pubs.acs.
org/OrgLett Letter
Photocatalytic 1,2-Iminosulfonylation and Remote 1,6-
Iminosulfonylation of Olefins
Xue-Ling Luo, Shan-Shan Li, Yu-Shi Jiang, Fu Liu, Shu-Hui Li,* and Peng-Ju Xia*
Cite This: https://doi.org/10.1021/acs.orglett.3c00437
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ABSTRACT: A new class of iminosulfonylation reagents were
developed and extensively used in the 1,2-iminosulfonylation of
various olefins. Olefins containing bioactive molecules, such as
indomethacin, gemfibrozil, clofibrate, and fenbufen, afforded the
desired iminosulfonylation products in synthetically useful yields.
Furthermore, the first remote 1,6-iminosulfonylation of alkenes was
realized by using oxime ester bifunctionalization reagents. Overall,
more than 40 structurally diverse β-imine sulfones were obtained in
moderate to excellent yields.
I n recent years, bifunctional reagents have been widely used
in organic synthesis because of their ability to form complex
organic structures and provide novel reaction pathways.1
Benzophenone oxime esters are considered as a highly
promising class of bifunctional reagents because they possess
weak N−O bonds (Scheme 1).2 These reagents can produce
persistent imine radicals and some other types of radicals in the
presence of visible-light-catalyzed energy transfer. In pioneer-
Scheme 1. Methodological Development of Bifunctionalized
Oxime Ester Reagents and Our Design
© XXXX American Chemical Society
Read Online
Article Recommendations *
sı Supporting Information
ing studies by Cho,3 Glorius,4 Wu,5 Han,6 Huo,7 and our
team,8 carbon-centered radicals (CCRs) and nitrogen-centered
radicals (NCRs) were produced simultaneously from corre-
sponding oxime ester bifunctionalization reagents. Oxygen-
centered radicals (OCRs) and NCRs were also generated and
used in the bifunctionalization of various olefins.
Very recently, Glorius’ group9 and Yang’s team10 independ-
ently developed the photosensitized amidylimination of
alkenes with oxime esters based on the long-lived iminyl
radical and the transient amidyl radical. During the same
period, our group11 also developed a series of bisimide radical
reagents, which were used for the modular cyanoalkylamina-
tion of alkenes. Despite these outstanding works, there are still
some issues worth exploring. First, the development of novel
bifunctionalized reagents, such as iminosulfonylation bifunc-
tionalization reagents, remains attractive. Second, all the above
difunctionalization reagents, except for those in Glorius and
Gutierrez’s work12 on an unprecedented radical relay 1,4-
oxyimination of two electronically differentiated olefins with a
class of bifunctional oxime carbonate reagents, were mainly
used to achieve the 1,2-bifunctionalization of olefins. The
remote difunctionalization of olefins with bifunctionalization
oxime reagents remains an unexplored area.
β-Sulfonyl amides, a class of molecular backbone com-
pounds with pharmaceutical activities, are ideal for medicinal
applications.13 Impressive progress has been made in the
Received: February 10, 2023
https://doi.org/10.1021/acs.orglett.3c00437
A Org. Lett. XXXX, XXX, XXX−XXX
Organic Letters pubs.acs.org/OrgLett
completion of the synthesis of such compounds.14 However, a
simple, facile, and general means of synthesizing such
compounds remains lacking. Aminosulfonylation bifunctional-
ization reagents appear to be an effective means to solve this
problem. To the best of our knowledge, only one class of
aminosulfonylation reagents relies on nickel catalysis with
more than one equivalent manganese metal.15 Therefore, the
development of novel aminosulfonylation bifunctionalization
reagents that do not rely on traditional transition metal
catalysis for the synthesis of 2-sulfonylethan-1-amines is worth
investigating. Very recently, an amino-sulfonylation of olefins
via energy transfer catalysis (EnT)16 mediated N−S bond
homolysis was reported by Glorius and co-workers.17
Herein, we expect to develop a class of novel bench-stable
and easy-to-handle bifunctionalization reagents capable of
producing nitrogen and sulfonyl radicals. Furthermore, we plan
to apply this new bifunctionalization oxime reagent not only to
the 1,2-iminosulfonylation of olefins but also to the remote 1,6-
iminosulfonylation of olefins.
In this study, a novel iminosulfonylation reagent 1a (CCDC
no. 2223342) was synthesized by linking sulfonyl oxime18 with
benzophenone oxime. Initial studies were explored by
performing the reaction between iminosulfonylation bifunc-
tionalization reagent 1a and 1,1-diphenylethylene 2a. As shown
in Table 1, we carried out the reaction at room temperature for
12 h under 395 nm blue LED radiation and an Ar atmosphere
Table 1. Optimization of the Reaction Conditionsa
a
Reaction conditions: 1a (0.2 mmol, 1.0 equiv), 2a (0.30 mmol, 1.5
equiv), catalyst (1 mol %), solvent (2 mL), 30 W blue LED (450 nm),
12 h, argon atmosphere, rt. bThioxanthone (10 mmol %), 30 W blue
LED (395 nm) instead of 30 W blue LED (450 nm). cWithout LED.
B https://doi.org/10.1021/acs.orglett.3c00437
Letter
with [Ir(dF(CF3)ppy)2(dtbbpy)](PF6) as the catalyst. First,
several solvents, including PhMe, MeCN, THF, DMF, and
DMSO, were screened. The yield can reach 88% with DMSO
as the reaction solvent. Then, several photocatalysts were
screened. A significant reduction in productivity was observed
when [Ir(ppy)2(dtbbpy)][PF6] or Ir(ppy)3 was employed in
the presence of a 30 W blue LED. When thioxanthone was
used as a photosensitizer, the product 3a (CCDC no.
2223343) was also successfully obtained. However, the yield
decreased to 68%. When the photocatalyst was removed from
the reaction system, the reaction could still be performed with
a 395 nm LED, affording 3a in 34% yield. No product 3a was
detected under the control conditions of irradiation with a low-
energy 450 nm LED without a photocatalyst. This finding
illustrated the important role of light sources in this reaction.
In the absence of a light source, the reaction could not be
performed at all.
The scope of aromatic olefins was examined with 1a when
the optimal reaction conditions were determined. Scheme 2
shows that this strategy was applied smoothly to the
iminosulfonylation of various substituted 1,1-diphenylethy-
lenes to synthesize 3b−3i in 76%−97% yields. Then, styrenes
with different substituents, including electron-donating and
electron-withdrawing groups, were used to afford 3j−3t in
26%−63% yields. The reduction in yield may be due to the
reduced stability of the intermediates produced by styrene and
sulfonyl radicals. Other aromatic olefins, including 2-vinyl-
naphthalene, 2-vinylpyridine, and prop-1-en-2-ylbenzene, were
successfully involved in the reaction to obtain products 3u−3x
in 50%−60% yields.
For the further extension of the adaptability of the reaction,
we expected to modulate the positional selectivity of the
reaction by using α-trifluoromethylstyrenes. The correspond-
ing iminosulfonylation product 3y was generated with single
selectivity in 86% yield. Subsequently, the reactions involving
different substituents were studied. These reactions yielded
products 3z−3ad in 53%−84% yields. Correspondingly, we
obtained 31%−39% isolated yields of products 3ae−3ag when
using different β-CF3-1,3-enynes. When unactivated olefins as
well as electron-rich olefins were used as substrates, the
corresponding products were not obtained, probably due to
the polarity matching and the stability of the radical
intermediates.
Then, olefins containing bioactive molecules, such as
indomethacin, gemfibrozil, clofibrate, and fenbufen, afforded
the desired iminosulfonylation products 3ak−3an in syntheti-
cally useful yields (45%−53%).
In the above substrate expansion study, we found that
obtaining 1,2-bifunctionalized products from unactivated
olefins was difficult. Hence, for the further study of the
reaction properties of this new class of bifunctionalization
reagents, we envisaged that the 1,5-HAT-triggered radical relay
strategy might offer the solution to obtaining the remote 1,6-
iminosulfonylation products of unactivated alkenes. In view of
the above, we made the first attempt at the 1,6-remote
bifunctionalization reactions of oxime ester bifunctionalization
reagents. When diethyl 2-allyl-2-(3-oxo-3-phenylpropyl)-malo-
nate 4a was selected as the model substrate, the 1,6-
iminosulfonylation product 5a was obtained in 40% yield
(Scheme 3). This result confirmed the feasibility of the 1,6-
bifunctionalization of unactivated alkenes. Then, the substrate
scope with respect to various alkenyl ketones was assessed, and
the results are summarized in Scheme 2. Several alkenyl aryl
Org. Lett. XXXX, XXX, XXX−XXX
Organic Letters
Scheme 2. Scope of the 1,2-Iminosulfonylation of Olefinsa
a
Conditions: 1 (0.20 mmol, 1.0 equiv), 2 (0.30 mmol, 1.5 equiv), catalyst (1 mol %), DMSO (2 mL), 30 W blue LED (450 nm), 12 h, argon
atmosphere, rt.
ketones, including those bearing electron-donating groups
(−Me, −OMe) and synthetically useful electron-withdrawing
groups (−Br) on the phenyl ring, were found to be suitable
substrates to afford the corresponding 1,6-iminosulfonylation
products 5b−5d in 23%−47% yields. Furthermore, alkenyl
arenes with different groups (−H, −Me, and −Cl) on the
phenyl ring were applicable under the optimal conditions.
When the reaction scale was expanded to 2 mmol, the yield
was somewhat reduced, but 0.49 g of product 3a was still
obtained (Scheme 4a). The simple acidic hydrolysis of the
iminosulfonylation product 3a delivered the corresponding 3a′
in near equivalent reaction yields (Scheme 4b). In the presence
of potassium tert-butoxide, 3p underwent an elimination
process to give the enamine product 3p′ in 48% yield. When
TEMPO or BHT was added to the reaction system, the
product 3a could not be observed, whereas the radical capture
products of sulfonyl radical by TEMPO and BHT were
detected by HRMS (Scheme 4c). Further studies revaled that
pubs.acs.org/OrgLett Letter
luminescence quenching occurred mainly between the
iminosulfonylation reagent 1a and [Ir(dF(CF 3 )-
ppy)2(dtbbpy)](PF6) (Scheme 4d). On/off experiments on
the reaction of 1a and 2a demonstrated that the corresponding
product 3a could be produced only under constant irradiation.
In addition, neither heating nor radical initiation with AIBN
alone can make the reaction proceed, which further confirms
the radical process.
In consideration of these results (Scheme 5), our
mechanistic proposal involved the activation of the Ir
photocatalyst upon irradiation that subsequently underwent
energy transfer with substrate 1a, thereby causing 1a to
undergo N−O bond homolysis to deliver an iminyl radical I
and a sulfonyl radical II with the release of carbon dioxide,
acetone, and cyanogen. When olefin 2 was present in the
system, the radical addition intermediate III was generated.
Then, the radical−radical cross-coupling process between the
imine radical I and the radical addition intermediate III
C https://doi.org/10.1021/acs.orglett.3c00437
Org. Lett. XXXX, XXX, XXX−XXX
Organic Letters pubs.acs.org/OrgLett
Scheme 3. Scope of the 1,6-Iminosulfonylation of Alkenesa
a
Conditions: 1 (0.20 mmol, 1.0 equiv), 4 (0.24 mmol, 1.2 equiv),
catalyst (1 mol %), DMSO (2 mL), 30 W blue LED (450 nm), 12 h,
argon atmosphere, rt.
Scheme 4. Synthesis Application and Control Experiments
Scheme 5. Possible Reaction Mechanism
D https://doi.org/10.1021/acs.orglett.3c00437
Letter
occurred, resulting in the 1,2-iminosulfonylation product 3.
When olefin 4 was utilized as the free radical receptor,
intermediate IV was obtained from the addition of sulfonyl
radical II to 4. Subsequently, the intramolecular 1,5-HAT of IV
afforded the alkyl radical intermediate V with increased
stability that also underwent radical−radical cross-coupling
with the long-lived imine radical I, affording the novel 1,6-
iminosulfonylation product 5.
In summary, through the development of iminosulfonylation
reagents, we realized 1,2-iminosulfonylation and the first
remote 1,6-iminosulfonylation of olefins. We achieved the
diversified functionalization of olefins for the first time by using
newly developed iminosulfonylation reagents. The achieve-
ment greatly expands the application scope of these oxime
ester bifunctionalization reagents. In conclusion, the strategy
developed in this work provides an efficient synthetic route for
the synthesis of iminosulfonylation molecules and provides
new ideas for the application of biradical functionalization
reagents.
■ 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.3c00437.
Experimental procedures, characterization data, NMR
spectra, and X-ray crystallography data for 1a and 3a
(PDF)
Accession Codes
CCDC 2223342−2223343 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
■ AUTHOR INFORMATION
Corresponding Authors
Shu-Hui Li − School of Chemistry and Pharmaceutical
Sciences, State Key Laboratory for Chemistry and Molecular
Engineering of Medicinal Resources, Guangxi Normal
University, Guilin 541004, P. R. China; Email: gxnulsh@
gxnu.edu.cn
Peng-Ju Xia − School of Chemistry and Pharmaceutical
Sciences, State Key Laboratory for Chemistry and Molecular
Engineering of Medicinal Resources, Guangxi Normal
University, Guilin 541004, P. R. China; orcid.org/0000-
0002-6587-3465; Email: xiapengju@gxnu.edu.cn
Authors
Xue-Ling Luo − School of Chemistry and Pharmaceutical
Sciences, State Key Laboratory for Chemistry and Molecular
Engineering of Medicinal Resources, Guangxi Normal
University, Guilin 541004, P. R. China
Shan-Shan Li − School of Chemistry and Pharmaceutical
Sciences, State Key Laboratory for Chemistry and Molecular
Engineering of Medicinal Resources, Guangxi Normal
University, Guilin 541004, P. R. China
Org. Lett. XXXX, XXX, XXX−XXX
Organic Letters pubs.acs.org/OrgLett
Yu-Shi Jiang − School of Chemistry and Pharmaceutical
Sciences, State Key Laboratory for Chemistry and Molecular
Engineering of Medicinal Resources, Guangxi Normal
University, Guilin 541004, P. R. China
Fu Liu − School of Chemistry and Pharmaceutical Sciences,
State Key Laboratory for Chemistry and Molecular
Engineering of Medicinal Resources, Guangxi Normal
University, Guilin 541004, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.3c00437
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We gratefully acknowledge the financial support from the
National Natural Science Foundation of China (22101059,
22161007), Guangxi Science and Technology Base and Special
Talents (AD21220104), Guilin Innovation Platform and
Talent Plan (20210218-4), and Guangxi Normal University.
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