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org/OrgLett Letter

Synthesis of Sulfur-Containing Oxindoles by Photoinduced Alkene

Difunctionalization via Sulfur 1,2-Relocation
Cong Lu, Rui Chen, Rui Wang, Dong Jing, and Ke Zheng*
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ABSTRACT: Organosulfur compounds are prevalent in various

natural products, which have been widely applied in agrochemicals
and pharmaceuticals. Herein, a new approach for the efficient
construction of sulfur-containing oxindoles by photoinduced
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alkene difunctionalization via sulfur 1,2-relocation is developed.

The method exhibited a high functional group tolerance and broad
substrate compatibility. A library of sulfur-containing oxindole
derivatives were synthesized under mild conditions (metal-,
photocatalyst-, and additive-free). Mechanistic investigations
revealed this photochemical process was triggered by the formation
of an EDA complex of oxindole enolates with a redox-active ester, and the in situ generation of alkenes from the C−S bond cleavage
of β-sulfanyl radicals was a key step in this transformation.

O rganosulfur compounds are highly important building

blocks or reagents in chemistry, finding widespread
applications in organic synthesis and drug discovery.1−3 Highly
Scheme 1. Difunctionalization of In Situ Generated Alkenes
via Sulfur 1,2-Relocation

selective activation or functionalization of the C−S bond can

accurately modify useful sulfur-containing natural products and
drug molecules.2,3 Recently, diverse transformations through
transition-metal-catalyzed C−S bond activation and cleavage
have been well developed.4 Radical reactions have become
valuable and essential tools in organic synthesis due to their
compatibility with various functional groups.5 In the past
decade, photochemistry has emerged with milder and more
versatile radical-based protocols.6 With the development of
photochemistry, photoinduced C−S bond activation has also
flourished rapidly.7−11 A diversity of radical precursors have
been designed to generate carbon radicals through radical-
mediated C−S bond cleavage. These radical precursors
consisted of bivalent sulfur salts,7 iodide aryl sulfide,8
xanthate,9 and so on. The C−S bond cleavage process of
these precursors is irreversible via the release of a suitable
leaving group. Alternatively, selective C−S bond cleavage of a
β-sulfanyl radical can also provide facile access to carbon
radicals or alkenes, which has recently drawn increased
attention (Scheme 1a).3,10,11 Fragmentation of the β-sulfanyl
radical is prone to generate a new carbon�carbon double
bond and a thiyl radical, which is a reversible process.3a This
reversible process has been applied to the isomerization of
alkene and allyl sulfide, the [3 + 2] cycloaddition reaction,10 Received: December 12, 2022
and the selective synthesis of alkene.11 Published: February 1, 2023
With the development of radical chemistry in recent
decades, different types of radical-mediated alkene difunction-
alization reactions with bifunctional reagents have been
achieved.12 However, the utilization of the β-fragmentation

© 2023 American Chemical Society https://doi.org/10.1021/acs.orglett.2c04189

750 Org. Lett. 2023, 25, 750−755
Organic Letters pubs.acs.org/OrgLett Letter

of a sulfanyl radical for alkene difunctionalization has never 1, entries 3−6). No product was observed when the reaction
been reported. The β-sulfur fragmentation process allows for was conducted under 460 nm light irradiation (Table 1, entry
the introduction of a new π-bond, especially when the reaction 7). The yield was further improved to 82% when the reaction
is conducted without a good hydrogen atom donor. The temperature was increased to 40 °C (Table 1, entry 8).
transformation is very fast when unstable carbon-centered Reducing the amount of RAE 2 to 1.5 equiv gave a slightly
radicals are involved. The newly formed carbon�carbon decreased yield (67%, Table 1, entry 9). Control experiments
double bond can be easily converted into other functional indicated that a nitrogen atmosphere and light were crucial for
groups.3a We hypothesize that if a suitable radical precursor
the reaction, and no reaction was observed without light
could be identified and smoothly converted into an unstable β-
sulfanyl radical I, further fragmentation of I would generate an irradiation (Table 1, entries 10 and 11, respectively).
alkene II and a thiyl radical (Scheme 1b). Then, the With the optimal conditions established, a variety of 3-aryl-
regioselective addition of the thiyl radical onto II will take substituted oxindoles were investigated first (Schem 2). Both
place at the terminal position (R1 = H) of the less hindered electron-donating and electron-withdrawing groups on the aryl
C�C bond to give a stable benzyl radical III,13 which can be
rapidly trapped by another suitable radical to give a Scheme 2. Scope of Oxindolesa
difunctionalization product (Scheme 1b).14 Herein, we report
a facile photoinduced difunctionalization of in situ generated
alkenes by a radical−radical coupling reaction. A variety of
alkenes together with thiyl radicals are efficiently produced via
C−S bond cleavage of a β-sulfanyl radical under redox-neutral
conditions. The reaction proceeds under mild conditions with
an absence of metals, photocatalysts, and other additives and
shows a high functional group tolerance and broad substrate
compatibility. A variety of sulfur-containing 3,3′-disubstituted
oxindole derivatives with diversifie functional groups are
synthesized in one step.
We first tested our hypothesis by employing 3-phenyl-
indolin-2-one 1 and β-sulfanyl redox-active ester (RAE) 2 as
model substrates. To our delight, the desired difunctionaliza-
tion product 3 was observed in a 64% yield in THF under
purple light-emitting diode (LED) irradiation at room
temperature (Table 1, entry 1). The halide TBAI could
accelerate the reaction, but a lower yield was obtained with
some unknown byproducts (54% yield, Table 1, entry 2). The
solvents and irradiation wavelengths were also investigated.
The best outcome was obtained with the desired product 3 in a
76% yield in 2-Me-THF under 415 nm light irradiation (Table

Table 1. Screening of the Reaction Conditionsa

entry variation from the “conditions” yield (%)b

1 using THF as the solvent 64%
2 with 0.5 mol % TBAI in THF 54%
3 using DCM as the solvent 61%
4 using MeCN as the solvent 54%
5 none 71%
6c with a 415 nm LED 76%
7c with a 460 nm LED NR
8d with a 415 nm LED at 40 °C 82%
9e with a 415 nm LED and 1.5 equiv of 2 67%
10 with air 58%
a
11 without light NR Reaction conditions are as follows: oxindole (0.1 mmol), RAE 2 (0.2
mmol), 2-Me-THF (1.0 mL), N2, and irradiation with 10 W LEDs
a
Reaction conditions are as follows: oxindole 1 (0.1 mmol), RAE 2 (415 nm) at 40 °C for 48 h. The dr value of the products was 1:1.
b
(0.2 mmol), solvent (1.0 mL), N2, and irradiation with 10 W LEDs at The reaction was performed with 405 nm irradiation, and the
room temperature for 36 h. TBAI = tetra-n-butylammonium iodide. reaction time was 96 h. cThe reaction time was 60 h. dThe reaction
b
Isolated yield. cThe reaction time was 72 h. dThe reaction time was time was 96 h. eThe reaction was performed with 395 nm irradiation,
48 h. e1.5 equiv of 2 was used. and the reaction time was 96 h.

751 https://doi.org/10.1021/acs.orglett.2c04189
Org. Lett. 2023, 25, 750−755
Organic Letters pubs.acs.org/OrgLett Letter

substituents at the 3-position of the oxindoles were compatible Scheme 3. Scope of RAEsa
with the reaction, affording the corresponding products in
good to excellent yields (4−11). o-Methyl-substituted oxindole
(10) gave the product in a high yield with a longer reaction
time due to its steric hindrance. Oxindoles with different
substituted groups on the phenyl ring, such as fluoro, methyl,
methoxy, chloro, bromo, and trifluoromethyl, were all well
tolerated, giving the corresponding products in good to
excellent yields (12−21). Among them the 7-substituted
oxindoles generally gave better results (19−21). The different
substituent groups on the nitrogen of the oxindoles had a great
effect on the reaction. The Boc-substituted oxindole (22) gave
an excellent yield, while no reaction was observed for the
methyl-substituted oxindole (23), with starting material
remaining. When 3-alkyl-substituted oxindoles (24−28) were
introduced to the system, moderate yields were obtained (45−
55%) due to their lower reactivities. 3-Phenyl benzofuranone
(29) and oxazolinone (30) were also compatible with this
system, giving the corresponding products with 96% and 67%
yields, respectively.
This transformation also displayed a remarkable scope with
respect to β-sulfanyl RAEs (the alkene precursors). As shown
in Scheme 3, both electron-donating groups (Me, OMe, SMe,
and CH3CONH; 31−34, 40, and 41) and electron-with-
drawing groups (OCF3, F, Cl, CF3, CN; 35−39, respectively)
were well tolerated and generated the corresponding products
in good to excellent yields (73−96%). The multifluoro-
substituted RAE (42) was also identified as a suitable partner
for this reaction (90% yield). Various RAEs with heterocycles
and condensed rings were next investigated. 1-Naphthyl- and
2-naphthyl-substituted RAEs were well tolerated, giving rise to
the corresponding products in excellent yields (43 and 44).
The RAEs with five-membered heterocycles, such as furan
(45), thiofuran (46 and 47), pyrrole (48), isoxazole (49),
pyrazole (50), and thiazole (51), could also conveniently
convert to the corresponding products in medium to high
yields. Quinoline- (52), pyridine- (53), and indole-substituted a
Reaction conditions are as follows: oxindole 1 (0.1 mmol), RAE (0.2
(54) RAEs gave the corresponding products in acceptable mmol, 2.0 equiv), 2-Me-THF (1.0 mL), N2, and irradiation with 10 W
yields (48−77%). To our delight, the 1,2-disubstituted olefin LEDs (415 nm) at 40 °C for 48 h. Unless otherwise stated, the dr
precursor (55) was also tolerated, generating the tetrasub- value of the products was 1:1. bThe reaction time was 60 h. cThe
stituted product in a 77% yield. A series of thiyl radical reaction time was 72 h. dThe reaction time was 96 h. eThe reaction
precursors were identified as suitable coupling partners for this was performed with 395 nm irradiation, and the reaction time was 96
methodology. As shown in Scheme 3, both primary and h. fThe reaction time was 24 h.
secondary alkyl thiyl radicals were well tolerated, affording the
corresponding products in high yields (80−92%, 56−60). The and 2 had no absorption around 400 nm (lines a, b, and d;
thiyl radicals with diverse functional groups were well tolerated Figure 1a). A significant red-shift of the UV−vis absorption
in the reaction (61, 62, and 64). The thiyl radical with an N- spectra was observed for the mixture of the base, 1, and 2
Boc amine group (63) was incompatible with the system, and (lines c, e, and f; Figure 1a). Moreover, we found that the
no product was observed. The benzyl thiyl radical (65) gave a reaction mixture turned a marked yellow color when the
moderate yield under standard conditions. Though the stable colorless solution was under light irradiation for a while. The
aryl thiyl radical (66) was compatible, only a 29% yield was color of the solution changed from light yellow to yellowish
obtained. The low yield might attribute to the existence of brown when the base TBAPhth was added to the reaction
competitive reactions, such as the direct coupling of an mixture (Figure 1a). These results indicated that the enolate of
oxindole radical with an aryl thiyl radical. Notably, this facile oxindole 1 would form an EDA complex with 2, which had
method was also illustrated by the gram-scale synthesis of strong absorption in the visible region. This phenomenon was
product 3 with a 77% yield (Figure 1b; for more details, see the consistent with our previous work.14 Because no additional
SI). base was added in the reaction, we considered that the reaction
Since there were only two substrates in the system without was started by the slow decomposition of RAE, which could
any additional additives or catalysts, we speculated that this release a catalytic amount of base Phth−. The decomposition
photocatalytic process was triggered by the formation of an experiments of RAE 2 under 415 and 425 nm LED irradiation
EDA complex. The UV−vis spectroscopic measurements were were investigated. While only 13% RAE 2 was recovered under
first performed to evaluate this hypothesis (Figure 1a). The 415 nm irradiation, almost no RAE 2 was decomposed under
results showed that oxindole 1, RAE 2, and the mixture of 1 425 nm irradiation (for more detail, see the SI, Figure S5).
752 https://doi.org/10.1021/acs.orglett.2c04189
Org. Lett. 2023, 25, 750−755
Organic Letters pubs.acs.org/OrgLett Letter

Based on the above mechanistic results and our previous

studies,14 the proposed mechanism is depicted in Figure 2.

Figure 2. Proposed mechanism.

Upon visible light irradiation, a catalytic amount of base Phth−

is released from the decomposition of RAE C under 415 nm
light irradiation. The base Phth− abstracts a hydrogen atom
from the oxindole A to form the corresponding enolate B.
Then, the EDA complex D of enolate B with RAE C is formed.
The secondary irradiation of EDA complex D generates the
oxindole radical E and unstable radical F via a SET process.
Then, rapid β-fragmentation of unstable radical F generates the
alkene G and the thiyl radical H. The regioselective addition of
Figure 1. Control experiments and gram-scale synthesis. (a) UV−vis the thiyl radical H to the less hindered position of the C�C
absorption. (b) Gram-scale synthesis. (c) Crossover experiment. (d) bond of the alkene forms stable benzyl radical I. Finally, the
Radical clock experiment. TBA = tetra-n-butylammonium.
selective coupling of the benzyl radical I and oxindole radical E
affords the difunctionalization product J.
These results indicated that the RAE 2 was not stable and In summary, we have developed a highly selectively
would be decomposed slowly under 415 nm light. The photoinduced alkene difunctionalization via sulfur 1,2-
decomposition process would provide a catalytic amount of relocation for the construction of sulfur-containing 3,3′-
Phth− as a base at an early stage of the reaction. These also disubstituted oxindoles. Over 50 sulfur-containing oxindoles
could explain why no products were observed for the reactions with diverse functional groups were synthesized under mild
under the blue and green light irradiation (for more data, see conditions (metal-, PC-, and additive-free). The reaction
the SI, Table S1). shows a high functional group tolerance and broad substrate
To gain some additional insights into the mechanism, compatibility. The transformation included a C−S bond
several control experiments were conducted (Figure 1c and d). cleavage process of the β-sulfanyl radical. The in situ generated
The crossover experiments were performed using oxindoles 1 alkenes were found to be key intermediates in the trans-
and 67 as substrates. When 1.0 equiv of styrene 68 was added, formation. We believe that our method provides a less-
the crossover product 3 was obtained in a 34% yield. When 3.0 expensive, nontoxic alternative to classical photocatalyst
equiv of styrene 68 was added, the crossover product 3 was reactions.
obtained in a 57% yield. The target product 34 and the β-
fragmentation product alkene 69 were also detected in the
reaction. These results suggested that the reaction underwent a
■ ASSOCIATED CONTENT
Data Availability Statement
C−S bond cleavage of the β-sulfanyl radical process, and an
alkene was generated in the reaction. Moreover, the radical The data underlying this study are available in the published
clock experiment was carried out with 3.0 equiv of 70. The article and its Supporting Information.
ring-opening product 71 was obtained in a high yield (89%), *
sı Supporting Information

suggesting that the reaction underwent a radical process. In The Supporting Information is available free of charge at
addition, we found that TEMPO could direct the oxidation of https://pubs.acs.org/doi/10.1021/acs.orglett.2c04189.
oxindole 1 to generate dimerization product 72 without light. General procedures, analytical data, and NMR spectra
The dimerization product 72 could regenerate the oxindole (PDF)
radical at 40 °C. These results indicated that the oxindole
radical was a long-lived intermediate in the reaction (for more
detail, see the SI, Figure S7).13 All these observations provided
direct evidence that the reaction underwent a radical pathway,
■ AUTHOR INFORMATION
Corresponding Author
and the generation of alkenes from C−S bond cleavage of β- Ke Zheng − Key Laboratory of Green Chemistry and
sulfanyl radicals was a key step in this transformation. Technology, Ministry of Education, College of Chemistry,
753 https://doi.org/10.1021/acs.orglett.2c04189
Org. Lett. 2023, 25, 750−755
Organic Letters pubs.acs.org/OrgLett Letter

Sichuan University, Chengdu, Sichuan 610064, P. R. China; bonds: recent advances in C−C bond formation reactions via C−S
orcid.org/0000-0002-3345-7715; Email: kzheng@ bond cleavage under photoredox catalysis. Chem. Asian J. 2020, 15,
scu.edu.cn 3637−3659. (c) Chu, X.-Q.; Ge, D.; Cui, Y.-Y.; Shen, Z.-L.; Li, C.-J.
Desulfonylation via Radical Process: Recent Developments in Organic
Authors Synthesis. Chem. Rev. 2021, 121, 12548−12680.
(4) For selected reviews, see: (a) Wang, L.; He, W.; Yu, Z.
Cong Lu − Key Laboratory of Green Chemistry and Transition-metal mediated carbon-sulfur bond activation and trans-
Technology, Ministry of Education, College of Chemistry, formations. Chem. Soc. Rev. 2013, 42, 599−621. (b) Modha, S. G.;
Sichuan University, Chengdu, Sichuan 610064, P. R. China Mehta, V. P.; Van der Eycken, E. V. Transition metal-catalyzed C−C
Rui Chen − Key Laboratory of Green Chemistry and bond formation via C−S bond cleavage: an overview. Chem. Soc. Rev.
Technology, Ministry of Education, College of Chemistry, 2013, 42, 5042−5055. (c) Lou, J.; Wang, Q.; Wu, P.; Wang, H.;
Sichuan University, Chengdu, Sichuan 610064, P. R. China Zhou, Y.-G.; Yu, Z. Transition-metal mediated carbon-sulfur bond
Rui Wang − Key Laboratory of Green Chemistry and activation and transformations: an update. Chem. Soc. Rev. 2020, 49,
Technology, Ministry of Education, College of Chemistry, 4307−4359.
Sichuan University, Chengdu, Sichuan 610064, P. R. China (5) For selected reviews, see: (a) Prier, C. K.; Rankic, D. A.;
Dong Jing − Key Laboratory of Green Chemistry and MacMillan, D. W. C. Visible Light Photoredox Catalysis with
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