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org/OrgLett Letter

Arenethiolate-Catalyzed 1,5-HAT of Aryl Halides: Synthesis of

γ‑Spirolactams
Wei Xiao, Shengyun Liu, Yuhui Lin, Xiaoyu Zhou,* and Jie Wu*
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ABSTRACT: γ-Spirolactam is a privileged building block that is found

in a wide range of natural products and bioactive compounds. Herein,
we report an arenethiolate-catalyzed 1,5-HAT of aryl halides to obtain
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γ-spirolactams through a SET reduction/intramolecular 1,5-HAT/

cyclization/HAT process. This protocol features metal-free conditions
and a broad substrate scope, furnishing the γ-spirolactams in moderate
to excellent yields. Notably, aryl bromides, aryl chlorides and even aryl
fluorides are well tolerated in this transformation. A mechanism
involving arenethiolate as a SET catalyst is proposed based on DFT
calculation.

S pirolactam is a privileged building block that is found in a

wide range of natural products and bioactive compounds
(Scheme 1a). For example, Curtachalasins B is isolated from
the endophytic fungus Xylaria curta E10 harbored in the plant
Solanum tuberosum.1 Ubrogepant is used in the treatment of
migraines.2 Compound C is demonstrated as a progesterone
receptor agonist,3 and compound D exhibits anticonvulsant
activity.4 Due to their established significance, the synthesis of
spirolactams has garnered considerable attention from the
synthetic chemistry community. Numerous strategies such as
metal-,5 organo-,6 visible light-7 and electro-promoted8 trans-
formations have been given to access spirolactams. Despite
these achievements, the development of convenient and metal-
free methods for the preparation of spirolactams is of
significance and highly desired.
Synergistic photoredox/HAT catalysis has been developed
as one of the most efficient methods to rapidly assemble
organic compounds with structural diversity and complexity.9
Recently, Shang’s group demonstrated that arenethiolates
could be photoactivated under visible light to perform as
both HAT catalysts and strongly reducing electron-donating
redox catalysts to reduce trifluoromethyls.10 Soon after,
Molander’s group utilized this strategy to access difluorinated
oxindole derivatives and heteroaryl-substituted oxindoles.11
Encouraged by these achievements and the importance of γ-
spirolactams, we envisioned that a SET reduction/intra-
molecular 1,5-HAT/cyclization/HAT process of aryl halides
with arenethiolate as a strong single- electron-reduction
catalyst would be feasible for the construction of γ-
spirolactams. Notably, Xu’s group developed the Ir(ppy)3
promoted 1,5-HAT of aryl iodides to access γ-spirolactams.12
However, precious Ir(ppy)3 and an additional HAT donor γ-
terpinene were essential for this transformation. Furthermore,
the substrate scope was limited to aryl iodide derivatives. The
activation of strong chemical bonds such as C−Br, C−Cl, and
C−F bonds could not be achieved through this method. The
application of this method to access γ-spirolactams suffered
from these limitations. Herein, we report a visible-light-
induced metal-free approach to generate γ-spirolactams
catalyzed by arenethiolate through a SET reduction/intra-
molecular 1,5-HAT/cyclization/HAT process. Notably, aryl
bromides, aryl chlorides, and even inert aryl fluorides undergo
the reactions smoothly.
We initially explored this arenethiolate-catalyzed metal-free
1,5-HAT reaction of N-allyl-N-(2-bromophenyl)-
cyclohexanecarboxamide (1a) in the presence of 20 mol %
4-methoxybenzenethiol (T1), 3.0 equiv of HCO2Na, 1.0 equiv
of KHCO3, and a 390 nm Kessil lamp in DMSO at room
temperature for 24 h. To our delight, desired γ-spirolactam 2a
was formed in 46% yield (Table 1, entry 1). Compared with
Xu’s work,12 which required 90 h for complete conversion, the
reaction time decreased remarkably with similar efficiency.
This method is also tolerant of ambient atmosphere as only a
slight reduction in the yield was displayed when changing the
reaction environment to air (Table 1, entry 2). Higher yields
were attained when formate salts were changed from HCO2Na
to HCO2Cs (Table 1, entries 3 and 4). No better results could
be obtained when 4-methylbenzenethiol (T2), methyl 2-
mercaptobenzoate (T3), and cyclohexylmercaptan (T4) were
tested (entries 5−7). The yield of 2a was increased to 85%
Received: February 23, 2024
Revised: March 29, 2024
Accepted: April 2, 2024

© XXXX American Chemical Society https://doi.org/10.1021/acs.orglett.4c00685

A Org. Lett. XXXX, XXX, XXX−XXX
Organic Letters pubs.acs.org/OrgLett Letter

Scheme 1. Representative Examples of Natural and
Bioactive Spirolactams and Arenethiolate Reactions
when switching the base to K2CO3 (Table 1, entries 8−12).
Inferior results were detected in other solvents (Table 1,
entries 13−16).
With the optimized conditions in hand, the generality of this
arenethiolate-catalyzed metal-free 1,5-HAT reaction was then
investigated, and the results are summarized in Scheme 2. To

Scheme 2. Scope Exploration for the Reaction of N-

Allylanilide Bromides 1a,b

Table 1. Optimization Studies for the Synthesis of γ-

Spirolactamsa

entry thiol base formate salts solvent yield (%)b

1 T1 KHCO3 HCO2Na DMSO 46
2c T1 KHCO3 HCO2Na DMSO 31
3 T1 KHCO3 HCO2K DMSO 51
4 T1 KHCO3 HCO2Cs DMSO 68
a
5 T2 KHCO3 HCO2Cs DMSO 55 Unless otherwise noted, reaction conditions are as follows: 1 (0.2
6 T3 KHCO3 HCO2Cs DMSO 67 mmol), T1 (0.04 mmol), K2CO3 (0.2 mmol), HCO2Cs (0.6 mmol),
7 T4 KHCO3 HCO2Cs DMSO 22 DMSO (2.0 mL), 390 nm Kessil lamp, 24 h, under a N2 atmosphere.
b
8 T1 KOH HCO2Cs DMSO 64
Isolated yields cHCO2Cs (1.0 equiv).
9 T1 DBU HCO2Cs DMSO 62
10 T1 Et3N HCO2Cs DMSO 58 our delight, aryl chlorides and even inert aryl fluorides could
11 T1 K2CO3 HCO2Cs DMSO 85 participate in this reaction efficiently, providing product 2a in
12 T1 Cs2CO3 HCO2Cs DMSO 40 70 and 61% yields, respectively. Anilide bromides with
13 T1 K2CO3 HCO2Cs MeCN 28 electron-donating substituents (Me, OMe) on the aromatic
14 T1 K2CO3 HCO2Cs DCE trace ring were well tolerated, providing the corresponding γ-
15 T1 K2CO3 HCO2Cs THF 35 spirolactams in good yields (2b−2d). Similarly, anilide
16 T1 K2CO3 HCO2Cs EA trace bromides with electron-withdrawing groups (OCF3, CF3, F,
Cl, CO2Me, and CN) on the aromatic ring gave the
a
Unless otherwise noted, reaction conditions are as follows: 1a (0.2 corresponding products (2e−2j) in moderate to good yields.
mmol), thiol (0.04 mmol), base (0.2 mmol), formate salts (0.6 Notably, a reduced amount of HCO2Cs is required to give
mmol), solvent (2.0 mL), 390 nm Kessil lamp, 24 h, under a N2 atm. higher yields of products 2f−2h. Anilide chlorides with m-
b
Isolated yields. cUnder air. methyl and p-chloride groups on the aromatic ring participated
B https://doi.org/10.1021/acs.orglett.4c00685
Org. Lett. XXXX, XXX, XXX−XXX
Organic Letters pubs.acs.org/OrgLett Letter

in the reaction smoothly, leading to products 2b and 2h in (Scheme 4a). To elucidate the possible mechanism of this 1,5-
moderate yields. Next, reaction of anilide bromides possessing HAT radical cyclization, a radical trapping experiment was
four−seven membered rings at the α-position of amide also
furnished the corresponding γ-spirolactams 2k−2o in 30−90% Scheme 4. Scale-up Preparation of 2a and Control
yields. Reaction of N-allyl-N-(2-chlorophenyl)- Experiments
cyclobutanecarboxamide gave rise to product 2k in similar
yield, while products 2k and 2l were afforded in slightly lower
yields when anilide fluorides bearing four and five membered
rings at the α-position of amide were employed. Furthermore,
Different acyclic alkyl groups attached to the amides were
examined. Isopropyl, isobutyl, and isohexane groups were
suitable for this reaction, providing the target γ-spirolactams
2p−2r in moderate to good yields. Finally, the influence of
olefin component was investigated. Disubstituted alkenes
underwent the reaction smoothly, affording the product 2s in
75% yield. Overall, aryl bromides, aryl chlorides, and aryl
fluorides could all be well tolerated in this transformation.
Unfortunately, anilide bromide with ethyl substitution at the α-
position of amide could not provide the target product 2t.
The ring-closing reaction of N-(prop-2-yn-1-yl) anilide
halides was also investigated under the same reaction conducted with the addition of 2,2,6,6-tetramethyl-1-piper-
conditions (Scheme 3). Both anilide bromide 3a and anilide idyloxy (TEMPO) (Scheme 4b). As expected, the yield of 2a
decreased remarkably, indicating that the reaction proceeded
Scheme 3. Scope Exploration for the Reaction of N-(Prop-2- via a radical pathway. Furthermore, two reductants (excited
yn-1-yl)anilide Halidesa,b *ArS− and CO2•−) were generated during the reaction process,
which allowed the reduction of aryl halides. Based on the result
that aryl bromides (Ered1/2 = −2.44 V), aryl chlorides (Ered1/2 =
−2.80 V), and aryl fluorides (Ered1/2 = −2.97 V) could
participate in this reaction smoothly, we considered that aryl
halides were reduced by photoexcited arenethiolates (E1/2 =
−3.31 V) instead of CO2•− (E1/2 = −2.2 V)13 (Scheme 5, path
a and path b).

Scheme 5. Proposed Mechanism

a
Unless otherwise noted, reaction conditions are as follows: 1 (0.2
mmol), T1 (0.04 mmol), K2CO3 (0.2 mmol), HCO2Cs (0.6 mmol),
DMSO (2.0 mL), 390 nm Kessil lamp, 24 h, under a N2 atmosphere.
b
Isolated yields.

chloride 3a′ were suitable for this transformation, and product

4a was generated in similar yields. Anilide bromides with 4-
OMe aromatic substituents, tetrahydropyrane, and cyclo-
heptane attached to the amides underwent this 5-exo-dig
radical cyclization reaction smoothly, leading to 4-methyl-
enepyrrolidones 4a−4d in moderate to good yields. Notably,
anilide bromides with cyclopropane at the α-position of amine
gave the ring-opening seven membered lactam 4e in 20% yield,
which was inaccessible through previous method.12 Further-
more, aryl fluorides with isobutyl groups attached to the amide
underwent the reaction smoothly, giving rise to product 4f in a
55% yield.
To verify the practicability of this 1,5-HAT radical
cyclization process, a scaled-up (5.0 mmol) experiment was
performed. Gratifyingly, a similar result was smoothly afforded
C https://doi.org/10.1021/acs.orglett.4c00685
Based on the above results and previous reports, a possible
reaction pathway for this arenethiolate-catalyzed metal-free
1,5-HAT reaction is verified by the density functional theory
(DFT) calculation (see Supporting Information Scheme S1 for
the energy profile), is outlined in Scheme 5. Initially, the
photoexcited thiolate (*ArS−) is quenched by anilide halides,
delivering the aryl radical intermediate 5 (−28.7 kcal/mol)
along with ArS• (path a). Due to the higher bond dissociation
energy (BDE) of the formate salt (BDE(C−H) = 88 kcal/
Org. Lett. XXXX, XXX, XXX−XXX
Organic Letters
mol), ArS• was reduced by CO2•− to regenerate the
arenethiolate (path c) rather than abstracting a hydrogen
atom from the formate salt to form ArSH (BDE(C−H) = 79
kcal/mol). This HAT process is an endergonic step with a
calculated energy of 9.0 kcal/mol, indicating that this process is
infeasible (Scheme S1). On the other hand, intermediate 5
underwent 1,5-HAT via the transition state TS56 (−23.9 kcal/
mol) to yield the stabilized tertiary carbon radical 6 (−48.5
kcal/mol). Subsequently, the carbon radical would add to the
alkene through the transition state TS67 (−40.5 kcal/mol),
leading to radical intermediate 7 (−63.4 kcal/mol), which
abstracts a hydrogen atom from the formate salt (TS72a,
−48.8 kcal/mol) to furnish the final γ-spirolactam 2a (−78.4
kcal/mol).
In summary, we developed an efficient and metal-free route
to access γ-spirolactams from aryl halides by using
arenethiolate as a photocatalyst. Compared with a previously
developed method,12 this reaction features metal-free con-
ditions, higher efficiency, short reaction time, and strong
chemical bonds (C−Br, C−Cl, and C−F) activation. Various
γ-spirolactams can be provided through a SET reduction/
intramolecular 1,5-HAT/cyclization/HAT process. Notably, a
mechanism involving arenethiolate as a SET catalyst is
proposed based on the DFT calculation.
■ ASSOCIATED CONTENT
Data Availability Statement
The data underlying this study are available in the published
article and its Supporting Information.
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.4c00685.
Computational data, experimental details, NMR spectra,
and characterization data for all new compounds (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Xiaoyu Zhou − School of Pharmaceutical and Chemical
Engineering & Institute for Advanced Studies, Taizhou
University, Taizhou 318000, China; Email: zhouxiaoyu@
tzc.edu.cn
Jie Wu − School of Pharmaceutical and Chemical Engineering
& Institute for Advanced Studies, Taizhou University,
Taizhou 318000, China; State Key Laboratory of
Organometallic Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, Shanghai 200032,
China; School of Chemistry and Chemical Engineering,
Henan Normal University, Xinxiang 453007, China; Key
Laboratory of the Ministry of Education for Advanced
Catalysis Materials, Zhejiang Normal University, Jinhua
321004, China; orcid.org/0000-0002-0967-6360;
Email: jie_wu@fudan.edu.cn
Authors
Wei Xiao − School of Pharmaceutical and Chemical
Engineering & Institute for Advanced Studies, Taizhou
University, Taizhou 318000, China
Shengyun Liu − School of Pharmaceutical and Chemical
Engineering & Institute for Advanced Studies, Taizhou
University, Taizhou 318000, China
pubs.acs.org/OrgLett Letter
Yuhui Lin − School of Pharmaceutical and Chemical
Engineering & Institute for Advanced Studies, Taizhou
University, Taizhou 318000, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.4c00685
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Financial support from the National Natural Science
Foundation of China (No. 22201202), Natural Science
Foundation of Zhejiang Province (No. LZ23B020001), Open
Foundation of Hunan Provincial Key Laboratory of Control-
lable Preparation and Functional Application of Fine Polymers
(E22307), Open Research Fund of School of Chemistry and
Chemical Engineering, Henan Normal University
(2020ZD04), and Open Research Fund of Key Laboratory
of the Ministry of Education for Advanced Catalysis Materials
and Zhejiang Key Laboratory for Reactive Chemistry on Solid
Surfaces, Zhejiang Normal University is gratefully acknowl-
edged.
■ REFERENCES
(1) Wang, W.-X.; Li, Z.-H.; Feng, T.; Li, J.; Sun, H.; Huang, R.;
Yuan, Q.-X.; Ai, H.-L.; Liu, J.-K. Curtachalasins A and B, Two
Cytochalasans with a Tetracyclic Skeleton from the Endophytic
Fungus Xylaria curta E10. Org. Lett. 2018, 20, 7758−7761.
(2) Scott, L. J. Ubrogepant: First Approval. Drugs 2020, 80, 323−
328.
(3) Fensome, A.; Adams, W. R.; Adams, A. L.; Berrodin, T. J.;
Cohen, J.; Huselton, C.; Illenberger, A.; Kern, J. C.; Hudak, V. A.;
Marella, M. A.; Melenski, E. G.; McComas, C. C.; Mugford, C. A.;
Slayden, O. D.; Yudt, M.; Zhang, Z.; Zhang, P.; Zhu, Y.; Winneker, R.
C.; Wrobel, J. E. Design, Synthesis, and SAR of New Pyrrole-Oxindole
Progesterone Receptor Modulators Leading to 5-(7-Fluoro-3,3-
dimethyl-2-oxo-2,3-dihydro-1H-indol-5-yl)-1-methyl-1H-pyrrole-2-
carbonitrile (WAY-255348). J. Med. Chem. 2008, 51, 1861−1873.
(4) Obniska, J.; Kolaczkowski, M.; Bojarski, A. J.; Duszynska, B.
Synthesis, anticonvulsant activity and 5-HT1A, 5-HT2A receptor
affinity of new N-[(4-arylpiperazin-1-yl)-alkyl] derivatives of 2-
azaspiro[4.4]nonane and [4.5]decane-1,3-dione. Eur. J. Med. Chem.
2006, 41, 874−881.
(5) (a) Shi, C.-Y.; Han, T.; Hong, F.-L.; Ye, L.-W.; Sun, Q.; Teng,
M.-Y. Construction of Spirolactams by Unexpected Oxidative
Cyclization of Alkenyl Diynes via Copper Catalysis. Org. Lett. 2023,
25, 1525−1529. (b) Hu, H.; Li, B.-S.; Xu, J.-L.; Sun, W.; Wang, Y.;
Sun, M. Rh(iii)-Catalyzed spiroannulation of ketimines with cyclo-
propenones via sequential C-H/C-C bond activation. Chem. Commun.
2022, 58, 4743−4746. (c) Yuan, W.-K.; Shi, B.-F. Synthesis of Chiral
Spirolactams via Sequential C-H Olefination/Asymmetric 4 + 1
Spirocyclization under a Simple CoII/Chiral Spiro Phosphoric Acid
Binary System. Angew. Chem., Int. Ed. 2021, 60, 23187−23192.
(d) Lee, E.; Hwang, Y.; Kim, Y. B.; Kim, D.; Chang, S.
Enantioselective Access to Spirolactams via Nitrenoid Transfer
Enabled by Enhanced Noncovalent Interactions. J. Am. Chem. Soc.
2021, 143, 6363−6369. (e) Vacala, T. L.; Carlson, P. R.; Arreola-
Hester, A.; Williams, C. G.; Makhoul, E. W.; Vadola, P. A. Gold-
Catalyzed Dearomative Spirocyclization of N-Aryl Alkynamides for
the Synthesis of Spirolactams. J. Org. Chem. 2018, 83, 1493−1501.
(f) Hwang, Y.; Park, Y.; Kim, Y. B.; Kim, D.; Chang, S. Revisiting
Arene C(sp2)-H Amidation by Intramolecular Transfer of Iridium
Nitrenoids: Evidence for a Spirocyclization Pathway. Angew. Chem.,
Int. Ed. 2018, 57, 13565−13569.
(6) (a) Chen, P.-F.; Zhou, B.; Wu, P.; Wang, B.; Ye, L.-W. Bronsted
Acid Catalyzed Dearomatization by Intramolecular Hydroalkoxyla-
D https://doi.org/10.1021/acs.orglett.4c00685
Org. Lett. XXXX, XXX, XXX−XXX
Organic Letters pubs.acs.org/OrgLett Letter

tion/Claisen Rearrangement: Diastereo- and Enantioselective Syn-

thesis of Spirolactams. Angew. Chem., Int. Ed. 2021, 60, 27164−27170.
(b) Habert, L.; Cariou, K. Photoinduced Aerobic Iodoarene-
Catalyzed Spirocyclization of N-Oxy-amides to N-Fused Spirolac-
tams**. Angew. Chem., Int. Ed. 2021, 60, 171−175. (c) Ding, Q.; He,
H.; Cai, Q. Chiral Aryliodine-Catalyzed Asymmetric Oxidative C-N
Bond Formation via Desymmetrization Strategy. Org. Lett. 2018, 20,
4554−4557.
(7) (a) Wu, L.; Hao, Y.; Liu, Y.; Song, H.; Wang, Q. Visible-light-
induced dearomative oxamination of indole derivatives and
dearomative amidation of phenol derivatives. Chem. Commun. 2020,
56, 8436−8439. (b) Manna, S.; Someswara Ashwathappa, P. K.;
Prabhu, K. R. Visible light-mediated ipso-annulation of activated
alkynes: access to 3-alkylated spiro 4,5 -trienones, thiaspiro 4,5
-trienones and azaspiro 4,5 -trienones. Chem. Commun. 2020, 56,
13165−13168.
(8) Nagar, R.; Suwalka, D.; Malviya, B. K.; Verma, V. P.; Jassal, A.
K.; Sharma, S. Electrochemical Post-Ugi Cyclization for the Synthesis
of Highly Functionalized Spirolactams. J. Org. Chem. 2023, 88,
13977−13994.
(9) (a) Capaldo, L.; Ravelli, D. Hydrogen Atom Transfer (HAT): A
Versatile Strategy for Substrate Activation in Photocatalyzed Organic
Synthesis. Eur. J. Org. Chem. 2017, 2017, 2056−2071. (b) Capaldo,
L.; Quadri, L. L.; Ravelli, D. Photocatalytic hydrogen atom transfer:
the philosopher’s stone for late-stage functionalization? Green Chem.
2020, 22, 3376−3396. (c) Chen, H.; Yu, S. Remote C-C bond
formation via visible light photoredox-catalyzed intramolecular
hydrogen atom transfer. Org. Biomol. Chem. 2020, 18, 4519−4532.
(d) Guo, W.; Wang, Q.; Zhu, J. Visible light photoredox-catalysed
remote C-H functionalisation enabled by 1,5-hydrogen atom transfer
(1,5-HAT). Chem. Soc. Rev. 2021, 50, 7359−7377. (e) Xiao, W.;
Wang, X.; Liu, R.; Wu, J. Quinuclidine and its derivatives as hydrogen-
atom-transfer catalysts in photoinduced reactions. Chin. Chem. Lett.
2021, 32, 1847−1856. (f) Bao, X.; Yu, W.; Wang, G. Thiols as
Powerful Atom Transfer Catalyst: Opportunities in Photoredox-
Mediated Reactions. Adv. Synth. Catal. 2023, 365, 2299−2309.
(g) Xing, L.; Zhang, Y. Recent Advances in Selective C-H Bonds
Functionalization through Aryl Radical-Mediated Hydrogen Atom
Transfer Strategy. Curr. Org. Chem. 2023, 27, 747−758.
(10) (a) Liu, C.; Li, K.; Shang, R. Arenethiolate as a Dual Function
Catalyst for Photocatalytic Defluoroalkylation and Hydrodefluorina-
tion of Trifluoromethyls. ACS Catal. 2022, 12, 4103−4109. (b) Liu,
C.; Shen, N.; Shang, R. Photocatalytic Defluoroalkylation of
Trifluoroacetates with Alkenes using 4-(Acetamido)thiophenol.
Synthesis 2023, 55, 1401−1409.
(11) (a) Matsuo, B.; Majhi, J.; Granados, A.; Sharique, M.; Martin,
R. T.; Gutierrez, O.; Molander, G. A. Transition metal-free
photochemical C−F activation for the preparation of difluorinated-
oxindole derivatives. Chem. Sci. 2023, 14, 2379−2385. (b) Majhi, J.;
Granados, A.; Matsuo, B.; Ciccone, V.; Dhungana, R. K.; Sharique,
M.; Molander, G. A. Practical, scalable, and transition metal-free
visible light-induced heteroarylation route to substituted oxindoles.
Chem. Sci. 2023, 14, 897−902.
(12) Chen, J.-Q.; Chang, R.; Lin, J.-B.; Luo, Y.-C.; Xu, P.-F.
Photoredox-Induced Intramolecular 1,5-H Transfer Reaction of Aryl
Iodides for the Synthesis of Spirocyclic γ-Lactams. Org. Lett. 2018, 20,
2395−2398.
(13) (a) Majhi, J.; Molander, G. A. Recent Discovery, Development,
and Synthetic Applications of Formic Acid Salts in Photochemistry.
Angew. Chem., Int. Ed. 2024, 63, No. e202311853. (b) Xiao, W.;
Zhang, J.; Wu, J. Recent Advances in Reactions Involving Carbon
Dioxide Radical Anion. ACS Catal. 2023, 13, 15991−16011. (c) Gui,
Y.-Y.; Yan, S.-S.; Wang, W.; Chen, L.; Zhang, W.; Ye, J.-H.; Yu, D.-G.
Exploring the applications of carbon dioxide radical anion in organic
synthesis. Sci. bull. 2023, 68, 3124−3128. (d) Matsumoto, A.
Generation of Carbon Dioxide Radical Anion from Formate Salts
and its Use in Photochemical Reactions. J. Syn. Org. Chem. Jpn. 2022,
80, 868−869.

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