Catalyst-free synthesis of thiazolidines: Via sequential hydrolysis/rearrangement reactions of 5-arylidenethiazolidin-4-ones at room temperature

Article abstract of DOI:10.1039/c7ob02924a

A catalyst-free sequential reaction involving hydrolysis and intramolecular aza-Michael addition was developed for synthesizing functionalized thiazolidines from 5-arylidenethiazolidin-4-ones at room temperature. A series of thiazolidine-5-carboxylic acids were prepared in good to excellent yields (up to 97% yield) and excellent diastereoselectivities (up to >20:1 dr). This methodology was applicable to the construction of derivatives of thiacloprid and flutianil with good yields.

Full text of DOI:10.1039/c7ob02924a

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Catalyst-free synthesis of thiazolidines via sequential hydrolysis/rearrangement
reactions of 5-arylidenethiazolidin-4-ones at room temperature
Fanxun Zeng a, Letian Zhang a, Xusheng Shao a, Zhong Li a, b, Xiaoyong Xu * a, b
a Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of
Science and Technology, 130 Meilong Road, Shanghai 200237, China
b
Shanghai Collaborative Innovation Center for Biomanufacturing Technology, 130 Meilong
Road, Shanghai 200237, China
*
Corresponding author. Tel.: +86-21-64252945; fax: +86-21-64252603. E-mail:
xyxu@ecust.edu.cn.
Abstract
A catalystꢀfree sequential reaction involving hydrolysis and intramolecular azaꢀMichael addition
was developed for synthesizing functionalized thiazolidines from 5ꢀarylidenethiazolidinꢀ4ꢀones at
room temperature. A series of thiazolidineꢀ5ꢀcarboxylic acids were prepared in good to excellent
yields (up to 97% yield) and excellent diastereoselectivities (up to >20:1 dr). This methodology
was applicable to the construction of derivatives of thiacloprid and flutianil with good yields.
Introduction
Thiazolidines are important N and Sꢀheterocycles due to their diverse biological activities,1
practical synthetic values2 and extensive applications in peptide synthesis.3 In particular, the
thiazolidine scaffold is the key structural component of many natural products4 and marketed
products including insecticide,5 fungicide6 and antibiotics.7 Four representative examples are
shown in Fig. 1. Latrunculin A and its analogs, marine toxins purified from the red sea sponge
Latrunculia magnifica, have been found to disrupt microfilament organization and inhibit actin
polymerization.8 Thiacloprid is one of neonicotinoid insecticides, whose discovery has been
regarded as a milestone in the past three decades.5,9 Flutianil is a fungicide mainly used for
grapevine and ornamental crops protection.6, 10 The clinical success of penicillin G prompted the
development of antibiotics, which is recognized as one of the most significant advances in modern
medicine.11

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O
O
CN
N
N
OH
S
O
H
Cl
N
HN
O
S
Latrunculin A
Thiacloprid
O
H
H
H
S
CN
S
CF3
N
N
S
N
O
O
COOH
F
Flutianil
Penicillin G
Fig. 1 Representative thiazolidines.
The synthesis of thiazolidineꢀcontaining compounds is a focus of research.12 For example, the
synthesis of 2ꢀiminoꢀ4ꢀ(trifluoromethyl) thiazolidinꢀ4ꢀol derivatives by oneꢀpot, threeꢀcomponent
reactions of primary amines, aryl isothiocyanates, and 3ꢀbromoꢀ1,1,1ꢀtrifluoroꢀpropanone has
been disclosed by Kumbhare and coꢀworkers (Scheme 1a).13 Efficient constructions of
thiazolidines by the reactions of primary amines, carbon disulphide and αꢀbromides have been
demonstrated by Yavari and Sun groups (Scheme 1b).14 Recently, Alꢀcatalyzed (3+2)
cycloaddition of inactivated chiral aziridines with isothiocyanates to prepare 2ꢀiminothiazolidines
has been reported (Scheme 1c).15 The generation of thiazolidines from alkyl
allyl(alkyl/aryl)ꢀdithiocarbamates via radical cyclization with the corresponding Sꢀalkyl Oꢀethyl
xanthates as the adscititious radical precursors has also been developed by Xu et al (Scheme 1d).16
In particular, Frost and coꢀworkers have reported rutheniumꢀcatalyzed Oꢀ to Sꢀalkyl migration to
prepare thiazolidine derivatives (Scheme 1e).17 Most of these methodologies, however, suffered
from drawbacks such as harsh conditions, limited substrate scopes or the use of catalysts.
Consequently, exploring practical and novel reaction types to prepare functionalized thiazolidines
are still greatly in demand.
Since the intermolecular conjugate addition of stabilized carbanions to electronꢀdeficient olefins
was discovered by Arthur Michael in 1887, Michael reactions have emerged as powerful synthetic
tools for mild constructions of carbonꢀcarbon or carbonꢀheteroatom bonds.18 Our research
program focusing on thiazolidinꢀ4ꢀones indicated that this scaffold was unstable under alkaline
condition.19 We envisioned that compounds 1 could be converted to intermediates IM and then
turned to the corresponding thiazolidines 2 via intramolecular azaꢀMichael addition reactions
(path a, Scheme 1) or 2,3ꢀdihydrothiophenes 3 via intramolecular conjugate addition reactions
(path b, Scheme 1) under basic conditions. The obtained products were finally proved to be
thiazolidines 2. Herein, we report a novel hydrolysis/azaꢀMichael addition reaction cascade for the
synthesis of thiazolidines from 5ꢀarylidenethiazolidinꢀ4ꢀones.

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DOI: 10.1039/C7OB02924A
S
DMF
r.t.
O
OH
(a)
(b)
R NH2
+
+
S C N
Br
CF3
N
N
F3C
R
S
N
O
Conditions
S
CS2
R
+
+
R'
OH
NH2
Br
R'
R
R
N
R'
N
5 mol % Al(salen)Cl
DCM, 23 oC
N C S
R'
+
(c)
S
N
R
Ph
Ph
S
S
S
R
O
S
R'
N
S
N
R
S
R'
(d)
R'
DLP, DCE, reflux
[RuCl2(p-cymene)]2 (1 mol %)
SPhos (2 mol %)
R''
R'
R''
R'
S
O
O
S
(e)
N
toluene, 0.2 M, 100 oC
N
R
R
R1
R2
path a, then H
N
b
S
NO2
our work
HOOC
R1
R2
OOC
R1
N
O
N
OH
2
a
S
S
NO2
NO2
NO2
R2
HOOC
R2
path b, then H
R1
N
S
H
1
IM
3
Scheme 1 Selected examples of thiazolidinones synthesis and the diagram of our work.
Results and discussion

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R
R
S
R
HN
(a)
EtOH/n-propanol
relux
HS
COOEt
TEA
S
O
+
N
NO2
S
H2N
NO2
IIa-h
S
NO2
Ia-h
IIIa-h
75-90% yields over two steps
S
O
EtOH
HS
COOEt
TEA
HN
S
N
S
(b)
CH3NH2 (aq)
+
S
NO2
NO2
NO2
Ii
IIi
IIIi
43% yield
75% yield
O
O
K
N
O
SH
CN
S
CN
N
(NH4)2CO3
N
N
(c)
S
CN
H2N
KOH, EtOH, reflux
S
S
EtOH, 60 oC
9a
9b
9c
73% yield over two steps
Cl
Cl
N
Cl
N
O
N
N
DMF, 50 oC
CN
S
9d
75% yield
R1
R1
O
N
NaOH, EtOH
40 oC
O
N
X
R2 CHO
+
(d)
R3
X
S
R3
S
R2
IIIa-i, 9d
1a-o, 9
80-92% yields
NO2
NO2
conditions
EtOH, NaOH
NO2
S
N
S
N
O
r.t.
S
N
+
CHO
O
IIIa'
(e)
HO
terrible mixture
O
references 20
IIIa
terrible mixture
Scheme 2 Preparation of starting materials 5ꢀarylidenethiazolidinꢀ4ꢀones and the example of
synthesis of alkylꢀsubstituted starting material.
Starting materials 5ꢀarylidenethiazolidinꢀ4ꢀones 1a-o and 9 were easily prepared by
Knoevenagel condensations of commercially available aromatic aldehydes with thiazolidinꢀ4ꢀones
IIIa-i and 9d in 80ꢀ92% yields (Scheme 2). Thiazolidinꢀ4ꢀones IIIa-i were synthesized by oneꢀpot
method. Nucleophilic substitutions of (2ꢀnitroetheneꢀ1,1ꢀdiyl)bis(methylsulfane) with arylamines
Ia–h gave intermediates IIa-h, which were further reacted with ethyl 2ꢀmercaptoacetate to give
key precursors IIIa-h. Compound IIIi was obtained through cyclization reaction of ethyl
2ꢀmercaptoacetate and compound IIi, which was prepared by nucleophilic substitution reaction of

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(2ꢀnitroetheneꢀ1,1ꢀdiyl)bis(methylsulfane) with methylamine. Pyridine derivative 9d was
synthesized by the reaction of 2ꢀchloroꢀ5ꢀ(chloromethyl)pyridine and intermediate 9c, which was
obtained by the oneꢀpot reaction of dimethyl cyanocarbonimidodithioate, ammonium carbonate
and methyl 2ꢀmercaptoacetate. The overall yields were generally high and the isolation was
typically simple.
5ꢀBenzylideneꢀ3ꢀphenylthiazolidinꢀ4ꢀone 1a was selected as the model substrate to optimize the
reaction conditions. Initially, a variety of solvents were explored using NaOH as a base (Table 1,
entries 1–8). No product was detected even under reflux with water as initial solvent, which may
be due to the poor solubility of 1a (Table 1, entry 1). Moreover, no desired product was observed
when SDS was added (Table 1, entry 2). Then the above experiments were performed in several
polar solvents in combination with 10 equivalents of water (Table 1, entries 3–8). To our delight,
product 2a with an excellent yield was obtained in ethanol at room temperature (Table 1, entry 7).
The yield of product 2a was further raised to 98% in methanol (Table 1, entry 8). The influence of
temperature was also investigated (Table 1, entries 9–11). Only yield of 7% was obtained even if
extended reaction time was consumed when the reaction was carried out at 0 oC (Table 1, entry 9).
o
When this experiment was conducted at 40 C or under reflux conditions, less time was needed
with slightly lower yields provided (Table 1, entry 8 vs. entries 10 and 11). Furthermore, the
reactions were tried using different bases (Table 1, entries 12–15). Similar result was observed
when KOH was used (Table 1, entry 8 vs. entry 12). Weaker bases led to lower yields and
prolonged reaction time (Table 1, entries 13 and 14). And no product was observed when TEA
was introduced (Table 1, entry 15). It was noticed that the amount of NaOH played a key role in
the reaction (Table 1, entries 8 and entries 16–18). Furthermore, the effect of the amount of water
was carefully studied (Table 1, entries 19–26). It was found that adding a litter bit of water slightly
increased the yield and further increasing the proportion of water decreased the yield of 2a. From
the above experimental conditions, it may conclude that the base of NaOH (1.5 equiv.) in
methanol combining with water (7.5 equiv.) at room temperature are the optimal reaction
conditions suited for this conversion (Table 1, entry 23).
Table 1 Optimization of reaction conditions a
Enty Base (equiv.) Solvent
Temp (ºC) Time (h)
Yieldc (%)
trace
trace
trace
trace
2
1
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
H2O
reflux
reflux
r.t.
12
12
12
12
12
2b
H2O
3
10 equiv. H2O + dioxane
10 equiv. H2O + ACN
10 equiv. H2O + DMF
4
r.t.
5
r.t.

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6
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
KOH (1.5)
LiOH (1.5)
K2CO3 (1.5)
TEA (1.5)
10 equiv. H2O + DMSO
r.t.
r.t.
r.t.
0
12
8
2
7
10 equiv. H2O + EtOH
10 equiv. H2O + MeOH
10 equiv. H2O + MeOH
10 equiv. H2O + MeOH
10 equiv. H2O + MeOH
10 equiv. H2O + MeOH
10 equiv. H2O + MeOH
10 equiv. H2O + MeOH
10 equiv. H2O + MeOH
10 equiv. H2O + MeOH
10 equiv. H2O + MeOH
10 equiv. H2O + MeOH
absolute MeOH
83
98
7
8
8
9
48
2.5
1
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
40
91
92
97
78
22
0
reflux
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
8
20
20
48
20
20
20
8
NaOH (0.8)
NaOH (1.0)
NaOH (1.2)
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
NaOH (1.5)
75
93
97
89
93
92
97
99(95d)
96
87
80
1 equiv. H2O + MeOH
2 equiv. H2O + MeOH
5 equiv. H2O + MeOH
7.5 equiv. H2O + MeOH
20 equiv. H2O + MeOH
0.1 mL H2O + 0.9 mL MeOH
0.2 mL H2O + 0.8 mL MeOH
8
8
8
8
10
15
20
a
b
c
Reaction conditions: substrate 1a (0.2 mmol), slovent (1 mL). 0.04 mmol SDS was added.
Yield was determined by UPLC (ultra performance liquid chromatography). d Isolated yield.
With the optimal conditions in hand, the substrate scope was explored (Table 2). The optimized
reaction conditions could be easily adapted to a variety of substituted thiazolidinones. As shown in
Table 2, diversified 5ꢀarylidenethiazolidinꢀ4ꢀones were transformed to the corresponding
thiazolidines in good to excellent yields. We explored the effect of substituents on the nitrogen
atoms. Substrates with phenyl and phenyl groups bearing electronꢀwithdrawing groups (Cl, CF3)
or electronꢀdonating groups (Me, OMe) at their para, meta or orthoꢀpositions were used under the
optimized conditions, affording the corresponding products 2aꢀ2h in excellent yields of over 95%.
Substituted groups and positions showed no obvious influence on the yields. However, the
substrates 1c and 1d with electronꢀwithdrawing groups had higher reaction rates. And the
reactivity was slightly decreased when the substrates 1f and 1h containing strong
electronꢀdonating groups were used. The reaction of the methylꢀsubstituted 1i gave 2i in relatively
low yield of 61%, and several byꢀproducts were observed. To further study the generalization of
the transformation, then we investigated the effect of the R2 group. Both electronꢀdeficient and
electronꢀrich phenyl groups were well tolerated, with the corresponding products 2j–2n being
formed in high yields of 70–96%. In the case of a 4ꢀnitrophenylꢀsubstituted substrate, a less
reaction time was required and only 70% yields was obtained. The substrates 1l and 1n with
strong electronꢀdonating substituent methoxy group also worked well but with a prolonged
reaction time. Finally, the furanꢀcontaining substrate was carried out under the optimized reaction
conditions. Product 2o was successfully obtained in 82% yield. In most cases, products could be

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easily purified by simple operation rather than column chromatography.
Unfortunately, we cannot verify whether this methodology would be applied to the preparation
of alkylꢀsubstituted derivatives (R2 = alkyl) because we failed to prepare corresponding starting
materials effectively. Some efforts to prepare the alkylꢀsubstituted raw materials using our general
method or according to literature methods were unsuccessful,20 with only terrible mixture was
obtained and very little target product formed which can be detected by LCꢀMS (Scheme 2e).
Table 2 Substrate scope of the thiazolidines synthesisa,b
O
H
R1
R1
R2
N
NaOH
N
H
S
R2
HOOC
S
MeOH, H2O, r.t.
NO2
NO2
1
2
Cl
Cl
CF3
H
H
H
H
Cl
N
N
N
N
H
H
H
H
HOOC
S
HOOC
S
HOOC
S
HOOC
S
NO2
NO2
NO2
NO2
2a
8 h, 95%, >20:1 dr
2b
8 h, 96%, >20:1 dr
2c
5 h, 95%, >20:1 dr
2d
3 h, 96%, >20:1 dr
OMe
H
H
H
N
H
N
OMe
NO2
N
H
N
H
HOOC
S
HOOC
S
HOOC
S
HOOC
S
NO2
NO2
NO2
2e
2f
2g
8 h, 95%, >20:1 dr
2h
20 h, 97%, 1.7:1 dr
8 h, 97%, >20:1 dr
24 h, 96%, >20:1 dr
Cl
O2N
MeO
H
H
H
H
N
H
N
H
N
N
H
H
HOOC
S
HOOC
S
HOOC
S
HOOC
S
NO2
NO2
NO2
NO2
2j
2k
0.5 h, 70%, >20:1 dr
2l
36 h, 93%, >20:1 dr
2i
8 h, 61%c, >20:1 dr
8 h, 96%, >20:1 dr
OMe
H
H
H
O
N
N
H
N
H
H
HOOC
S
HOOC
S
HOOC
S
NO2
NO2
NO2
2m
2n
2o
10 h, 95%, >20:1 dr
48 h, 95%, >20:1 dr
24 h, 82%, >20:1 dr
a Reaction conditions: All reactions were performed with 0.5 mmol of 1, 1.5 equiv. of NaOH, 7.5
equiv. of H2O, and 2.5 mL of MeOH at r.t. for 0.5ꢀ48 h. b Isolated yield. c The solvent was

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changed to EtOH.
In order to illustrate the potential synthetic utility of this methodology, the reactions of 7 and 9
were carried out to prepare the derivatives of thiacloprid and flutianil (Scheme 3). Flutianil was
synthesized by the reaction of compounds 4, 5 and 1,2ꢀdibromoethane in yield of only 7%.10a In
this study, compound 8, the derivative of flutianil, was obtained from the same starting materials 4
and 5 in a total yield of about 21% over 3 steps (Scheme 3a), which is three times of that of
flutianil. Compound 10, the derivative of thiacloprid, could be smoothly obtained in yield of 81%
from compound 9 (Scheme 3b).
O
CN
S
CF3
N
S
BrCH2CH2Br
NaH, DMF
7%
NC
F
S
F
CF3
(a)
O
Flutianil
+
NCS
4
5
O
BrCH2COCl
O
CN
S
CF3
N
S
NaH, DMF
30%
6
F
NaOH, EtOH
85%
CHO
O
O
O
CN
CF3
N
NaOH
CN
S
CF3
N
S
S
MeOH, H2O, r.t.
82%
S
HOOC
F
F
8
7
N
Cl
N
O
N
H
Cl
NaOH
N
N
(b)
S
H
EtOH, H2O, r.t.
81%, >20:1 dr
N
CN
S
HOOC
CN
9
10

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Scheme 3 Synthesis of the derivatives of thiacloprid and flutianil.
Moreover, the stereochemistry of the products was also preliminary investigated. The
1
diasteromeric ratio of 2a was determined to be >20:1 anti/syn by the analysis of the H NMR
spectrum and singleꢀcrystal Xꢀray diffraction structure of 2a (Fig. 2). The major stereoisomer
formed was transꢀisomer owing to steric hindrance. Compounds 2b-2g, 2i-2o and 10 were also
obtained with excellent diastereoselectivities (>20:1 dr). But 2ꢀmethoxy substituted derivatives 2h
and 8 were obtained with poor dr values of 1.7:1 and 1.17:1.
Fig. 2 Singleꢀcrystal Xꢀray diffraction structure and transꢀisomers of 2a.
Conclusions
In summary, we developed the general and operationally simple rearrangement reactions of
5ꢀarylidenethiazolidinꢀ4ꢀones, affording functionalized thiazolidines. The reactions were carried
out with high yields and excellent diastereoselectivities at room temperature without any catalyst,
additive or ligand. These advantages illustrated the potential using of this reaction in industrial
production. The synthetic utility of this protocol was further demonstrated by efficient synthesis of
the derivatives of thiacloprid and flutianil.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was financial supported by National Key Research Program of China
(2017YFD0200505, 2016YFD0300709ꢀ02) and National Natural Science Foundation of China
(21272071). This work was also partly supported by the Shanghai Foundation of Science and
Technology (15431902100) and Fundamental Research Funds for the Central Universities
(222201718004).
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Table of Contents Entry
Functionalized thiazolidines were obtained via the rearrangement reactions of
5-arylidenethiazolidin-4-ones at room temperature.