A novel approach toward thioester bond formation mediated by N,N’ -diisopropylcarbodiimide in water

Article abstract of DOI:10.1080/10426507.2020.1799367

A simple and efficient method has been developed for the synthesis of thioesters from carboxylic acids and thiols using N,N'-diisopropylcarbodiimide (DIC). The reactions were carried out in water as an environmentally friendly and green solvent. The devel

Full text of DOI:10.1080/10426507.2020.1799367

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/gpss20
A novel approach toward thioester
bond formation mediated by N,N’ -
diisopropylcarbodiimide in water
Nadia Fattahi , Najmeh Varnaseri & Ali Ramazani
To cite this article: Nadia Fattahi , Najmeh Varnaseri & Ali Ramazani (2020): A novel approach
toward thioester bond formation mediated by N,N’ꢀ-diisopropylcarbodiimide in water, Phosphorus,
Sulfur, and Silicon and the Related Elements, DOI: 10.1080/10426507.2020.1799367
To link to this article: https://doi.org/10.1080/10426507.2020.1799367
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2020.1799367
A novel approach toward thioester bond formation mediated by
N,N’-diisopropylcarbodiimide in water
Nadia Fattahia, Najmeh Varnaseria, and Ali Ramazania,b
b
aDepartment of Chemistry, University of Zanjan, Zanjan, Iran; Research Institute of Modern Biological Techniques (RIMBT), University
of Zanjan, Zanjan, Iran
ABSTRACT
ARTICLE HISTORY
Received 5 March 2020
Accepted 18 July 2020
A simple and efficient method has been developed for the synthesis of thioesters from carboxylic
acids and thiols using N,N’-diisopropylcarbodiimide (DIC). The reactions were carried out in water
as an environmentally friendly and green solvent. The developed procedure presents an economic,
efficient, mild, and very simple protocol for thioesterification reaction in aqueous media.
KEYWORDS
Thioesterification; N,N’-
diisopropylcarbodiimide;
aqueous reactions
GRAPHICAL ABSTRACT
Introduction
acid,[13] thiocarbonylation of aryl halides and thiols with
carbon monoxide in the presence of palladium catalyst,[14]
the cross-dehydrogenative coupling of aldehydes with disul-
fides or thiols in the presence of a radical initiator, with the
Thioesters are valuable building blocks in chemical biology
and useful intermediates in organic synthesis that are
applied for acyl transfer,[1,2] peptide coupling,[3] coupling
partners in organometallic reactions[4,5] and also as protect-
ing groups for thiols.[6] Thioesters are also significant inter-
mediates in a variety of biological systems,[7–9] and are
broadly exist in many medicinal agents and biologically
active compounds.[10] Therefore, in the past few years, con-
sidering the biological and chemical importance of thioest-
ers, numerous methods for their synthesis have been
developed, such as condensation of thiol and carboxylic acid
by dehydrating reagents,[11] trans-thioesterification of active
carboxylic acid derivatives with thiol,[12] thioesterification of
combination
of
N-Heterocyclic
carbene
catalyst,
Dess–Martin periodinane, as well as metal catalysts such as
FeBr2 and CuCl.[15–20]
Recently, the utilization of water as an environmentally
benign solvent has received remarkable interest in organic
synthesis, owing to its very favorable qualities such as safety,
nontoxicity, availability, environmental friendliness, and
greater chemo-selectivity compared to organic sol-
vents.[21–24] Moreover, it is unnecessary to dry reagents, sol-
vents, and substrates before utilization in aqueous media.
carboxylic acids with thiol in the presence of trifluoroacetic Thus, time, drying agents, and energy can be saved.
CONTACT Ali Ramazani
aliramazani@gmail.com; Nadia Fattahi
nadia.fatahi89@yahoo.com
Department of Chemistry, University of Zanjan, P.O. Box
45195-313, Zanjan, Iran.
Supplemental data for this article is available online at https://doi.org/10.1080/10426507.2020.1799367.
ß 2020 Taylor & Francis Group, LLC

2
N. FATTAHI ET AL.
Scheme 1. Thioesterification of carboxylic acids in water.
In connection with our studies on the evaluation and bearing halogen substituents such as –Br and –Cl at the
development of various types of organic reactions in aque-
ous media,[25–37] we recently presented the preparation of
two abundant and important functional groups "ester and
amide" in the presence of DIC in water as a safe and easily
available solvent.[38] In a continuation of this work, we wish
to report herein a new strategy for thioester bond formation
in water. This procedure presents simple and efficient access
to highly functionalized thioesters under mild and environ-
mentally friendly conditions (Scheme 1).
para and meta positions also reacted smoothly with thiol
samples to form the corresponding thioesters in excel-
lent yields.
In the present work, we also used benzoic acids bearing
–NO2 and –CN moieties, but the yields were poor (10–20%)
in these cases.
The important role of water in the progress of reaction,
was also demonstrated by additional experiments in the
presence of dichloromethane as an example of an organic
solvent. In this regard, the obtained product from the reac-
tion of DIC with benzoic acid as an acid moiety was lower
as compared to in a water solvent. Because, acid cannot ion-
ize in organic solvents, thus, its activity is low, and some
Results and discussion
Using water as a green reaction medium has received
remarkable interest, from the environmental and economical amount of acid remains in the reaction mixture. As a result,
point of view. It is clear that, in a water solvent, a hydrogen the yield of thioester was reduced. In addition, it is neces-
ion of carboxylic acid is transported to a water molecule.
Therefore, in aqueous media reactivity of carboxylic acids is
increased, thus, carboxylate ion can react easily and quickly
with DIC. Giving this fact, in the previous work, we selected
DIC as a suitable coupling reagent and water as a green and
efficient solvent, for the synthesis of two valuable, abundant
and basic functional moieties in nature.[38] In the present
study, we aimed to investigate thioester bond formation, in
connection with our previous study.[38] In this regard, the
reaction of thiol (1 mmol), carboxylic acid (1 mmol), and
DIC (1 mmol) in water leads to the formation of corre-
sponding thioester in high yield. The structures of the prod-
sary to mention that thiol cannot be ionized in the organic
solvents, thus, its nucleophilic reactivity was lower in
organic solvents, compared to water.
In addition, in order to prove the importance of DIC as
an efficient coupling reagent in the present work, we used
DCC instead of DIC. However, the reaction time was higher
and further purification was needed.
Based on our experiments and previous studies,[37,38]
a
possible mechanism for thioester bond formation in the
water solvent was proposed (Scheme 2). Firstly, carboxylic
acid A in water ionizes to give hydronium ion and carboxyl-
ate ion. Then, intermediate B is formed from the reaction of
carboxylate ion with DIC D. Finally, the nucleophilic attack
of thiol to intermediate B provides thioester C.
Moreover, we compared the performance of our proced-
ure with some other previous methods in thioester bond
formation (Table 2). It can be clearly seen that our proced-
ure is superior to most of the other procedures in terms of
yield and reaction conditions.
1
ucts were deduced from their IR, H NMR, and 13C NMR
spectra (see experimental section). For example, the IR spec-
trum of entry 1 showed strong absorption at 1671 cmꢀ1
which is attributed to the carbonyl group of thioester
1
(O ¼ C–S). The H-NMR spectrum of entry 1 showed sig-
nals at d ¼ 7.54-8.38 ppm for aromatic protons of phenyl
1
and naphthyl groups. The H-decoupled 13C NMR spectrum
of entry 1 is in agreement with the proposed structure.
In view of the success of the above-mentioned reaction,
we explored the scope of this promising reaction by varying
the structure of the carboxylic acid and thiol component. As
presented in Table 1, both aromatic and aliphatic carboxylic
acids reacted easily with DIC to give the corresponding N-
acylurea derivatives B,[37] and then in the presence of thiol
functionality, aromatic and aliphatic samples, derivatives B
can be easily converted to the related thioesters at room
temperature in high yields. As shown in Table 1, benzoic
acids containing electron-donating groups such as methyl
and tert-butyl provided corresponding thioesters in high
Experimental section
Materials and methods
All chemical compounds were purchased from Sigma-
Aldrich (USA), Fluka (Switzerland), and Merck (Germany),
and were used without additional purification. The methods
used to monitor the reactions are TLC and NMR. The FTIR
spectra were obtained using a Jasco 6300 FTIR spectrometer
in the range of 400–4000 cmꢀ1 with samples dispersed in
KBr pellets at room temperature. H and 13C NMR spectra
1
yields (entry 3 and entry 8). N-acylurea derivatives B, were acquired in CDCl3 on a Bruker DRX-250 Avance

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
Table 1. Thioesterification reactions of carboxylic acids in water.a
O
O
O
O
N
C
N
R2 SH
8 h
H2O, R.T.
R2
R1 OH
A
R1
S
R1
N
B
N
H
1 h
C
Entry
1
Acid
Thiol
Product
Yieldb
Ref.
[39]
O
SH
95
O
OH
S
[40]
O
2
SH
93
O
OH
S
Cl
Cl
-
O
3
4
SH
93
92
O
OH
S
[41]
O
O
O
SH
OH
O
S
O
O
O
Cl
Cl
[42]
O
5
91
O
O
SH
SH
O
OH
S
Cl
O
Cl
[43]
O
6
7
94
91
O
O
OH
S
[40]
O
SH
OH
S
S
-
O
8
94
SH
SH
O
OH
[44]
O
9
91
92
O
OH
16
S
16
[45]
O
10
O
O
SH
O
OH
S
O
O
Br
Br
(continued)

4
N. FATTAHI ET AL.
Table 1. Continued.
O
R1 OH
A
O
O
O
N
C
N
R2 SH
8 h
H2O, R.T.
1 h
R2
R1
S
R1
N
B
N
H
C
Entry
11
Acid
Thiol
Product
Yieldb
Ref.
O
93
–
SH
O
OH
S
Cl
Cl
aReaction conditions: carboxylic acid (1 mmol), thiol (1 mmol), DIC (1 mmol), 2 mL H2O, R.T.
bIsolated yield.
spectrometer at 250.13 and 62.90 MHz, respectively. The Ethyl 2-((3-chlorobenzoyl) thio) acetate (entry 4)
1
Supplemental Materials contains sample H and 13C NMR
White solid; m.p: 51-53 ꢁC; IR (KBr) 2966, 1614, 1246, 1463,
1686, 668 cmꢀ1 1H NMR (250.13 MHz, CDCl3) d 1.15 (t,
and IR spectra of the known products (Figures S1–S23).
;
J ¼ 5.2 Hz, 3H), 3.81 (s, 2 H), 4.20 (m, 2 H), 7.36-7.94 (m,
3H), 8.06 (s, 1 H); 13C NMR (62.90 MHz, CDCl3): d 14.1,
31.5, 61.9, 128.0, 128.7, 129.0, 129.3, 131.4, 131.8,
168.4, 189.0.
General procedure for the synthesis of thioester
in water
A typical experimental procedure is described below. To stirred
solution of 1 mmol of carboxylic acid in H2O at room tempera-
ture, was added DIC (1 mmol), and then the reaction mixture
was stirred for 1 h. After this time, the 1 mmol of thiol was
added and the reaction mixture was stirred for 8 h at room
temperature. Then, the water was removed by filtration and the
obtained solid washed with lukewarm water several times in
order to eliminate the by-product diisopropyl urea (DIU).
Ethyl 2-((4-chlorobenzoyl) thio) acetate (entry 5)
1
White solid; m.p: 53-55 ꢁC; H NMR (250.13 MHz, CDCl3)
d 1.15 (t, J ¼ 5.5 Hz, 3H), 3.87 (s, 2 H), 4.21 (m, 2 H), 7.44-
8.03 (m, 4H); 13C NMR (62.90 MHz, CDCl3): d 14.1, 31.4,
61.7, 128.1, 128.7, 129.2, 129.4, 131.6, 131.8, 168.4, 189.2.
S-(naphthalen-2-yl) naphthalene-2-carbothioate
(entry 6)
S-(naphthalen-2-yl) benzothioate (entry 1)
White solid; m.p: 105-107 ꢁC; IR (KBr) 3062, 1671, 1447,
White solid; m.p: 165-167 ꢁC; IR (KBr) 3052, 1708, 1425, 1171,
1
1204, 903, 684 cmꢀ1; H NMR (250.13 MHz, CDCl3) d 7.54-
1
1061, 771 cmꢀ1; H NMR (250.13 MHz, CDCl3) d 7.46-8.46 (m,
8.38 (m, 12H); 13C NMR (62.90 MHz, CDCl3): d 125.5,
126.7, 127.2, 127.5, 127.8, 128.6, 128.8, 131.4, 133.7, 134.9,
136.5, 137.1, 190.2.
13 H), 9.16 (d, J¼ 8.5 Hz, 1H); 13C NMR (62.90 MHz, CDCl3):
d 124.5, 124.9, 125.7, 126.2, 126.5, 126.8, 127.5, 127.7, 128.1,
128.4, 128.8, 131.9, 132.1, 134.0, 135.5, 188.8.
S-(naphthalen-2-yl) 4-chlorobenzothioate (entry 2)
S-phenyl benzothioate (entry 7)
White solid; m.p: 129-131 ꢁC; IR (KBr) 2926, 1662, 1425,
1
White solid; m.p: 55-57 ꢁC; H NMR (250.13 MHz, CDCl3)
1
1203, 875 cmꢀ1; H NMR (250.13 MHz, CDCl3) d 7.47-8.09
d 7.54-8.18 (m, 10 H); 13C NMR (62.90 MHz, CDCl3): d
(m, 11H); 13C NMR (62.90 MHz, CDCl3): d 126.6, 127.3,
127.8, 128.1, 129.3, 129.7, 130.1, 134.2, 135.6, 137.1, 190.5.
127.8, 128.9, 129.1, 129.4, 131.2, 131.9, 135.0, 189.8.
S-(naphthalen-2-yl) 4-methylbenzothioate (entry 3)
S-(naphthalen-2-yl) 4-(tert-butyl) benzothioate (entry 8)
White solid; m.p: 72-74 ꢁC; IR (KBr) 3062, 2924, 1669, 1205, White solid; IR (KBr) 3082, 2926, 2857, 1668, 1215, 908,
857 cmꢀ1 1H NMR (250.13 MHz, CDCl3) d 2.44 (s, 3H), 818 cmꢀ1 1H NMR (250.13 MHz, CDCl3) d 1.37 (s. 9H),
; ;
7.29-8.06 (m, 11H).13C NMR (62.90 MHz, CDCl3): d 21.8, 7.51-8.05 (m, 11H); 13C NMR (62.90 MHz, CDCl3): d 31.1,
124.9, 126.5, 1271, 127.6, 127.8, 128.0, 128.8, 129.5, 131.5, 35.2, 125.7, 126.5, 127.1, 1267.4, 127.8, 128.0, 128.7, 131.5,
133.4, 134.1, 135.0, 144.7, 190.1.
134.9, 157.2, 189.9.

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
Scheme 2. Proposed mechanism for thioesterification reaction in water.
Table 2. Comparison of the results with some other previously reported methods in thioesterification reactions.
Entry
Catalyst & Conditions
Time
Yield (%)a
Refs.
[46]
[47]
[48]
[14]
[18]
[49]
[50]
1
2
3
4
5
6
7
8
PPh3/N-chlorobenzotriazole (NCBT), CH2Cl2, 0 ꢁC to room temperature
40–200b
80–95
67–94
76–97
43–97
31–94
49–75
51–98
91–94
Sulfonated porous carbon, 100 ꢁC, Solvent-free
45b
Trifluoromethanesulfonic acid, toluene, reflux
6–48c
18c
Pd(OAc)2/PPh3, triethylamine, phosphonium salt ionic liquid, carbon monoxide, 100 ꢁC
Tert-butyl hydroperoxide, CuCl, 100 ꢁC, N2, H2O
1c
Cu(OAc)2ꢂ2H2O, tert-butyl hydroperoxide, 95 ꢁC
6–17c
12c
Poly(3,4-dimethyl-5-vinylthiazolium), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), phenazine, DMF, 27 ꢁC
N,N’-diisopropylcarbodiimide, H2O, room temperature
8c
This work
aIsolated yield.
bTime (min).
cTime (h).
S-(naphthalen-2-yl) octadecanethioate (entry 9)
Conclusions
White solid; m.p: 56-58 ꢁC; IR (KBr) 3085, 2918, 2848, 1686,
In summary, the reported method offers a cost-effective, easy,
ecofriendly, and effective route for the preparation of thioesters
from carboxylic acids and thiols in the presence of DIC in
water as a green solvent. The developed method is general for a
variety of carboxylic acids and thiols including aliphatic and
aromatic samples, to afford the desired thioesters. Considering
the importance of the thioester bond, we hope that our new
approach may inspire researchers to develop alternative meth-
ods for the formation of thioester bond in the coming years.
1
1636, 1471, 697 cmꢀ1; H NMR (250.13 MHz, CDCl3) d 0.87
(t, J ¼ 6.7 Hz, 3H), 1.26 (m, 26 H), 1.55 (m, 2 H), 1.73 (m,
2 H), 2.69 (m, 2 H), 7.44-7.98 (m, 7H); 13C NMR
(62.90 MHz, CDCl3): d 14.1, 22.6, 25.6, 29.0, 29.3, 29.6, 31.9,
43.8, 125.7, 126.2, 126.5, 127.0, 127.4, 127.7, 128.7, 128.9,
130.9, 134.2, 192.0.
Ethyl 2-((4-bromobenzoyl) thio) acetate (entry 10)
1
Yellow solid; m.p: 40-42 ꢁC; H NMR (250.13 MHz, CDCl3)
d 1.14 (t, J ¼ 5.2 Hz, 3H), 3.80 (s, 2 H), 4.20 (m, 2 H), 7.36-
8.04 (m, 4H); 13C NMR (62.90 MHz, CDCl3): d 14.1, 31.2,
61.7, 128.0, 128.7, 129.0, 129.3, 131.2, 131.8, 168.4, 190.0.
Conflict of interest
The authors hereby declare that, there was no conflict of
interest in the present study.
Funding
S-(naphthalen-2-yl) 3-chlorobenzothioate (entry 11)
This work was supported by "Iran National science Foundation: INSF".
White solid; m.p: 129-131 ꢁC; IR (KBr) 3082, 2960, 1668, 1418,
1
1195, 875 cmꢀ1; H NMR (250.13 MHz, CDCl3) d 7.55-8.04 (m,
ORCID
11H); 13C NMR (62.90 MHz, CDCl3): d 125.6, 126.6, 127.3,
127.5, 128.0, 128.9, 130.1, 131.2, 133.6, 135.0, 189.2.
Ali Ramazani
http://orcid.org/0000-0003-3072-7924

6
N. FATTAHI ET AL.
Intermolecular Radical Reaction in Water. Chemistry 2005, 11,
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