A Mild Method for Access to α-Substituted Dithiomalonates through C-Thiocarbonylation of Thioester: Synthesis of Mesoionic Insecticides

Article abstract of DOI:10.1002/adsc.202100369

An efficient method for targeting a variety of symmetrical and asymmetrical α-substituted dithiomalonates (DTMs) is described, utilizing 1H-imidazole-1-carbothioates as reactive acylating agents and MgBr₂?OEt₂/DBU or LiHMDS for soft or hard enolization conditions of thioesters, respectively. The utility of this methodology was demonstrated through the synthesis of the pyridopyrimidine mesoionic insecticides: triflumezopyrim and dicloromezotiaz. (Figure presented.).

Full text of DOI:10.1002/adsc.202100369

Title: A Mild Method for Access to α-Substituted Dithiomalonates
through C-Thiocarbonylation of Thioester: Synthesis of Mesoionic
Insecticides
Authors: Xinyue Yang, Yanrong Ma, Huiming Di, Xiaochen Wang, Hui
Jin, Do Hyun Ryu, and Lixin Zhang
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202100369
Link to VoR: https://doi.org/10.1002/adsc.202100369

10.1002/adsc.202100369
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
A Mild Method for Access to α-Substituted Dithiomalonates
through C-Thiocarbonylation of Thioester: Synthesis of
Mesoionic Insecticides
Xinyue Yang,a Yanrong Ma,a Huiming Di,a Xiaochen Wang,a Hui Jin,a,* Do Hyun
Ryu,b,* and Lixin Zhanga,*
a
Institute of Functional Molecules, Shenyang University of Chemical Technology; National-Local Joint Engineering
Laboratory for Development of Boron and Magnesium Resources and Fine Chemical Technology; Liaoning Province
Key Laboratory of Green Functional Molecular Design and Development, Shenyang, 110142, China
Fax: (+86)-24-8938-5213; e-mail: hjin@syuct.edu.cn, zhanglixin@syuct.edu.cn
b
Department of Chemistry, Sungkyunkwan University, Suwon 440-746, Korea
Fax: (+82)-31-290-5976; e-mail: dhryu@skku.edu
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: An efficient method for targeting a variety of
symmetrical and asymmetrical α-substituted
dithiomalonates (DTMs) is described, utilizing 1H-
imidazole-1-carbothioates as reactive acylating agents and
MgBr2·OEt2/DBU or LiHMDS for soft or hard enolization
conditions of thioesters, respectively. The utility of this
methodology was demonstrated through the synthesis of
Thiocarbonylation is a nice procedure for thioesters
synthesis[5] and C-acylation of enolates has been
recognized as a fundamental and useful C-C bond
forming reaction to synthesize 1,3-dicarbonyl
compounds.[6] Therefore, we became interested in
whether α-substituted DTMs could be obtained
through the direct C-thiocarbonylation of thioester
enolate. Nature freely uses the enzymatic
decarboxylative activation of malonic acid half-
thioesters (MAHTs) to generate simple thioester
enolates during the biosynthesis of polyketides and
fatty acids (Scheme 1, b).[7] Inspired and motivated
by nature, synthetic chemists have paid considerable
attention toward exploring mild enolate forming
methods.[8] The formation of enolates through the use
of a Lewis acid and a weak base has been termed
“soft” enolization, which does not employ a strong
base (used in “hard” enolization) and therefore can be
conducted under mild conditions.[9] For example,
Coltart used MgBr2·Et2O and i-Pr2NEt to generate
thioester enolates from simple thioesters via soft
enolization. These were then employed in Claisen
condensations with alkyl acid chlorides and N-
acylbenzotriazoles to obtain β-keto thioesters in good
yield (Scheme 1, c).[9] However, to the best of our
knowledge, there has been no precedent with regard
to the C-thiocarbonylation of thioester enolates to
produce DTMs. The scarcity of such transformations
may be due to the lack of effective C-
thiocarbonylating agents. Only one specific example
of the C-thiocarbonylation of a ketone enolate was
reported by the Hale group, where S-phenyl O-
pentafluorophenyl carbonothioate was used as a C-
thiocarbonylating agent.[10]
the
pyridopyrimidine
mesoionic
insecticides:
triflumezopyrim and dicloromezotiaz.
Keywords: α-substituted dithiomalonates; soft enolization;
thioester enolates; C-thiocarbonylation; mesoionic
insecticides
Thioesters play an important role in many
biosynthetic reactions[1] and have also become
attractive for synthetic chemists as they can be
readily transformed into a variety of other functional
groups such as aldehydes, ketones, esters, and
amides.[2] Additionally, due to smaller orbital overlap
of the C(2p) and S(3p) orbitals, the α-proton acidity
of thioesters is higher than that of the related
oxoesters, making thioesters useful enolate precursors
in nature as well as in the laboratory. In this
connection, dithiomalonates (DTMs) have been
widely employed as reactivity-enhanced malonate
surrogates in many C−C bond forming reactions.[3]
Despite their prevalence, few synthetic methods exist
with regard to α-substituted DTMs and very few
examples to asymmetrical analogues. They have so
far been prepared through the thioesterification of the
corresponding α-substituted malonic acid,[4a] which
were
prepared
through
a
two-step
α-
alkylation/hydrolysis process[4b,c] (Scheme 1, a).
1
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10.1002/adsc.202100369
Advanced Synthesis & Catalysis
Herein, we report the first application of 1H-
imidazole-1-carbothioates as efficient C-
understanding of this reaction, a control experiment
was carried out in which thioester 1a and S-ethyl 1H-
imidazole-1-carbothioate (2c) was combined with 1.5
equiv. of MgBr2·OEt2; the desired product was
obtained only in 44% yield after 24 h (Table 1, entry
4), thus we hypothesized 2 equiv. of Lewis acid was
essential to activate both the thioester 1a and
acylating agent 2c (Figure 1, b).
thiocarbonylating agents enabling mild C-acylation of
thioester enolates to produce a series of symmetrical
and asymmetrical α-substituted DTMs via soft and
hard enolizations (Scheme 1, d). Furthermore, the
synthetic utility of the obtained α-substituted DTMs
were highlighted through their successful application
toward mesoionic insecticide synthesis.
Encouraged by the above results, further
optimization of the reaction conditions was carried
out. Firstly, a range of bases Et3N, DABCO, and
DBU were examined (Table 1, entries 5-7); DBU
gave the highest yield of 80% (entry 7). Furthermore,
screening solvents (Table 1, entries 8-11) determined
chlorobenzene to be the best choice, providing 3a in
93% yield, which was identified as the optimized
conditions (entry 11). Additionally, other Lewis acids
Zn(OTf)2, Fe(OTf)3, and Sc(OTf)3 were examined in
place of MgBr2·OEt2 under the optimized conditions
(Table 1, entries 12-14). With Zn(OTf)2 and
Fe(OTf)3, no reaction occurred (entries 12 and 13),
however, Sc(OTf)3 can promote the reaction despite
the yield was only 30%. (entry 14). We then applied
these optimized “soft” conditions to other 1H-
imidazole-1-carbothioates 2d-2g (Table 1, entries 15-
18). S-Alkyl 1H-imidazole-1-carbothioates 2d-2f
were tolerated well, providing the desired products
3b-3d with yields of 85, 83, and 68%, respectively
(entries 15-17). However, S-(p-tolyl) 1H-imidazole-1-
carbothioate 2g produced product 3e only in 21%
yield (entry 18). In addition, the reaction of 1a with
2c under “hard” enolization conditions were also
explored by using a strong base LiHMDS; however,
in the absence of MgBr2·OEt2 at rt (see the
Supporting Information for optimization details).
Excitingly, with 1.5 equiv. of LiHMDS in toluene, the
desired product 3a was obtained with 72% yield
(Table 1, entry 19) in a much shorter reaction time (2
h). We then applied these “hard” conditions with 2b
and 2g (Table 1, entries 20 and 21) which reveal low
yields under “soft” conditions (Table 1, entries 2 and
18). Extraordinary, carbonodithioate 2b provided the
desired product 3e in 44% yield (entry 20). However,
with 2g, no desired product 3e was obtained (entry
21). It was noteworthy that the reaction conditions of
our hard enolization/C-acylation reaction were
extremely mild, allowing for the use of untreated
reagent-grade solvent at room temperature rather than
anhydrous conditions at ultra-low-temperatures.
Scheme 1. Pre-existing method for access to α-substituted
DTMs and α-acylation of thioester enolates.
Based on the above-mentioned literature,[9,10] we
anticipated that carbonothioates could also be used as
acyl donors in the C-thiocarbonylation of thioester
enolates. To explore the use of soft enolization in
DTM synthesis, thioester 1a was firstly combined
with S-ethyl O-(4-nitrophenyl) carbonothioate 2a,
MgBr2·OEt2 (2.5 equiv.) and i-Pr2NEt in CH2Cl2
(Table 1, entry 1); disappointingly, no apparent
reaction took place. Then, carbonodithioate 2b was
investigated and the desired product 3e was obtained
only in 4% yield (Table 1, entry 2). However, when
S-ethyl 1H-imidazole-1-carbothioate 2c was deployed
as an acylating agent, the desired product 3a was
obtained cleanly with a promising yield of 75%
(Table 1, entry 3). Considering that the leaving group
abilities of 2a, 2b, and 2c are related to the pKa
values of each conjugate acid, 4-nitrophenol, 4-
methylthiophenol, and imidazole (Figure 1, a), the
result of 2c was unexpected.[11] To gain a deeper
Table 1. Optimization of reaction conditions.[a]
2
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10.1002/adsc.202100369
Advanced Synthesis & Catalysis
Figure 1. a) pKa values of 4-nitrophenol, 4-
methylthiophenol, and imidazole. b) Mechanistic
considerations in the Lewis acid-promoted C-acylation
with 1H-imidazole-1-carbothioates.
Having established the optimized reaction
conditions, we investigated the reactions of a variety
of α-substituted thioesters 1 with S-ethyl 1H-
imidazole-1-carbothioate 2c under both “soft” and
“hard” conditions (Scheme 2). As summarized in
Scheme 2, regardless of the electronic and steric
nature of the aromatic substituent on α-phenyl
substituted thioesters, most of the products 3a-3n
were obtained in moderate to high yields, while soft
conditions generally gave higher yields. In addition to
α-phenyl substituted thioesters, naphthyl and
thiophenyl substituted thioesters were also smoothly
converted into the desired products 3o-3q with good
yields (63-75%). Aryloxyl and alkoxyl substituted
thioesters were also tolerated and yielded the desired
products 3r and 3s in moderate yields under soft
conditions (3r, 70%; 3s, 55%), while hard conditions
gave reduced yields by comparison (3r, 22%; 3s,
15%). Aliphatic substituted thioesters were also
tested; the desired products 3t and 3u were obtained
with lower yields (“soft” condition: 3t, 30%; 3u, 47%,
“hard” condition: 3t, 40%; 3u, 62%). To our delight,
challenging α,α-disubstituted thioesters also worked
via soft enolization to yield the corresponding α,α-
disubstituted DTMs 3v-3x (in 30-37% yields),
although the chemical yield still requires further
optimization.
yield
entry
2
Lewis acid
base
solvent
3
(%)[b]
1
2
2a
2b
MgBr2·OEt2
MgBr2·OEt2
i-Pr2NEt
i-Pr2NEt
CH2Cl2
CH2Cl2
3a
3e
NR[c]
4
3
4[d]
5
2c
2c
2c
2c
2c
2c
2c
2c
2c
2c
2c
2c
2d
2e
2f
MgBr2·OEt2
MgBr2·OEt2
MgBr2·OEt2
MgBr2·OEt2
MgBr2·OEt2
MgBr2·OEt2
MgBr2·OEt2
MgBr2·OEt2
MgBr2·OEt2
Zn(OTf)2
Fe(OTf)3
i-Pr2NEt
i-Pr2NEt
Et3N
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
PhMe
THF
3a
3a
3a
3a
3a
3a
3a
3a
3a
3a
3a
3a
3b
3c
3d
3e
3a
3e
3e
75
44
67
6
DABCO
DBU
24
7
80
8
DBU
38
9
DBU
76
10
11
12
13
14
15
16
17
18
19[e]
20[e]
21[e]
DBU
MeCN
PhCl
83
DBU
93
DBU
PhCl
NR[c]
NR[c]
30
DBU
PhCl
Sc(OTf)3
DBU
PhCl
MgBr2·OEt2
MgBr2·OEt2
MgBr2·OEt2
MgBr2·OEt2
-
DBU
PhCl
85
DBU
PhCl
83
DBU
PhCl
68
2g
2c
2b
2g
DBU
PhCl
21
LiHMDS
LiHMDS
LiHMDS
PhMe
PhMe
PhMe
72
-
44
-
0
[a] Unless otherwise noted, the reactions were carried out
with 1a (0.2 mmol), 2 (0.4 mmol), Lewis acid (0.5 mmol),
and base (0.6 mmol) in 1 mL of solvent.
[b] Isolated yield.
[c] No reaction occured.
[d]
The reaction was carried out with 1.5 equiv. of
MgBr2·Et2O (0.3 mmol).
[e] The reaction was carried out with 1a (0.2 mmol), 2b (0.4
mmol), and LiHMDS (0.3 mmol) in toluene (1 mL) at rt
for 2 h.
3
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10.1002/adsc.202100369
Advanced Synthesis & Catalysis
triflumezopyrim and dicloromezotiaz have become
commercial insecticides for hemipteran and
lepidopteran pest control, respectively (Scheme 3,
a).[14] So far, these mesoionic compounds have been
prepared through the condensation of an
appropriately substituted 2-aminopyridine with an
active malonate derivative such as malonyl chlorides
or 2,4,6-trichlorophenyl malonates (Scheme 3, b).[12]
However, these malonate derivatives are not ideal
from the perspective of preparation, storage, or atom
economy. Compared with malonyl chlorides, DTMs
3 are much more stable that can be stored for several
months at rt. Additionally, the DTMs 3 are better
than 2,4,6-trichlorophenyl malonates in terms of atom
economy. Recognizing the great potential of using
DTMs as new intermediates for mesoionic compound
synthesis, we tested some of our obtained DTMs 3
and report our primary results.
Scheme 3. Synthesis of mesoionic insecticides.
a
Scheme 2. Substrate scope.
Isolated yield, unless
Initially, DTM 3a was combined with substituted
2-aminopyridine 5a and refluxed in chlorobenzene
for 3 h. Excitingly, the desired product 6a was
obtained in an excellent yield of 93% after simple
crystallization (Table 2, entry 1). Then, DTMs 3h and
3n were applied toward the synthesis of
triflumezopyrim 6b and dicloromezotiaz 6c, and gave
the desired products in 87 and 62% yields,
respectively (Table 2, entries 2 and 4). These results
were remarkably better than those reported in
literature[12b] (58 and 13%) where bis(2,4,6-
trichlorophenyl) malonates were employed (Table 2,
entries 3 and 5). Additionally, DTM 3h and 2-
aminopyridine 5d also provided the desired product
6d in a good yield of 85% (Table 2, entry 6).
otherwise noted, the reactions were carried out with 1 (0.2
mmol), 2 (0.4 mmol), MgBr2·Et2O (0.5 mmol), and DBU
(0.6 mmol) in 1 mL of chlorobenzene at rt. b Isolated yield,
unless otherwise noted, the reactions were carried out with
1 (0.2 mmol), 2 (0.4 mmol), and LiHMDS (0.3 mmol) in 1
mL of toluene at rt for 2 h. c The reactions were carried out
with 1 (1.0 mmol) at 50 oC for 5 days.
To demonstrate the synthetic utility of this
methodology, the obtained α-aryl substituted DTMs 3
were
applied
toward
the
synthesis
of
pyridopyrimidine mesoionic insecticides. Mesoionic
insecticides are a hot spot with regard to the
discovery of new insecticides.[12] Since DuPont first
disclosed the application of pyridopyrimidine
mesoionic compounds as agricultural insecticides in
2009,[13a] numerous researchers from BASF,[13b]
Bayer,[13c] Nippon Kayaku,[13d] Sumitomo,[13e] and
Syngenta[13f] et al., have devoted extensive attention
Table 2. Synthesis of mesoionic insecticides using α-
substituted DTMs.[a]
to
the
field.
Among
these
compounds,
4
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10.1002/adsc.202100369
Advanced Synthesis & Catalysis
In conclusion, we developed an efficient C-
thiocarbonylation reaction of α-substituted thioesters
using 1H-imidazole-1-carbothioates as acylating
agents via soft and hard enolization. The process can
give direct access to a variety of symmetrical and
asymmetrical α-substituted DTMs under mild
conditions using untreated reagent-grade solvent at rt.
Most of the obtained α-substituted DTMs were bench
stable with higher reactivities than those of related
oxomalonates and thus will be used as reactivity-
yield
entry
3 or 4
5
solvent
time (h)
6
(%)[b]
enhanced malonate surrogates
for various
applications in organic synthesis. As examples, the
obtained α-aryl substituted DTMs were successfully
applied toward the synthesis of the pyridopyrimidine
mesoionic insecticides triflumezopyrim 6b and
dicloromezotiaz 6c, demonstrating higher efficiency
than pre-existing methods.
1
2
3a
3h
5a
5b
PhCl
PhCl
3
6
6a
93
6b 87
6b 58
3[c]
4
4a
3n
4b
3h
5b
5c
5c
5d
toluene
6
6
2
2
mesitylene
toluene
6c
6c
62
13
5[c]
6
mesitylene
6d 85
Experimental Section
[a] The reactions were carried out with 3 (0.2 mmol) and 5
(0.1 mmol) in 1.5 mL of solvent.
Synthesis of α-substituted dithiomalonates (3)
General procedure under “soft” conditions:
[b] Isolated yield.
[c] Data collected from the literature.[12b]
Moreover,
a
gram scale synthesis of
To a stirred solution of thioester 1 (0.2 mmol, 1 equiv.) in
PhCl (1 mL) was added MgBr2·OEt2 (0.5 mmol, 2.5
equiv.), DBU (0.6 mmol, 3 equiv) and 1H-imidazole-1-
carbothioates 2 (0.4 mmol, 2 equiv.) successively. The
reaction mixture was stirred for 24 h at rt and then was
added acetic acid (4 equiv.). The reaction mixture was
stirred for additional 5 min then was partitioned between
EtOAc (2 mL) and H2O (2 mL). The aqueous phase was
extracted with EtOAc (2 × 10 mL). The combined organic
extracts were washed with brine, dried over Na2SO4, and
concentrated in vacuo to give the crude product, which was
purified by column chromatography to afford the desired
product 3.
triflumezopyrim 6b was achieved successfully
(Scheme 4). Firstly, the C-thiocarbonylation of 1h
was performed at 4.6 and 9.6 mmol scale under both
“soft” and “hard” conditions respectively to produce
the key intermediate DTM 3h. Yields of 3h were
even higher than those using small scale reactions
(Scheme 4, a). Then, the condensation of 3h with 2-
aminopyridine 5b at gram-scale was carried out
(Scheme 4, b), affording triflumezopyrim 6b in a
84% isolated yield from crystallization (see the
Supporting Information for details).
General procedure under “hard” conditions:
To a stirred solution of thioester 1 (0.2 mmol, 1 equiv.) in
PhMe (1 mL) was added LiHMDS (0.3 mL, 1 M sol. in
THF, 0.3 mmol) and 1H-imidazole-1-carbothioates 2 (0.4
mmol, 2 equiv.) successively at rt. The reaction mixture
was stirred for 2 h at rt and then was quenched with
saturated NH4Cl solution (2 mL) and extracted with ethyl
acetate (2 × 10 mL). The combined organic layer was
washed with water, brine and dried over Na2SO4. After
removing the solvent, the residue was purified by column
chromatography to afford the desired product 3.
Synthesis
of
mesoionic
insecticide:
triflumezopyrim (6b)
To S,S-diethyl 2-(3-(trifluoromethyl)phenyl)propanebis
(thioate) 3h (67.2 mg, 0.2 mmol) in PhCl (1.5 mL) was
added N-(pyrimidin-5-ylmethyl)pyridin-2-amine 5b (18.6
mg, 0.1 mmol). The reaction mixture was refluxed for 6 h.
After cooling down to room temperature, the reaction
Scheme 4. Gram-scale synthesis of triflumezopyrim.
5
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10.1002/adsc.202100369
Advanced Synthesis & Catalysis
mixture was added petroleum ether. The precipitate was
filtered off, washed and dried to provide triflumezopyrim
6b as a yellow crystal (34.6 mg, 87% yield).
Org. Chem. 1985, 50, 4877; d) A. Lida, S. Nakazawa,
T. Okabayashi, A. Horii, T. Misaki, Y. Tanabe, Org.
Lett. 2006, 8, 5215.
[7] a) R. J. Heath, C. O. Rock, Nat. Prod. Rep. 2002, 19,
581; b) M. B. Austin, M. Izumikawa, M. E. Bowman,
D. W. Udwary, J. L. Ferrer, B. S. Moore, J. P. Noel, J.
Biol. Chem. 2004, 279, 45162.
Acknowledgements
This work was supported by the Science and Technology
Project of Liaoning Education Department (No.
LQ2020025) and Nanning Scientific Research and
Technology Development Program (No. 20201043) and by
National Research Foundation of Korea (NRF) grants (No.
NRF-2019R1A4A2001440, No. 2019R1A2C2087018).
[8] a) N. Utsumi, S. Kitagaki, C. F. Barbas, Org. Lett. 2008,
10, 3405; b) J. H. Park, J. H. Hun Sim, C. E. Song, Org.
Lett. 2019, 21, 4567; c) S. J. Sauer, M. R. Garnsey, D.
M. Coltart, J. Am. Chem. Soc. 2010, 132, 13997.
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