Synthesis of 2-(Arylthio)indolenines via Chemoselective Arylation of Thio-Oxindoles with Arynes

Article abstract of DOI:10.1002/adsc.202000308

A chemoselective S-arylation reaction of thio-oxindoles with arynes is presented. The reaction was performed under mild conditions and provided a straightforward synthesis of 2-(arylthio)indolenines in good to excellent yields. Besides, this simple operat

Full text of DOI:10.1002/adsc.202000308

Title: Facile Synthesis of 2-(Arylthio)indolenines via Chemoselective
Arylation of Thio-oxindoles with Arynes
Authors: Adi Saputra, Rong Fan, Tuanli Yao, Jian Chen, and Jiajing
Tan
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10.1002/adsc.202000308
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Synthesis of 2-(Arylthio)indolenines via Chemoselective
Arylation of Thio-oxindoles with Arynes
Adi Saputra,a Rong Fan,a Tuanli Yao,b* Jian Chen,a and Jiajing Tana*
a
Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029,
China.
E-mail: tanjj@mail.buct.edu.cn
College of Chemistry and Chemical Engineering, Shaanxi University of Science and Technology, 6 Xuefu Road,
b
Weiyang District, Xi’an, Shaanxi 710021, China.
E-mail: yaotuanli@sust.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))
A chemoselective S-arylation reaction of thio-oxindoles with should allow for the expansion of chemical space via
arynes is presented. The reaction was performed under mild developing new scaffolds of thioimidates that are difficult to
conditions and provided a straightforward synthesis of 2- synthesize otherwise.
(arylthio)indolenines in good to excellent yields. Besides, this
simple operational protocol is not only scalable but also has
good functional group compatibilities and substrate scope.
Thus, our protocol
Keywords: Chemoselective S-arylation; thio-oxindoles;
Aryne; 2-(Arylthio)indolenines; Chemical space
known that indoles, indolenines, oxindoles, and their
derivatives are endowed with diverse applications in
pharmaceutical chemistry.[7] For instance, the indole
motifs bearing C2-thioether scaffolds, although less
explored from synthetic perspectives, have displayed
promising applications as potential anti-HIV, anti-
cancer, anti-inflammatory, and anti-bacterial agents.[8]
In fact, the expansion of chemical space through the
generation of structural diversity still represented the
key piece in discovering new drugs.[9] Given their
importance along with abovementioned gap in
technology, our aim of this project was to identify an
efficient S-arylation process that was capable of
delivering divergent sulfur-containing indolenines and
explore the reactivities of these moieties.
Introduction
Thioimidates are not only widespread in bioactive
molecules, but also important synthetic intermediates
toward various nitrogen and sulfur-containing
compounds.[1] Classical methods to prepare such
structural units relied on reactions of sulfur
nucleophiles with C-N multiple bonds containing
components including imidoyl chlorides, ketenimines
or nitriles (Scheme 1a).[2] An alternative strategy was
to react carbon source with thioamide derivatives.
Although many advances have been witnessed on S-
alkylation reactions to access alkyl thioimidates,[3]
synthesis of aryl thioimidates via chemoselective S-
arylation continues to be underdeveloped.[4] A critical
challenge would be the side N-arylation reaction, as
thioamides are bidentate nucleophiles containing both
thio-carbonyl and N-H groups.[1-2] Only until recently,
Olofsson and co-workers reported an efficient S-
arylation reaction of acrylic secondary thioamides
using diaryliodonium salts, whereas cyclic substrates
gave less satisfying selectivities.[5] To the best of our
knowledge, the S-arylation of cyclic thioamides
The past decades have witnessed the renaissance of
innovative aryne chemistry.[10-11] Under mild
conditions, aryne species could undergo a variety of
unique
transformations
(including
insertion,
cycloaddition, multicomponent reaction, etc.) to build
molecular complexity in high efficacy.[10-11] Given our
group’s long-standing interests in aryne and
organosulfur chemistry,[12] the authors questioned
whether it would be feasible to employ arynes to
remained to be an unsolved task in chemical literatures, achieve the direct S-arylation of thioamides. We
which was probably due to the poor conjugation of
nitrogen lone pair in thioamide moiety and resulting
lower nucleophilicity of sulfur.[6]
Among cyclic thioamide motifs, we were
particularly interested in thio-oxindoles. It’s well-
hypothesized that polarizable aryne species with their
low-lying LUMO should offer enough “soft”
electrophilic nature, and might pair reactivity with the
“soft” sulfur center of thioamides to enable the
chemoselective S-arylation (Scheme 1b).[13-14] As such,
1
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10.1002/adsc.202000308
Advanced Synthesis & Catalysis
we herein would like to report our recent efforts in
developing the chemoselective arylation reaction of
thio-oxindoles with arynes to provide direct access to
structurally diverse 2-(arylthio)indolenine derivatives.
Lowering the reaction temperature to 0 °C only led to
a trace amount of 3a (entry 5), while increasing it to
70 oC gave the desired product in a 92% isolated yield
(entry 7). Finally, decreasing the amount of CsF or
switching the reactant ratio failed to improve the
overall reaction outcomes (entries 8-9).
Table 2. Substrate Scope for Thio-oxindoles.[a]
Scheme 1. Synthesis of Thioimidates.
Results and Discussion
Table 1. Optimization of the Reaction Conditions.[a, b]
Temp.
(°C)
Yield
(%)
Entry
“F-”/Base
Solv.
1
2
CsF
MeCN
THF
25
25
25
25
0
69
60
KF/18-Crown-6
3
TBAF
THF
48
4
Cs2CO3/18-Crown-6
THF
28
5
CsF
CsF
CsF
CsF
CsF
MeCN
MeCN
MeCN
MeCN
MeCN
trace
85
92(92)[c]
6
50
70
70
70
7
8[d]
9[e]
75
90
[a] 1a (0.11 mmol), 2a (0.13 mmol) and F- source (0.33
mmol) solvent (2.0 mL) for 4 h. [b] Determined by 1H NMR
using an internal standard. [c] Isolated yield. [d] CsF (2.0
equiv.). [e] 1.0 equiv. of 2a used.
[a]
Standard reaction conditions: 1a-1p (0.28 mmol, 1.0
equiv.), 2a (0.34 mmol, 1.2 equiv.), CsF (3.0 equiv.) in
We commenced our investigations with 3,3-
MeCN (3 mL) at 70 oC for 4 h under N2.
dimethyldihydroin-dole-2-thione
(1a)
and
2-
(trimethylsilyl)-phenyl trifluoromethanesulfonate (2a)
as model substrates (Table 1). To our delight, the
reaction proceeded in the presence of cesium fluoride
(CsF) under N2 atmosphere, gave the S-arylation
product 3a exclusively in 69% yield (entry 1). Various
aryne formation conditions were then investigated,
and none of them increased the chemical yields
(entries 2-4). To further improve the reaction
efficiency, the temperature effect was evaluated.
With optimal conditions in hands, we next explored
the substrate scope of 2-indolinethiones (Table 2). A
variety of substituent groups were well-tolerated to
offer the desired products (3a-3o) in good yields. First,
we examined 2-indolinethiones containing several
acyclic substituent groups on 3 and 3’ positions, all of
which were successful coupling partners (3a-3f, 87-
2
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10.1002/adsc.202000308
Advanced Synthesis & Catalysis
[a] Standard reaction conditions: 1 (0.28 mmol, 1.0 equiv.),
2b-2j (0.34 mmol, 1.2 equiv), CsF (3.0 equiv.) in MeCN
(3 mL) at 70 oC for 4 h under N2.
92% yields). Substrates bearing spirocyclic motifs
were also amenable, providing good yields of the
desired products (3g-3j). Interestingly, the
heterocyclic fragments, which were well known to
react with arynes, proved to be tolerated under
standard reaction conditions (3k-3l).[15] Substrates
containing acetal groups as latent synthetic handles at
the 3-position also proceeded smoothly to give
corresponding products 3m and 3n in 89% and 87%
yields, respectively. Moreover, the Diels-Alder
product was not observed, when the substrate with
hetero-diene moiety was employed (3o). Finally, 6-
bromo-substituted thio-oxindole 1p was utilized, and
the absolute configuration of corresponding product
3p was unambiguously determined by X-ray
diffraction studies.[16] It should be noted that complete
chemoselectivity for bond formation at the sulfur was
observed for all substrates.
Variation of the aryne species was evaluated next
(Table 3). A series of functionalized thio-oxindoles
readily reacted with symmetrical arynes to afford the
coupled products in 83-90% yields (4a-4e). 3-
methoxybenzyne also underwent the reaction
smoothly to give 4f with significant regioselectivity,
which is in accordance with the distortion/interaction
model reported by Houk, Garg and et al.[17] Generally,
the electronic effects of the substituent groups on
arynes had no significant impacts on reaction
outcomes. Furthermore, when unsymmetrical arynes
were reacted with thio-oxindoles, the desired products
(4g-4i) were obtained as regioisomeric mixtures.
Further studies to gain insights into the reactivities
of 1a with other aryne precursors were performed
(Scheme 2). We reacted 1a with benzyne that was
generated from aprotic diazotization of anthranilic
acid followed by thermal decomposition of the
diazonium carboxylate, gave 3a with 86% isolated
yield. Treating 1a with aryne that was thermally
generated via hexadehydro-Diels-Alder gave product
5 in 45% yield.[18] Given that the transformation
occurred under base-free conditions, it should offer
great synthetic flexibility. Next, we investigated the
reactivity of indoline-2-thiones with three possible
nucleophilic sites. In all cases, the aromatization
products were obtained (7a-7d, 73-87% yields), which
offered a complement method to direct sulfenylation
of indoles that usually proceeded at 3-positions.
Table 3. Substrate Scope for Aryne Precursors.[a]
Scheme 2. Reaction with Other Substrates.
3
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10.1002/adsc.202000308
Advanced Synthesis & Catalysis
The synthetic utilities of our strategy toward
treated with CsF at 70 oC, we observed no changes in
the chemical shift of C-S double bond in 13C NMR
spectrum.[21] Based on this finding along with
experimental results in Scheme 2, a plausible
mechanism was proposed. Initially, the nucleophilic
addition of 1 to in-situ formed aryne species gave the
key zwitterionic intermediate A. The proton transfer
eventually generated the final product.
expanding the chemical space have been demonstrated
in various aspects (Scheme 3). First, an additive-based
robustness screen was undertaken.[19] The experiments
were performed in the presence of one equivalent of
additives, and 3a was still obtained in good yields
under otherwise same conditions. Meanwhile, the
additives were mostly recovered, suggesting that our
protocol be potentially well-suited for complex
substrates. Undeniably, the observed functional group
tolerance and preservation attributed to the inherent
nucleophilic scale differentiation.[20] Second, we used
1c (1.0 gram) with a slight excess of the aryne
precursor 2a, and the desired product 3c was obtained
in 82% yield (1.01 gram) at gram scale.
Scheme 4. NMR Experiments and Proposed Mechanism.
Conclusion
In summary, we have reported a chemoselective S-
arylation reaction of thioamides under transition-metal
free conditions. This mild protocol has been applied to
a range of structurally diverse building blocks as well
as being scaled effectively to gram scale. The
robustness screen and derivatization studies further
demonstrated its potentials in exploring chemical
space for medicinal chemistry use. We thus strongly
believe that the operational simplicity and broad
functional group tolerance of our protocol should
make it suitable for target synthesis projects in both
academic and industrial settings.
Experimental Section
Scheme 3. Synthetic Applications.
Preparation of Compounds 3 and 4: In an oven-dried 10
mL schlenk tube, a mixture of thio-oxindole (0.28 mmol,
1.0 equiv.), CsF (3.0 equiv.), in acetonitrile (3 mL) was
added aryne precursor (0.34 mmol, 83 µL, 1.2 equiv.) under
Moreover, sulfide 7a could be readily oxidized to
sulfone 8 and sulfoxide 9 in 90% and 86% yields,
respectively. Product 3b could be also converted to
sulfoximine 10 in 74% yield via N and O-transfer.
Finally, when 3a was reacted with excess reductants or
Grignard reagents, it remained stable even at reflux
conditions with 95-98% recovery yields of 3a.
o
N2. The resulting mixture was stirred at 70 C for 4 hours.
The reaction mixture was then cooled to room temperature
and diluted with dichloromethane (10 mL). The organic
layer was washed with water (10 mL, three times). The
combined organic layers were dried over with Na2SO4. The
solvent was removed under reduced pressure, and the
resulting residue was purified by column chromatography to
afford the desired products.
To probe the reaction mechanism, the NMR
experiment was performed (Scheme 4). When 1h was
4
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10.1002/adsc.202000308
Advanced Synthesis & Catalysis
Acknowledgements
Spiliotopoulos, C. Nevado, A. Caflisch, ACS Cent. Sci.
2018, 4, 180-188.
JJT is grateful for the support of the National Natural Science
Foundation of China (21702013) and the Fundamental Research
Funds for the Central Universities (XK1802-6, buctrc201721). T.
L. Yao thanks Shaanxi University of Science and Technology for
financial support of this research (BJ15-33).
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Advanced Synthesis & Catalysis
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[21] The chemical shift changes of C7 and C8 might be
caused by the hydrogen bonding interaction between 1h
with CsF.
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
6
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Advanced Synthesis & Catalysis
FULL PAPER
Synthesis of 2-(Arylthio)indolenines via
Chemoselective Arylation of Thio-oxindoles with
Arynes
Adv. Synth. Catal. 2020, Volume, Page – Page
Adi Saputra,a Rong Fan,a Tuanli Yao,b* Jian Chen,a
and Jiajing Tan a*
7
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