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Photoredox-Catalyzed Three-Component Sulfonaminoalkynylation

of Alkenes via a Radial/Polar Crossover
Lixian Shen,⊥ Jie Liu,⊥ Xue Peng, Zhengwen Lei,* Zhen Wang,* and Yao-Fu Zeng*
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ABSTRACT: We report a photoredox-catalyzed three-component

sulfonaminoalkynylation of alkenes with N-aminopyridine salts and
potassium alkynyltrifluoroborate salts. This aminoalkylation re-
action underwent a radial/polar crossover mechanism, which was
distinguished from the previous reports. A variety of β-alkynylated
sulfonamides were obtained in moderate to excellent yields. The
versatility of this method was further evidenced by its successful
application in modifying biological molecules in advanced stages of
development.

■ INTRODUCTION
Alkyne and amino groups are valuable motifs, which widely exist
which was trapped by an ethynylbenziodoxolone (EBX) reagent
to deliver the β-alkynylated amides (Scheme 1b).10 Sub-
in many research fields such as biochemistry, material science, sequently, a copper-catalyzed method for the enantioselective
and pharmaceuticals.1−3 Besides, they can undergo various aminoalkynylation of alkenes was reported by Liu, Cao, and
transformations in organic synthesis to afford N-heterocycles, their colleagues. This process involves a radical relay process,
amino acids, nitriles, and so on.4 Therefore, the development of utilizing N-fluoro-N-alkysulfonamides as precursors for nitro-
convenient and mild methods for the integration of these two gen-centered radicals and alkynyltrimethoxysilanes as the
groups into organic frameworks has attracted great attention alkynylating agents (Scheme 1b). Mechanistically, the addition
from many chemists. One of the powerful strategies to access β- of a nitrogen radical to alkenes produced a carbon radical, which
alkynylated amines is via aminoalkynylation of alkenes.5 At was captured by alkynyl-copper species. A reductive elimination
present, the reported methods were mainly focused on the two- occurred to give the products.11 Thus, it can be seen that a
component reactions, which involved a prefunctionalized alkene carbon-centered radical captured by the alkynylating reagent
containing an amino group with alkynyl reagents under the was involved in the two aminoalkynylation reactions. However,
catalysis of different transition metals (Scheme 1a).6−9 In as far as we know, the aminoalkynylation reaction underwent a
contrast, the three-component aminoalkylation of alkenes has process of a carbocation captured by a nucleophilic alkynylating
been relatively less explored. In 2019, Studer and co-workers reagent that was rarely reported.
reported a photoredox-induced 1,2-amidoalkynylation of In recent years, a photoredox-catalyzed radical/polar cross-
over (RPC) has increasingly become a powerful strategy for
unactivated alkenes. The amidyl radical generated from α-
amido-oxy acid reacted with alkenes to afford the carbon radical, assembling molecular complexity under mild reaction con-
ditions, which featured both radical and ionic modes of
reactivity.12 Besides, no extra oxidants or reductants were
Scheme 1. Methods for the Aminoalkynylation of Alkenes
needed for net-neutral RPC reactions. In this context, we
envisioned that the nitrogen-centered radical addition to alkenes
would generate a carbon radical, which can be oxidized by the
photocatalyst to produce a carbocation intermediate. The
carbocation intermediate would be captured by nucleophilic
alkynylating reagents to deliver β-alkynylamines (Scheme 1b).

Received: November 13, 2024

Revised: January 6, 2025
Accepted: January 10, 2025
Published: January 21, 2025

© 2025 American Chemical Society https://doi.org/10.1021/acs.joc.4c02796

1656 J. Org. Chem. 2025, 90, 1656−1662
The Journal of Organic Chemistry pubs.acs.org/joc Article

Table 1. Optimization of the Reaction Conditionsa

entry ratio (1a/2a/3a) photocatalyst (mol %) yieldb

1 1:1.2:1 thioxanthen-9-one (1.0) N.D.
2 1:1.2:1 eosin Y (1.0) N.D.
3 1:1.2:1 4CzIPN (1.0) N.D.
4 1:1.2:1 fac-Ir(ppy)3 (1.0) 64%
5 1:1.2:1.5 fac-Ir(ppy)3 (1.0) 75%
6 1:1.2:2.0 fac-Ir(ppy)3 (1.0) 73%
7 1:1.2:2.5 fac-Ir(ppy)3 (1.0) 60%
8 1:1.0:1.5 fac-Ir(ppy)3 (1.0) 67%
9 1:1.4:1.5 fac-Ir(ppy)3 (1.0) 68%
10 1:1.2:1.5 fac-Ir(ppy)3 (1.5) 72%
11 1:1.2:1.5 fac-Ir(ppy)3 (2.0) 83% (77%)e
12 1:1.2:1.5 fac-Ir(ppy)3 (2.5) 66%
13 1:1.2:1.5 - 0%
14c 1:1.2:1.5 fac-Ir(ppy)3 (2.0) 0%
15d 1:1.2:1.5 fac-Ir(ppy)3 (2.0) trace
a
Reaction conditions: 1a (0.10 mmol), 2a, 3a, photocatalyst, DCM (2 mL), 30 W blue LEDs, Ar, 6 h. bYields were determined by1H NMR analysis
using 1,3,5-trimethoxybenzene as the internal standard. cNo light. dUnder an air atmosphere. N.D.: not detected. eIsolated yield.

Scheme 2. Scaled-up Experiment and Derivatization of the Product

Although the envisaged three-component aminoalkynylating potassium (2-phenylethynyl)trifluoroborate 3a14 were used as
reaction based on the RPC reaction mode looks promising, two the model substrates. First, several photocatalysts were screened
challenges still need to be overcome: (1) a β-hydrogen (Table 1, entries 1−4). Delightfully, the desired β-alkynylsulfo-
elimination of the carbocation intermediate may occur before namide 4a was obtained in 64% yield in DCM by using fac-
it was captured by the alkynylating reagents and (2) the Ir(ppy)3 as the photocatalyst under irradiation with 30 W blue
competitive two-component reaction between the electrophilic LEDs at room temperature for 6 h (entry 4). Increasing the
nitrogen-centered radical with the nucleophilic alkynylating loading of 3a to 1.5 equiv produced product 4a in 75% yield
reagents. (entry 5), while further increasing its loading led to lower yields

■ RESULTS AND DISCUSSION

To examine the feasibility of the above designed reaction, 4-Ph-
(entries 6−7). Subsequently, the amount of N−Me and N-Ts-1-
aminopyridinium salt 2a was explored, and no better results
were obtained (entries 8−9). Screening of the loading of the
styrene 1a, N−Me, N-Ts-1-aminopyridinium salt 2a,13 and photocatalyst demonstrated that the usage of 2 mol %
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The Journal of Organic Chemistry pubs.acs.org/joc Article

Table 2. Scope of Styrenesa

a
Reaction conditions: 1 (0.1 mmol), 2a (0.12 mmol, 1.2 equiv), fac-Ir(ppy)3 (2.0 mol %), 3a (0.15 mmol, 1.5 equiv), DCM (2 mL), Ar, 6 h.
Isolated yield.

Scheme 3. Control Experiments

photocatalyst displayed better reaction efficiency, and the air atmosphere, the reaction produced only a minimal amount of
product was produced in 83% yield (entry 11). Control product (entry 15).
With the optimized reaction conditions in hand, the substrate
experiments suggested that removing the photocatalyst or scope of this sulfonaminoalkynylation reaction of various
light source led to no product formation (entries 13−14). In an styrenes was then explored (Table 2). Generally, both
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Table 3. Scope of N-Aminopyridinium Salts and Potassium Trifluoroborate Saltsa

a
Reaction conditions: 1 (0.1 mmol), 2 (0.12 mmol, 1.2 equiv), fac-Ir(ppy)3 (2.0 mol %), 3 (0.15 mmol, 1.5 equiv), DCM (2 mL), Ar, 6 h. Isolated
yield.

electron-donating and -withdrawing styrenes were tolerated, The scope of the N-aminopyridinium salts was then examined
providing the corresponding products in moderate to good (Table 3). The electronic property of the functional groups at
yields. Common functional groups such as alkyl (4c, 4d, 4m, the para-position of phenylsulfonamides displayed little effects
4q), −OMe (4e, 4n), halide (4f−4h, 4l, 4o, 4p), ester (4j, 4k), on the reaction efficiency, which was demonstrated by the
and −CN (4i) were amenable. The position of the substituents examples of compounds 5b (t-Bu) and 5c (CF3). Thienyl (5d)-
had no obvious effects on the reaction efficiency, as ortho- and naphthyl (5e)-substituted sulfonamides exhibited good
methyl-substituted styrene proceed this reaction smoothly (4q). reactivity. The N−Et and N-Ts-1-aminopyridinium salt could
also be converted to the desired product (5f). A good yield was
In addition, other (hetero)aromatic alkenes such as naphthalene
obtained for the N-aminopyridinium salt bearing a free NH
(4r), thiophene (4t), and pyridine (4u) proved to be successful. group (5g). Subsequently, the substrate scope of potassium
E-β-Methylstyrene was amenable to this reaction, affording the alkynyltrifluoroborate salts was explored. Potassium alkynyltri-
product with excellent diastereoselectivity (4s). Notably, when fluoroborate salts bearing electron-rich and -poor functional
1-Ph-substituted 1,3-diene was used as the substrate, the 1,4- groups were all compatible (6a−6f). Naphthyl-substituted
aminoalkynylation product was generated (4v). Unfortunately, alkynyltrifluoroborate salt exhibited excellent performance in
1-Me styrene (1y), aliphatic alkene(1w), and enamine (1x) this reaction, affording the product with a yield of 85% (6g).
were not compatible. Besides, terminal and alkyl alkynyltrifluoroborate salts engaged
1659 https://doi.org/10.1021/acs.joc.4c02796
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Table 4. Late-Stage Modification of Biological Moleculesa

a
Reaction conditions: 1 (0.1 mmol), 2a (0.12 mmol, 1.2 equiv), fac-Ir(ppy)3 (2.0 mol %), 3a (0.15 mmol, 1.5 equiv), DCM (2 mL), Ar, 6 h.
Isolated yields.

in the reaction successfully to furnish the product in 85% (6h) Besides, the ring-opening aminoalkynylated product 13 was
and 57% yields (6i), respectively. generated when compound 12 was used as the substrate
Subsequently, this protocol was implemented in the late-stage (Scheme 3c). The experiments described above implied that a
modification of multiple styrene-derived pharmaceuticals as well sulfonamidyl radical partook in this reaction.
as natural products (Table 4). The derivatives originating from In light of the aforementioned mechanistic investigations and
flurbiprofen, L-menthol, piperonyl alcohol, naproxen, fluoro-
quinolonic acid, and probenecid were well tolerated, affording prior reports,15 a RPC mechanism via an oxidative quenching
the aminoalkynylated products in yields ranging from 57% to pathway for this photocatalytic aminoalkynylation of alkenes is
83% (7a−7f), which demonstrated the extensive application delineated in Scheme 4. N-methylsulfonamidyl radical A
range of our method.
To showcase the practicability of this photocatalyzed Scheme 4. Proposed Mechanism
sulfonaminoalkynylation of alkene, the reaction scale was
enlarged to 1.0 mmol, and product 4a was obtained in an
isolated yield of 69% (Scheme 2a). Next, further transformation
of the aminoalkynylated products were studied. Compound 4a
could be isomerized to allene 8 in the presence of
triazabicyclodecene (Scheme 2b). A copper-catalyzed click
reaction was realized by the reaction of compound 6h with
benzyl azide to afford 1,2,3-triazole 9 in 84% yield (Scheme
2c).11
To explore the potential reaction mechanism, a series of
control experiments were conducted. Addition of TEMPO
(2,2,6,6-tetramethyl-1-piperidinyloxy) to the reaction mixture
led to no product formation (Scheme 3a). Replacement of
styrene with 1,2-diphenylethylene under the standard con-
ditions provided compound 11 in 85% yield (Scheme 3b).
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generated by means of single electron transfer between the Jie Liu − School of Pharmaceutical Science, The First Affiliated
excited photocatalyst *[Ir]III and sulfonaminopyridinium salt 2a Hospital, Hengyang Medical School, University of South
attacks styrene 1a to afford benzyl radical B. Subsequently, China, Hengyang, Hunan 421001, China
benzyl radical B is oxidized by [Ir]IV, thereby giving rise to Xue Peng − School of Pharmaceutical Science, The First
benzyl cation C and simultaneously regenerating photocatalyst Affiliated Hospital, Hengyang Medical School, University of
[Ir]III. Ultimately, the benzyl cation C is captured by the South China, Hengyang, Hunan 421001, China
potassium alkynyltrifluoroborate salt, leading to the formation of Complete contact information is available at:
target product 4. https://pubs.acs.org/10.1021/acs.joc.4c02796

■ CONCLUSIONS
In summary, a photocatalyzed three-component sulfoaminoal-
Author Contributions
⊥
L.S and J.L contributed equally to this work.
kynylation of alkenes was developed. The N-aminopyridine salts Notes
were used as the sulfonamidyl radical precursors, and potassium The authors declare no competing financial interest.
alkynyltrifluoroborate salts were used as the alkynyl sources.
Both electron-rich and electron-poor styrenes were tolerated. It
should be noted that the protocol is applicable to the late-stage
■ ACKNOWLEDGMENTS
The project was supported by the National Natural Science
modification of drugs and natural products, which indicates the Foundation of China (no. 22101126), the Natural Science
remarkable potential of the method. A radical-polar crossover Foundation of Hunan Province (no. 2024JJ5323), and the
mechanism via an oxidative quenching pathway has been put Foundation of Hunan Provincial Key Laboratory
forward. (2023TP1014).

■ ASSOCIATED CONTENT
Data Availability Statement
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