Nickel-Catalyzed Thiolation of Aryl Halides and Heteroaryl Halides through Electrochemistry

Article abstract of DOI:10.1002/anie.201900956

Transition-metal-catalyzed coupling reactions are useful tools for synthesizing aryl sulfur compounds. However, conventional transition-metal-catalyzed thiolation of aryl bromides and chlorides typically requires the use of strong base under elevated reaction temperature. Herein, we report the first examples of nickel-catalyzed electrochemical thiolation of aryl bromides and chlorides in the absence of an external base at room temperature using undivided electrochemical cells.

Full text of DOI:10.1002/anie.201900956

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Accepted Article
Title: Nickel-Catalyzed Thiolation of Aryl Halides and Heteroaryl
Halides via Electrochemistry
Authors: Dong Liu, Hong-Xing Ma, Ping Fang, and Tian-Sheng Mei
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10.1002/anie.201900956
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Nickel-Catalyzed Thiolation of Aryl Halides and Heteroaryl
Halides via Electrochemistry
Dong Liu,[a] Hong-Xing Ma,[b] Ping Fang,[a] and Tian-Sheng Mei*[a]
Abstract: Transition-metal-catalyzed coupling reactions are useful
tools to synthesize aryl sulfur compounds. However, conventional
transition-metal-catalyzed thiolation of aryl bromides and chlorides
typically requires the use of strong base under elevated reaction
temperature. Herein, we report the first examples of nickel-catalyzed
electrochemical thiolation of aryl bromides and chlorides in the
absence of an external base at room temperature using undivided
electrochemical cells.
Transition-metal catalyzed thiolation of aryl halides is an
efficient way to synthesize aryl sulfur compounds, which are
abundant in pharmaceuticals, materials, and natural products.[1,2]
However, conventional transition-metal-catalyzed thiolation of
aryl halides typically requires the use of strong base to generate
Scheme 1. Catalytic Thiolation of Aryl Halides
thiolates from thiols. In addition, an elevated reaction
temperature (up to 200 °C), and/or specially designed ligands
Table 1. Reaction Optimization with Substrate 1a[a]
are almost always necessary due to transition-metal catalysts
deactivation by the strong coordination of thiolates to catalysts
(Scheme 1a).[3–6] The requirement of strong bases and elevated
reaction temperatures largely limits functional group tolerance.[7]
To address these issues, in 2013, Peters, Fu, and co-workers
elegantly developed a photoinduced copper-catalyzed thiolation
of aryl halides under mild conditions (0 °C), in which strong base
(NaOt-Bu) is still needed.[8] Inspired by this seminal work,
several other protocols for photoredox-mediated thiolation of aryl
halides in presence of weak base under room temperature have
been developed (Scheme 1b).[9] However, catalytic thiolation of
aryl halides and heteroaryl halides without an external base
under room temperature remains undeveloped.
Recently, we have reported C–O, C–C, and C–N bond
formation via organometallic electrochemistry,[10] which uses
electrical energy to drive chemical transformations, avoiding the
use of stoichiometric chemical oxidants and reductants.[11,12] We
questioned whether thiolation of aryl halides would take place
without an external base under mild reaction conditions via
electrochemistry.[13] In 2017, Baran and co-worker have reported
Ni-catalyzed amination of aryl halides under mild reaction
conditions via paired electrolysis,[14] in which various oxidation
states of nickel catalyst can be accessible in the same pot.[15]
Herein, we establish for the first time that Ni-catalyzed thiolation
of aryl halides and heteroaryl halides in the absence of an
external base under room temperature (Scheme 1c).
[a]
D. Liu, P. Fang, Prof. Dr. T.-S. Mei
State Key Laboratory of Organometallic Chemistry, Center for
Excellence in Molecular Synthesis, Shanghai Institute of Organic
Chemistry, Chinese Academy of Science
345 Lingling Lu, Shanghai 200032, China
E-mail: mei7900@sioc.ac.cn
[b]
Dr. H.-X. Ma
School of Chemistry and Chemical Engineering, Yancheng Institute
of Technology, Yancheng 224051, China
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[a] Standard conditions: 1a (0.3 mmol), 2a (3.0 equiv),
NiBr2·glyme (10 mol%), L1 (10 mol%), LiBr (4.0 equiv), and
DMF (3 mL), in an undivided cell with a Ni foam electrode (2.0 ×
3.0 cm2) and a magnesium sheet (0.5 × 1.5 cm2) as a sacrificial
anode, rt, 4.0 mA, 6 h. [b] The yield was determined by 19F NMR
using 1-fluoronaphthalene as the internal standard. [c] Isolated
yield. RVC = reticulated vitreous carbon.
To initiate the study, we examined this electrochemical
thiolation
of
4-bromobenzotrifluoride
(1a)
with
4-
methylbenzenethiol (2a) under various reaction conditions
(Table 1, and see Tables S1–S6 in the Supporting Information).
To our delight, 85% isolated yield of the desired product (3a)
could be obtained under constant-current electrolysis at 4.0 mA
in the presence of 10 mol% NiBr2·glyme, and four equivalents of
LiBr in DMF at room temperature for 6 h (Table 1, entry 1). NiBr2,
NiCl2·glyme, Ni(OAc)2·4H2O, or Ni(acac)2 led to decreased
yields or no reaction (entries 2–5). Different ligands were
examined and 4,4'-di-tert-butyl-2,2'-bipyridine (di-tBubpy), L1
afforded the best yield (entries 6–10). Mg electrode is better,
although Al sacrificial anode give moderate yield (entry 11).
However, other anodic electrodes such as Pt, RVC are not
effective (entries 12 and 13). Not surprisingly, in the end of
reaction, most of Mg anode was oxidized. At this stage, we are
not sure why other anodes such as Pt, RVC are not working,
although the use of sacrificial anodes could prevent the
reoxidation of Ni(0) species through anodic oxidation.[16] Besides
Ni-foam electrode, other cathodic electrodes including RVC,
graphite, and Pt, are also effective (entries 14–16). On the basis
of atom-absorption spectroscopy, there is no noticeable amount
of Ni particles leaching from Ni-foam after electrolysis.
NiBr2·glyme and electrical current are necessary for this reaction
on the basis of control experiments (entries 17 and 18).
Scheme 3. Evaluation of Heteroaryl Bromides
With the optimized reaction conditions in hand, next, we
investigate the scope and limitation of the reaction. As shown in
Scheme 2, arenes substituted with a variety of functional groups
such as ester, nitrile, nitro, trifluoromethylthio, acetyl, aldehyde,
sulfonyl, chloro, fluoro, and methoxy groups were tolerated (3b–
3s), affording good to excellent yields. In general, aryl bromides
with electron-deficient substituents reacted particularly well. In
addition, various heterocycles, such as pyridine, quinoline,
pyrimidine, pyridazine, benzothiophene, and indole substrates
are also well tolerated in this electrochemical thiolation protocol
(Scheme 3). However, electron-rich arenes are not effective at
current conditions, due to the issue of oxidative addition of the
corresponding aryl halides with Ni(0) species
Next, we moved on to investigate the reactivity of a series of
aryl chlorides, which are readily available and cheap. Again,
electron-deficient aryl chlorides and pyridinyl chlorides are
effective under standard reaction conditions, providing the
corresponding aryl sulfides in good yields (Scheme 4). In
addition, a wide range of aryl thiols bearing various functional
groups, including methoxy, alkyl, fluoro, trifluomethyl groups are
tolerated (Scheme 5).
Scheme 2. Evaluation of Aryl Bromides
Scheme 4. Evaluation of Aryl Chlorides
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well (Scheme 7a). The disulfide might be generated from
dimerization of thiyl radicals.15 The formation of thiyl radical was
further supported by trapping the thiyl radical with TEMPO,
affording 11 in 30% yield. Similarly, compound 11 was also
obtained in the absence of Ni catalyst (Scheme 7b). In order to
understand why the thiyl radical could be generated on Mg
anode, we carried out cyclic voltammetry (CV) experiments to
reveal the redox potential of Mg anode, thiol 2a, and thiolate 9,
(See Figure S1–S7 in the Supporting Information). The onset
oxidation potential of Mg is around -0.7 V vs. Ag/Ag+ (see Figure
S6 in Supporting Information for the details). Although the
observation of oxidation waves for thiol 2a and thiolate 9 are
unsuccessful due to the oxidation of Mg. However the oxidative
electric current is decreased significantly in the presence of
thiolate 9, which might indicate the oxidation of thiolates to thiyls
is occurring (Figure S6 in the Supporting Information). To our
delight, oxidation wave of thiolate 9 was observed when
aluminum or galssy carbon anodes are used and the onset
oxidation waves are around -1.2 V and -0.8 V vs. Ag/Ag+
respectively (Figure S7 and S2). These data suggests that
oxidation of thiolates to thiyl radicals is possible.
Scheme 5. Evaluation of Aryl Thiols
Furthermore, we demonstrated preparative utility of this
electrochemical thiolation reaction by using a reaction containing
6.0 mmol of substrate 1h, which furnished the desired product
3h in 60% yield (Scheme 6).
According to literature reports and our experimental data, a
plausible mechanism is presented in the Scheme 8. Ni(0)
species could be formed from Ni(II) or Ni(I) by cathodic reduction
(Scheme 8).[17] Oxidative addition of Ni(0) to an aryl halide
generates an aryl Ni(II) complex 12, which reacts with a thiolate,
deriving from cathodic reduction of a thiol (RSH) to give
intermediate 13. Reductive elimination from resulting 13 delivers
the product and Ni(0) species (path a, Scheme 8).[18]
Alternatively, path b, which involves in thiyl radicals, could not be
ruled out at this stage.
Scheme 6. Gram-Scale Experiment
Scheme 8. Plausible reaction mechanism.
In conclusion, we have developed the first example of Ni-
catalyzed electrochemical thiolation of aryl bromides and
chlorides in an undivided cell at room temperature without an
external base. These findings provide a new avenue for
transition-metal-catalyzed cross-coupling reactions. Further
efforts to understand the reaction mechanism are currently
underway in our laboratory.
Scheme 7. Trapping of the Thiyl Radicals With TEMPO.
Although the reaction mechanism is not well understood at
this stage, we have made a few important observations. The
magnesium anode is almost consumed after the reaction, which
suggests that the oxidation of Mg0 to Mg2+ is taking place on the
Mg anode. Surprisingly, under the standard condition, disulfide
10 was obtained with good yields along with desired product 3a
and the disulfide 10 was formed in the absence of Ni catalyst as
Acknowledgements
This work was financially supported by the Strategic Priority
Research Program of the Chinese Academy of Sciences (Grant
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XDB20000000), NSF of China (Grant 21772222, 21821002),
and S&TCSM of Shanghai (Grant 17JC1401200, 18JC1415600).
We thank Professor Hai-Chao Xu (Xiamen University) for helpful
discussion on the reaction mechanism.
Keywords: organic electrochemistry • organometallic
electrochemistry• thiolation • nickel • thiyl radical
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10.1002/anie.201900956
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Dong Liu, Hong-Xing Ma, Ping Fang and
Tian-Sheng Mei*
Page No. – Page No.
Nickel-Catalyzed Thiolation of Aryl
Halides and Heteroaryl Halides via
Electrochemistry
The first example of nickel-catalyzed electrochemical thiolation of aryl halides in the
absence of an external base at room temperature using undivided electrochemical
cells is reported, thereby providing a practical solution for the construction of aryl
and heteroaryl C–S bonds.
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