loading of CuBr2 was 30 mol%. The
loading of Et3N was 0.6 mmol. fThe loading of Et3N was
1.0 mmol. gHeating at 110 oC. hHeating at 130 oC.
In the experiments examining the scope of the 2,3-
dihydrobenzothiazinone synthesis, a broad range of
o-iodobenzamides 1 were employed to react with
elemental sulfur and dichloromethane under the
optimized conditions. As outlined in Table 2, the
titled synthesis exhibited general tolerance to the N-
substituted o-iodobenzamides. Generally, N-benzyl
2
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801221
Advanced Synthesis & Catalysis
(4a-4f, Table 2), N-phenylethyl (4g-4h, Table 2), N-
also displayed satisfactory tolerance to the substrates.
alkyl (4i-4l, Table 2) as well as N-aryl (4o-4t, Table 2) The benzamides 1 with divergent substitution,
functionalized substrates 1 could participate in the
synthesis of products 4 with moderate to good yields.
including benzyls (5a-5g, Table 3), phenylethyl (5k-
5l, Table 3), alkyls (5m-5p, Table 3) as well as aryls
(5q-5s, Table 3) all reacted with elemental sulfur to
give corresponding product with moderate to good
When substrate
1
with electron withdrawing
substituent on the phenyl ring was utilized, the
product was also smoothly afforded (4m-4n, Table 2). yields. What’s more, the benzamides with a
On the other hand, when N-benzyl 2-iodo-5-methyl
benzamide was used to react with 2 and 3, complex
mixture was provided, indicating the presence of
unfavoured side reactions resulted from the electron
donating methyl group in the phenyl ring. In addition,
the o-iodobenzamide without N-substitution failed to
take part in this domino reaction to yield expected N-
unsubstituted product. The reaction employing 1,1-
dichloroethane as the alternative substrate of DCM
was also performed, but not corresponding product of
type 4 was observed, either.
substituent such as methyl, methoxyl and chloro in
the phenyl ring were also successfully utilized for the
expected synthesis (5h-5j, Table 1), supporting the
general tolerance of the present synthetic method to
the
N-substituted
o-iodobenzamides
S-N
via
intramolecular
dehydrogenative
bond
formation.[24] However, the employment of N-
unsubstituted o-iodobenzamide for the synthesis of
corresponding NH benzoisothiazolone was not
realized, either.
Table 3 Scope on the synthesis of benzoisothiazolonesa,b
Table
2
Scope on the synthesis of 2,3-
dihydrobenzothiazinonesa,b
aGeneral condition: o-iodobenzmide 1 (0.2 mmol), sulfur
powder 2 (1.0 mmol), CuBr2 (0.02 mmol), Et3N (1.2
aGeneral condition: o-iodobenzmide 1 (0.2 mmol), sulfur
powder 2 (1.0 mmol), DCM 3 (0.5 mL), CuBr2 (0.05
mmol), 1,10-phenanthroline (0.06 mmol), Et3N (0.8 mmol)
o
mmol) and DMSO (2 mL), irradiated at 120 C with MW
b
for 10 min in sealed tube under air atmosphere. Yield of
isolated product based on 1.
o
and DMSO (2 mL), stirred at 120 C for 12 h in sealed
tube under air atmosphere. bYield of isolated product based
on 1.
In further investigation, related control experiments
were designed and executed to probe the potential
reaction pathway. At first, the o-iodobenzamide 1b as
well as elemental sulfur was employed to react under
the standard heating condition without employing
DCM. Instead of the 2-mercaptobenzamide 6, the
product 5b was directly obtained from this reaction
(eq 1), suggesting that 6 was unstable under the
present conditions. In addition, subjecting 5b with
DCM under standard reaction conditions smoothly
given six-membered heterocyclic product 4b (eq 2),
supporting that 5b could act as an intermediate during
the formation of products 4. Actually, the analysis by
GC observed the formation of 5a in the reaction
synthesizing 4a (see SI). In addition, the control
experiment of 1a, sulfur powder and DCM provided
4a with only 8% yield in the presence of radical
Interestingly, when we tried to synthesize and isolate
the potential 2-mercaptobenzamide intermediate from
the reaction without using DCM, we observed the
formation of benzoisothiazolone (see the proposed
mechanism in Scheme 1). This result encouraged us
to further examine this catalytic system in hope of
providing a generally applicable Ar-X bond thiolation
approach for the synthesis of benzoisothiazolones.
After brief exploration on reaction conditions, the
microwave irradiation turned out to be a practical tool
enabling highly efficient and rapid synthesis of 5a.
Thus, the scope on this microwave-assisted, copper-
catalyzed domino synthesis of benzoisothiazolones
was then studied. As shown in Table 3, the method
3
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801221
Advanced Synthesis & Catalysis
scavenger HBT, and the compound 7 resulting from
the oxidation of BHT was obtained with 59% yield
(eq 3), implying that free radical was generated
during the reaction process.[25]
Scheme 1 The proposed reaction mechanism
The intramolecular free radical substation on 10 gives
rise to product 4 and Cl· radical. Simultaneously, the
homo-coupling of the Cl· yielding molecular chlorine
takes place as the free radical chain expiration step.
Conclusion
In summary, we have developed for the first time
the domino reactions on the synthesis of 2,3-
dihydrobenzothiazinones and switchable synthesis of
benzoisothiazolones based on the key transformation
of Ullmann-type Ar-I bond thiolation. The easy
availability, stable, operator friendly, and low cost of
all the reagents constitute the individual advantages
of the present methods. In addition, the interesting
ring opening of the benzoisothiazolones observed in
the experiment can be useful clue in understanding
and devising more divergent reactions involving the
C-heteroatom bond cleavage based on these featured
transformations.
According to the results from the controls
experiments, the general mechanisms for the
reactions providing products 4 and 5 are proposed
(Scheme 1). First, in the presence of copper catalyst
and elemental sulfur, the Ar-I bond undergoes the
typical Ullmann-type thiolation to give thiol
functionalized benzamide 6.[26] This intermediate, as
observed in the experiments, can be quickly
transformed into products 5 under the catalytic
conditions of both microwave irradiation or
conventional heating. Subsequently, in the presence
of DCM, two reaction pathways may take place. One
is the direct double nucleophilic substitution of the
SH and NH group to DCM promoted by the base
additive (path A). On the other hand, since
compounds 5 can also be transformed into products 4
(Eq 2), another possible pathway involving in the ring
opening of the heterocycle in 5 is also possible (path
B). This pathway might be initiated by the single
electron transfer (SET) between Cu(II) and DCM
Experimental Section
General procedure for dihydrobenzothiazinones 4
To a 10 mL test tube equipped with stirring bar and
condenser was charged with o-iodobenzamide 1 (0.2
mmol), sulfur powder 2 (1.0 mmol), DCM 3 (0.5 mL),
CuBr2 (0.05 mmol), 1,10-phenanthroline (0.06 mmol),
Et3N (0.8 mmol) and DMSO (2 mL). The test tube was
sealed with Teflon cap, and the resulting mixture was
o
stirred at 120 C for 12 h. Upon completion (TLC), the
reaction mixture was allowed to cool down to room
temperature, and H2O (5 mL) was added to the vessel. The
resulting suspension was extracted with ethyl acetate (3 ×
10 mL). The organic phases were combined and dried over
Na2SO4. After filtration, the solution obtained therein was
employed to reduced pressure to remove the solvent. The
residue was subjected to silica gel column chromatography
to give pure products by using mixed petroleum ether and
ethyl acetate (v / v = 10:1).
+
which produces Cu(I), Cl· radical and ClCH2 cation
8. This cation coupling 5 to trigger the ring
opening[27] to provide N-chloromethylated S+ cation
intermediate 9. This cation then incorporate Cu(I) to
give free radical intermediate 10 and regenerate Cu(II)
via SET.
General procedure for benzoisothiazolones 5
To a 10 mL microwave reaction tube equipped with
stirring bar was charged with o-iodobenzamide 1 (0.2
mmol), sulfur powder 2 (1.0 mmol), CuBr (0.02 mmol),
Et3N (1.2 mmol) and DMSO (2 mL). The tube was then
sealed, and the resulting mixture was subjected to
microwave irradiation at 120 oC in a NOVA-2S
microwave reactor for 10 min. After stopping the
irradiation, the reaction mixture was allowed to cool down
to room temperature, and H2O (5 mL) was added to the
vessel. The resulting suspension was extracted with ethyl
acetate (3 × 10 mL). The organic phases were combined
and dried over Na2SO4. After filtration, the solvent was
removed from the solution under reduced pressure. The
residue was subjected to silica gel column chromatography
to give pure products by using mixed petroleum ether and
ethyl acetate (v / v = 10:1).
Acknowledgements
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801221
Advanced Synthesis & Catalysis
This work is financially supported by the National Natural
Science Foundation of China (no. 21562024).
Shi, F. Li, D. Chen, Org. Biomol. Chem. 2016, 14,
6279.
[12] T. Ramana, P. Saha, M. Das, T. Punniyamurthy, Org.
Lett. 2010, 12, 84.
References
[13] a) X. Mao, T. Tong, S. Fan, L. Fang, J. Wu, X. Wang,
H. Kang, X. Lv, Chem. Commun. 2017, 53, 4718; b) J.
Tang, B. Xu, X. Mao, H. Yang, X. Wang, X. Lv, J. Org.
Chem. 2015, 80, 11108.
[1] For reviews, see: a) C. Sambiagio, S. P. Marsden, A. J.
Blacker, P. C. McGowan, Chem. Soc. Rev. 2014, 43,
3525; b) J. Hassan, M. Sévignon, C. Gozzi, E. Schulz,
M. Lemaire, Chem. Rev. 2002, 102, 1359; c) K. Kunz,
U. Scholz, D. Ganzer, Synlett 2003, 2428; d) F.
Monnief, M. Taillefer, Angew. Chem. Int. Ed. 2009, 48,
6954; e) D. Ma, Q. Cai, Acc. Chem. Res. 2008, 41,
1450; f) S. Mondal, ChemTexts 2016, 2, 17.
[14] For reviews, see: a) R. Mayer, Elemental Sulfur and
its Reactions, in Organic Chemistry of Sulfur, Ed. S.
Oae, Springer, 1977, pp. 33–69; b) B. Meyer, Chem.
Rev. 1976, 76, 367; c) H. Liu, X. Jiang, Chem. Asian J.
2013, 8, 2546; c) T. B. Nguyen, Adv. Synth. Catal.
2017, 359, 1066.
[2] For selected reviews and examples, see: a) Y. Liu, J.-P.
Wan, Org. Biomol. Chem. 2011, 9, 6873; b) Y. Liu, J.-
P. Wan, Chem. Asian J. 2012, 7, 1488; c) D. Schmidt,
C. C. Malakar, U. Beifuss, Org. Lett. 2014, 16, 4862; d)
B. Li, S. Guo, J. Zhang, X. Zhang, X. Fan, J. Org.
Chem. 2015, 80, 5444; e) Kavala, V.; Janreddy, D.;
Raihan, M. J.; Kuo, C.-W. Ramesh, C.; Yao, C.-F. Adv.
Synth. Catal. 2012, 354, 2229; f) C. J. Ball, J. Gilmore,
M. C. Willis, Angew. Chem. Int. Ed. 2012, 51, 5718; g)
N. Aljaar, C. C. Malakar, J. Conard, S. Strobel, T.
Schleid, U. Beifuss, J. Org. Chem. 2012, 77, 7793; h)
M. Jiang, J. Li, F. Wang, Y. Zhao, F. Zhao, X. Dong,
W. Zhao, Org. Lett. 2012, 14, 1420; i) F.-C. Jia, C. Xu,
Q. Cai, A.-X. Wu, Chem. Commun. 2014, 50, 9914; j) J.
An, H. Alper, A. M. Beauchemin, Org. Lett. 2016, 18,
3482; k) V. Murugesh, B. Harish, M. Adiseshu, J. B.
Nanubolu, S. Suresh, Adv. Synth. Catal. 2016, 358,
1309; l) S. Dhiman, K. Pericherla, N. K. Nandwana, D.
Kumar, A. Kumar, J. Org. Chem. 2014, 79, 7399; m) P.
Sang, Y. Xie, J. Zou, Y. Zhang, Org. Lett. 2012, 14,
3894.
[15] Y. Liu, S. Liu, Y. Xiao, Beilstein J. Org. Chem. 2017,
13, 589, and related references cited therein.
[16] For a review, see: M. Feng, B. Tang, S. H. Liang, X.
Jiang, Curr. Top. Med. Chem. 2016, 16, 1200.
[17] a) F. Voss, E. Herdtweck, T. Bach, Chem. Commun.
2011, 47, 2137; b) A. Zarghi, T. Zebardast, B. Daraie,
M. Hedayati, Bioorg. Med. Chem. 2009, 17, 5369; c) R.
Tiwari, P. A. Miller, S. Cho, S. G. Franzblau, M. J.
Miller, ACS Med. Chem. Lett. 2015, 6, 128; d) V. R.
Solomon, W. Haq, K. Srivastava, S. K. Puri, S. B. Katti,
J. Med. Chem. 2007, 50, 394.
[18] a) W. P. Unsworth, C. Kitsiou, R. J. K. Taylor, Org.
Lett. 2013, 15, 258; b) K. Johannes, J. Martens,
Tetrahedron 2010, 66, 242; c) C. Kitsiou, W. P.
Unsworth, G. Coulthard, R. J. K. Taylor, Tetrahedron
2014, 70, 7172.
[19] a) W. R. Dolbier, Jr., C. Burkholder, K. A. Abbound,
D. L. J. Org. Chem. 1994, 59, 7688; b) D. Chen, J. Wu,
J. Yang, L. Huang, Y. Xiang, W. Bao, Tetrahedron Lett.
2012, 53, 7104.
[3] D. Ma, S. Xie, P. Xue, X. Zhang, J. Dong, Y. Jiang,
Angew. Chem. Int. Ed. 2009, 48, 4222.
[4] D. Ma, X, Lu, L. Shi, H. Zhang, Y. Jiang, X. Liu,
[20] a) H. Zinnes, R. A. Comes, J. Shavel, J. Org. Chem.
1964, 29, 2068; b) J. Nyitrai, J. Fetter, Gy, H.; K.
Zauer, K. Lempert, I. Koczka, I. Sági, C. Rétháti,
Tetrahedron 1978, 34, 1031.
Angew. Chem. Int. Ed. 2011, 50, 1118.
[5] X. Lv, Y. Liu, W. Qian, W. Bao, Adv. Synth. Catal.
2008, 350, 2507.
[6] C. Dai, X. Sun, X. Tu, L. Wu, D. Zhan, Q. Zeng, Chem. [21] H.-H. Wang, T. Shi, W.-W. Gao, H.-H. Zhang, Y.-Q.
Commun. 2012, 48, 5367.
Wang, J.-F. Li, Y.-S. Hou, J.-H. Chen, X. Peng, Z.
Wang, Org. Biomol. Chem. 2017, 15, 8013.
[7] L.-R. Wen, S.-L. Li, J. Zhang, M. Li, Green Chem.
2015, 17, 1581.
[22] a) Y. Liu, M. Huang, L. Wei, New J. Chem. 2017, 41,
4776; b) X. Chen, W. Hao, Y. Liu, Org. Biomol. Chem.
2017, 15, 3423; c) X. Chen, Y. Liu, RSC Adv. 2017, 7,
37839; d) X. Chen, C. Hu, J.-P. Wan, Y. Liu,
Tetrahedron Lett. 2016, 57, 5116; d) Y. Liu, H. Wang,
J.-P. Wan, J. Org. Chem. 2014, 79, 10599; e) J.-P. Wan,
H. Wang, Y. Liu, H. Ding, Org. Lett. 2014, 16, 5160.
[8] D. Chen, Z.-J. Wang, W. Bao, J. Org. Chem. 2010, 75,
5768.
[9] D. J. C. Prasad, G. Sekar, Org. Biomol. Chem. 2013, 11,
1659.
[10] a) G. Shen, X. Lv, W. Bao, Eur. J. Org. Chem. 2009,
5897; b) Q. Ding, X. He, J. Wu, J. Comb. Chem. 2009,
11, 587; c) Y.-J. Guo, R.-Y. Tang, P. Zhong, J.-H. Li,
Tetrahedron Lett. 2010, 51, 649; d) S. K. Sahoo, A.
Banerjee, S. Chakraborty, B. K. Patel, ACS Catal. 2012,
2, 544.
[23] For examples on the Ullmann thiolation-based
synthesis of benzoisothiazolones, see: a) B. S. Bhakuni,
S. J. Balkrishna, A. Kumar, S. Kumar, Tetrahedron
Lett. 2012, 53, 1354; b) R. Paul, T. Punniyamurthy,
RSC Adv. 2012, 2, 7075.
[24] a) Z. Wang, Y. Kuninobu, M. Kanai, J. Org. Chem.
2013, 78, 7337; b) Ş. D. Doğan, Tetrahedron Lett. 2017,
73, 2217.
[11] a) F. Wang, C. Chen, G. Deng, C. Xi, J. Org. Chem.
2012, 77, 4148; b) Z. Wang, Y. Kuninobu, M. Kanai, J.
Org. Chem. 2013, 78, 7337; c) T. Li, L. Yang, K. Ni, Z.
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801221
Advanced Synthesis & Catalysis
[25] W. Baik, H. J. Lee, J. M. Jang, S. Koo, B. H. Kim, J.
Org. Chem. 2000, 65, 108.
[27] A. Henke, J. Srogl, Chem. Commun. 2010, 46, 6819.
[26] a) Y. Jiang, Y. Qin, S. Xie, X. Zhang, J. Dong, D. Ma,
Org. Lett. 2009, 11, 5250; b) H.-J. Xu, Y.-F. Liang, Z.-
Y. Cai, H.-X. Qi, C.-Y. Yang, Y.-S. Feng, J. Org.
Chem. 2011, 76, 2296.
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801221
Advanced Synthesis & Catalysis
FULL PAPER
Domino Reactions Initiated by Copper-Catalyzed
Aryl-I Bond Thiolation For the Switchable
Synthesis of 2,3-Dihydrobenzothiazinones and
Benzoisothiazolones
Adv. Synth. Catal. Year, Volume, Page – Page
Jin Xiong, Guofeng Zhong, Yunyun Liu*
7
This article is protected by copyright. All rights reserved.