Nickel-Catalyzed N-Arylation of NH-Sulfoximines with Aryl Halides via Paired Electrolysis

Article abstract of DOI:10.1002/anie.202016310

A novel strategy for the N-arylation of NH-sulfoximines has been developed by merging nickel catalysis and electrochemistry (in an undivided cell), thereby providing a practical method for the construction of sulfoximine derivatives. Paired electrolysis is employed in this protocol, so a sacrificial anode is not required. Owing to the mild reaction conditions, excellent functional group tolerance and yield are achieved. A preliminary mechanistic study indicates that the anodic oxidation of a Ni^II species is crucial to promote the reductive elimination of a C?N bond from the resulting Ni^III species at room temperature.

Full text of DOI:10.1002/anie.202016310

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How to cite: Angew. Chem. Int. Ed. 2021, 60, 9444–9449
International Edition:
German Edition:
doi.org/10.1002/anie.202016310
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Paired Electrolysis
Nickel-Catalyzed N-Arylation of NH-Sulfoximines with Aryl Halides
via Paired Electrolysis
Dong Liu+, Zhao-Ran Liu+, Cong Ma, Ke-Jin Jiao, Bing Sun, Lei Wei, Julien Lefranc,
Simon Herbert, and Tian-Sheng Mei*
Abstract: A novel strategy for the N-arylation of NH-
sulfoximines has been developed by merging nickel catalysis
and electrochemistry (in an undivided cell), thereby providing
a practical method for the construction of sulfoximine
derivatives. Paired electrolysis is employed in this protocol,
so a sacrificial anode is not required. Owing to the mild
reaction conditions, excellent functional group tolerance and
yield are achieved. A preliminary mechanistic study indicates
that the anodic oxidation of a NiII species is crucial to promote
À
the reductive elimination of a C N bond from the resulting
NiIII species at room temperature.
T
ransition-metal-catalyzed N-arylation of sulfoximines has
received significant attention[1] since N-arylated sulfoximines
are essential structural units in chiral auxiliaries,[2] ligands for
various catalytic asymmetric reactions,[3] building blocks in
pseudopeptides,[4] and bioactive molecules (Figure 1a).[5] For
instance, in 1998 Bolm and Hildebrand reported an elegant
example of Pd-catalyzed N-arylation of sulfoximines with aryl
bromides at 1108C for 48 h using BINAP as the ligand.[6]
Inspired by this seminal work, various protocols for Pd-
catalyzed N-arylation of sulfoximines using different arene
sources have been developed.[7] Additionally, Cu-catalyzed N-
arylation of sulfoximines with aryl iodides, aryl bromides, aryl
boronic acids, and diaryliodonium salts has been developed
by Bolm and others, although the coupling with aryl chlorides
has not been disclosed.[8] In contrast, N-arylation of sulfox-
imines with aryl halides using nickel catalysis is less explored,
although nickel catalysts are inexpensive and exhibit high
reactivities toward less reactive electrophiles such as aryl
chlorides in cross-coupling reactions between aryl halides and
Figure 1. a) Representative examples of bioactive sulfoximines. b) Con-
ventional transition-metal-catalyzed N-arylation of NH-sulfoximines.
c) Our hypothetical nickel-catalyzed electrochemical approach. d) This
work.
amines.[9,10] Bolm and co-workers reported the sole example,
specifically using Ni(COD)2 with BINAP to catalyze the N-
arylation of sulfoximines with aryl tosylates, although ele-
vated temperatures was required, only two substrate exam-
ples were shown, and yields were modest (Figure 1b).[11]
Common drawbacks to these catalytic N-arylations of sulfox-
imines with aryl halides include the need for high temper-
atures, restricted substrate scope, and the reliance on alkoxide
bases. To address the aforementioned issues, Kçnig and
Wimmer recently developed N-arylation of sulfoximines with
aryl bromides at room temperature, by merging Ni catalysis
with Ir photocatalysis.[12] Subsequently, Hande and co-work-
ers reported a similar transformation with aryl iodides.[13]
Unfortunately, expensive Ir catalysts are needed for these
protocols, and N-arylation of NH-sulfoximines using readily
available aryl chlorides has not been reported.
[*] D. Liu,[+] Z.-R. Liu,[+] C. Ma, K.-J. Jiao, B. Sun, L. Wei, Prof. Dr. T.-S. Mei
State Key Laboratory of Organometallic Chemistry
Center for Excellence in Molecular Synthesis
Shanghai Institute of Organic Chemistry
University of Chinese Academy of Sciences
Chinese Academy of Sciences
345 Lingling Road, Shanghai 200032 (China)
E-mail: mei7900@sioc.ac.cn
Dr. J. Lefranc
Nuvisan Innovation Campus Berlin GmbH
13353 Berlin (Germany)
Dr. S. Herbert
Pharmaceuticals, Research and Development, Bayer AG
13353 Berlin (Germany)
[+] These authors contributed equally to this work.
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.202016310.
The past few years have witnessed a renaissance of
organic electrochemistry, since this approach avoids the use of
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Table 1: Reaction optimization and control studies.[a]
chemical oxidants or reductants and also provides alternative
reactivity and selectivity modes.[14] In particular, the merger of
nickel catalysis and electrochemistry has emerged as a useful
strategy for cross-coupling reactions.[15] For instance, Baran
and co-workers reported Ni-catalyzed amination of aryl
halides under mild reaction conditions,[16] whereby more
than two oxidation states of nickel can be accessed in the
same pot.[17] Our group has a long-standing interest in Ni-
catalyzed electrochemical couplings with aryl halides.[18] We
hypothesized that Ni-catalyzed electrochemical N-arylation
of NH-sulfoximines with aryl halides could take place under
mild reaction conditions via paired electrolysis,[19] wherein
anodic oxidation could generate a NiIII species to promote
C-N reductive elimination while cathodic reduction could
produce a NiI species from a NiII precatalyst. The resulting NiI
species could oxidatively add to an aryl halide to give
ArNiIIIX2, which could readily undergo cathodic reduction
to produce a ArNiIIX intermediate (Figure 1c). Herein, we
establish that Ni-catalyzed N-arylation of NH-sulfoximines
using aryl bromides and chlorides can be executed efficiently
at room temperature (Figure 1d). A preliminary mechanistic
study indicates that the anodic oxidation of a NiII species is
Entry Deviation from standard conditions Conv. [%][b] Yield [%][b]
1
2
3
4
5
6
7
8
none
C in lieu of RVC
100
35
28
10
5
91 (90)[c]
20
15
NR
NR
80
55
78
60
11
5
55
70
30
55
20
50
15
Pt in lieu of RVC
C in lieu of Ni foam
Pt in lieu of Ni foam
NiBr2 in lieu of NiBr2·glyme
NiCl2·glyme in lieu of NiBr2·glyme
NiI2 in lieu of NiBr2·glyme
DBN in lieu of DBU
DABCO in lieu of DBU
Et3N in lieu of DBU
L2 in lieu of L1
L3 in lieu of L1
L4 in lieu of L1
L5 in lieu of L1
L6 in lieu of L1
L7 in lieu of L1
L8 in lieu of L1
L9 in lieu of L1
L10 in lieu of L1
85
56
80
71
14
10
70
74
31
60
22
58
30
85
100
90
100
<5
<5
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
À
crucial to promote the C N bond reductive elimination from
the resulting NiIII species.
53
80
Initially, we employed NH-sulfoximine 1a and bromo-
arene 2a as model reactants and probed various reaction
conditions in an undivided cell for the envisioned electro-
chemical N-arylation (Table 1; see Tables S1 and S2 in the
Supporting Information for additional details). After exten-
sive optimization, we found that 90% isolated yield of the
desired N-arylated sulfoximine 3a could be obtained under
constant-current electrolysis at 4.0 mA in the presence of
5.0 mol% of NiBr2·glyme, 6.0 mol% 4,4’-dimethoxy-2,2’-
bipyridine L1, two equivalents of DBU, and two equivalents
of n-Bu4NBr in DMAc at room temperature after 6 h
(Table 1, entry 1). The reactivity diminished significantly
when an electrode such as carbon or platinum was used
(entries 2–5). Other Ni catalysts such as NiBr2, NiCl2·glyme,
and NiI2 resulted in lower yields (entries 6–8). Additionally,
other bases such as DBN, DABCO, and Et3N proved
ineffective. Finally, evaluating different bipyridine ligands
and phenanthroline ligands revealed that L1 is optimal
(entries 12–20). 76% isolated yield is obtained when the
reaction is carried out with IKA ElectraSyn 2.0 at room
temperature (entry 21). Control experiments indicated that
the Ni catalyst, electric current, and ligand are all required for
this reaction (entries 23–24, Table 1).
With optimized reaction conditions in hand, the substrate
scope was investigated to probe the generality and to identify
limitations of this Ni-catalyzed electrochemical N-arylation of
NH-sulfoximines. As shown in Table 2, the catalytic system
exhibits excellent functional group tolerance. In general, both
electron-deficient and electron-rich aryl bromides afford
good yields under the standard conditions (3b–3i). A variety
of functional groups are readily accommodated, including
ester (3b), cyano (3c), sulfone (3d and 3e), amino (3 f, 3g,
and 3x), ethers (3h, 3i, 3l, 3m), thioethers (3j and 3k), fluoro
(3n), chloro (3o), boronic acid pinacol ester (3p), alcohol
(3q), aryl (3r and 3s), and alkyl (3t–3v) groups. The presence
IKA ElectraSyn 2.0
gram scale
no electric current
no NiBr2·glyme or L1
76[c]
85[d]
0
0
[a] Standard reaction conditions: 1a (1.5 equiv), 2a (0.2 mmol)
NiBr2·glyme (5.0 mol%), L1 (6.0 mol%), DBU (2.0 equiv), n-Bu4NBr
(2.0 equiv), and DMAc (2.0 mL) at rt, in an undivided cell subject to
4.0 mA of current for 6 h using RVC (1.2ꢀ1.2ꢀ0.3 cm3) and Ni foam
(2.0ꢀ3.0 cm2) electrodes, argon, 4.97 FmolÀ1. [b] Determined by
19F NMR analysis using 1-fluoronaphthalene as an internal standard.
[c] Isolated yield in parentheses. [d] Gram Scale (5.0 mmol of 2a), see
the Supporting Information for details. RVC=reticulated vitreous
carbon, DMAc=N,N-dimethylacetamide, DBN=1,5-diazabicyclo-
[4.3.0]non-5-ene, DBU=1,8-diazabicyclo[5.4.0]undec-7-ene,
DABCO=1,4-diazabicyclo[2.2.2]octane.
of a methyl group in the ortho position reduced reactivity
(3w), presumably because of increased steric encumbrance.
Heterocycles such as carbazole (3x), benzodioxine (3y), and
benzodioxole (3z) are well tolerated. Additionally, various
heteroaryl bromides are also competent coupling partners,
including carbazole (3aa), indole (3ab), pyridine (3ac–3af),
pyrimidine (3ag), benzofuran (3ah–3ai) benzothiophene
(3aj–3al), and thiophene (3am), affording the corresponding
arylated sulfoximines in good yields. Encouraged by the
above results, the scope of NH-sulfoximine was examined
using 4-bromobenzotrifluoride 2a as a mode aryl halide as
shown in Table 2. Electron-neutral (3an), electron-rich (3aq),
and electron-deficient (3ar–3av) sulfoximines were tested,
and the corresponding products were furnished in good to
excellent yields. Notably, sulfoximines bearing cyclopropyl
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Table 2: Evaluation of substrate scope.[a]
[a] Yield of isolated products unless otherwise indicated. The reaction was carried out in an undivided cell with NiBr2·glyme (5.0 mol%), L1
(6.0 mol%), DMAc (0.1 M), n-Bu4NBr (2.0 equiv), DBU (2.0 equiv), RVC anode (1.2ꢀ1.2ꢀ0.3 cm3), Ni foam cathode (2.0ꢀ3.0 cm2), constant current
(I=4.0 mA, 6.0 h for 0.2 mmol scale), RT. [b] NiBr2·glyme (5.0 mol%), L1 (15.0 mol%). [c] NiBr2·glyme (10.0 mol%), L1 (12.0 mol%). [d] NiBr2·glyme
(10.0 mol%), L1 (30.0 mol%).
(3aw), diaryl (3ax), and dialkyl (3ay–3be) groups are well
tolerated and afford the respective products in good to
excellent yields. To further demonstrate the utility of our
method, we reacted enantiopure NH-methylphenylsulfoxi-
mine with 4-bromobenzotrifluoride 2a and no racemization
was observed (3an-R, 3an-S).
readily available than aryl bromides or aryl iodides. To our
delight, the developed protocol could be applied to the
diversification of medicinally relevant compounds containing
aryl chlorides (4a–4 f), showcasing the utility of this chemistry
(5a–5l). In contrast, Cu-catalyzed reactions with aryl chlor-
ides[8j] lead to low yields as shown in Figure 2a.
Ni-catalyzed N-arylation of NH-sulfoximines with aryl
chlorides is unknown, although aryl chlorides are more
To gain insight into the mechanism of this electrochemical
N-arylation of NH sulfoximines, we first treated 2-bromo-
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Figure 2. Diversification of pharmaceutical agents, mechanistic study, and proposed catalytic cycle. [a] NiBr2·glyme (10.0 mol%), L1 (30.0 mol%).
[b] NiBr2·glyme (15.0 mol%), L1 (30.0 mol%), 8.0 h. [c] aryl chloride (2.0 equiv), CuI (10.0 mol%), DMEDA (20.0 mol%), NaI (4.0 equiv), dioxane,
1108C, 20 h, then addition of sulfoximine(1.0 equiv), Cs2CO3 (2.5 equiv) followed by further stirring at 1108C for 20 h. DMEDA stands for N,N-
dimethylethylene diamines.
toluene 2w with 4,4’-tert-butyl-2,2’-bipyridine L10 in the
presence of one equivalent of Ni(COD)2 at room temperature
for four hours, affording NiII complex 6 in 70% yield.
Treatment of 6 with sulfoximine 1a at room temperature,
1208C did not give significant amounts of product 3w.
However, when 6 and 1a were subjected to electric current,
3w was formed in 41% yield, indicating that anodic oxidation
of ArNiII species to form ArNiIII is crucial for the product
formation (Figure 2b).
species. However, we cannot rule out other possible pathways
at this stage, in which a Ni0/NiII/NiIII/NiI catalysis sequence is
involved[20] instead of the aforementioned NiI/NiIII/NiII/NiI
sequence.
In summary, we have demonstrated the first example of
Ni-catalyzed electrochemical N-arylation of NH sulfoximines
with aryl bromides and chlorides in an undivided cell at room
temperature, affording sulfoximidoyl derivatives with good to
excellent yields. The protocol is operationally simple and
robust. Owing to the mild reaction conditions, excellent
functional group tolerance is achieved and the developed
protocol is amenable to the diversification of medicinally
relevant compounds. Further research to explore the mech-
anism and to develop metal-catalyzed electrochemical cross-
couplings is currently underway in our laboratory.
Based on literature support[17] and our own cyclic
voltammetric studies (see Figures S1–S4 in the Supporting
Information for details), we propose a plausible catalytic cycle
as shown in Figure 2c. First, the NiII catalyst is reduced to NiI
species (A) by cathodic reduction. Then, after the oxidative
addition, an ArNiIII intermediate (B) is generated. Upon
cathodic reduction of B, the resulting ArNiII species can
undergo ligand exchange with a NH-sulfoximine in the
presence of a base, affording the corresponding ArNiII species
(D). After anodic oxidation of the resulting D, the ArNiIII
species (E) is formed, which undergoes reductive elimination
to give the arylated product 3 or 5 and regenerate the NiI
Acknowledgements
This work was financially supported by the Strategic Priority
Research Program of the Chinese Academy of Sciences
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(Grant XDB20000000), the NSF of China (Grants 21821002,
21772222, and 91956112), the S&TCSM of Shanghai (Grants
18JC1415600 and 20JC1417100), and Bayer AG (Germany).
Conflict of interest
The authors declare no conflict of interest.
Keywords: arylation · Ni catalysis · organic electrochemistry ·
paired electrolysis · sulfoximines
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Manuscript received: December 8, 2020
Revised manuscript received: January 31, 2021
Accepted manuscript online: February 12, 2021
Version of record online: March 17, 2021
Angew. Chem. Int. Ed. 2021, 60, 9444 –9449
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