An electrochemical method for deborylative seleno/thiocyanation of arylboronic acids under catalyst- And oxidant-free conditions

Article abstract of DOI:10.1039/c9gc03797g

An electrochemical deborylative seleno/thiocyanation of arylboronic acids has been well established to synthesize the corresponding aryl seleno/thiocyanates with good functional group tolerance under ambient conditions. A gram-scale reaction has been performed to highlight the advantages of the protocol. Preliminary mechanistic studies indicate that the oxidation of the seleno/thiocyanate anion occurs prior to that of the arylboronic acid substrate in galvanostatic mode, and that free radicals are involved in the process.

Full text of DOI:10.1039/c9gc03797g

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DOI: 10.1039/C9GC03797G
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An electrochemical method for deborylative seleno/thiocyanation
of arylboronic acids under catalyst- and oxidant-free conditions
Dongdong He,a Jiaojiao Yao,a Boling Ma,a,+ Jinghao Wei,a,+ Guangguo Hao,a Xun Tuo,a Shengmei
Received 00th January 20xx,
Accepted 00th January 20xx
Guo,a Zhengjiang Fu,a,b,* and Hu Cai a,*
DOI: 10.1039/x0xx00000x
An electrochemical deborylative seleno/thiocyanation of electrochemical selenocyanation of electron-rich arenes with KSeCN
arylboronic acids has been well established to synthesize has been described as a powerful alternative to construct aryl
corresponding aryl seleno/thiocyanates with good functional selenocyanates using electricity as the driving force.9 Arylboronic
group tolerance under ambient conditions. A gram-scale reaction acids are stable and broadly available materials, significant progress
has been performed to highlight advantage of the protocol. has been made for electrochemical conversion of arylboronic acids
Preliminary mechanistic studies indicated the oxidation of into biaryls,10 aryl amines and phenols11, very recently, our group
seleno/thiocyanate anion should be prior to arylboronic acid has also revealed an efficient method to form aryl halides via ipso-
substrate under this galvanostatic mode, and the involvement of halogenation of arylboronic acids with NaX (X = I, Br) under
conditions.12
To
date,
electrocatalytic
free radicals in the process.
electrochemical
selenocyanation of arylboronic acids to produce certain organic
selenocyanates under metal-free conditions still remain in high
demand.
As an indispensable element in life, selenium can participate in
metabolism process of human body to improve immunity and
enhance physical fitness.1 Furthermore, the incorporation of
selenium into organics has dramatic impact on their physical,
chemical and biological properties. As a result, organoseleniums are
important structural constituents that are present in biologically
active reagents and functional materials.2 In this regard, many
efforts have been devoted into developing powerful methods to
create C-Se bond in the past decades.3 Traditionally, organic
selenocyanates were prepared by employing triselenium
dicyanide,4 potassium selenocyanate KSeCN,5 selenocyano-
benziodoxolone,6 and the combination of elemental selenium and
TMSCN7 as selenocyanide sources in organic synthesis. Although
KSeCN is a simple inorganic chemical with the advantage of low cost,
however, K2S2O8,5a-b selectfluor,5c iodonium reagent,5d TBHP,5e
photocatalyst,5f and CAN5g were usually used as unfavorable
additives in above reports.
Recently, electrochemistry has emerged as an attractive tool for
organic synthesis, since the replacement of stoichiometric amounts
of chemical reagents or oxidants in conventional synthesis methods
with electrons as mass-free reagent can minimize waste
dramatically. As a consequence, organic electrochemical synthesis
has been realized as an efficient and environmentally benign
strategy to build various molecules.8 In this context,
Besides organic selenocyanates, organic thiocyanates are also
important structural motifs in a wealth of natural products.13
Additionally, organic thiocyanates can act as versatile synthetic
precursors to form valuable sulfur-containing derivatives.14 As a
part of our efforts in developing novel functionalization
transformations with cheap coupling partners and green catalytic
methods,12,15 herein, an efficient, practical and scalable
seleno/thiocyanation strategy for arylboronic acids has been
unraveled in a transition metal-free manner under constant-current
electrolytic conditions. Significantly, this electrochemical
deborylative seleno/thiocyanation transformation has several
advantages over traditional seleno/thiocyanation conversion,4-7,16
first of all, the overall process is sustainable in which electricity
served as the driving force, and what's more, a range of arylboronic
acids effectively participated into this simple and metal-free
approach under air atmosphere without any unfavorable additive.
Initially, electrochemical deborylative selenocyanation of 4-
methylphenylboronic acid 9 with KSeCN was chosen as model
reaction to probe various reaction parameters in an undivided cell,
as shown in Table 1. By employing a two-electrode system with a
graphite felt as anode and the other graphite felt as cathode, when
the model reaction was performed with KSeCN (4.0 equiv) under
constant-current electrolysis at 10 mA in anhydrous CH3CN/H2O
(10:0.05, 10.05 mL) mixed solvents at room temperature for 5 hours,
to our delight, the conversion afforded desired p-methylphenyl
selenocyanate 9a in 65% isolated yield (entry 1). In term of solvents,
replacing the mixed solvents with anhydrous CH3CN as a single
solvent or changing the ratio of mixed solvents led to diminished
a. College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, China.
b. State Key Laboratory of Structural Chemistry, Fuzhou, Fujian 350002, China .
† These authors contributed equally to the work.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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Table 1 Optimization of the reaction conditionsa
Although substrates (8-10) with alkyl groups at the ortho and para
positions gave moderate to good yields in five hours reaction time,
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DOI: 10.1039/C9GC03797G
however, owing to steric hindrance of two substituents in ortho
positions, only 42% yield was detected for electrochemical
deborylative selenocyanation of 2,6-dimethylphenylboronic acid
(11). By contrast, electro-neutral phenylboronic acid (12) was
reluctant to undergo electrochemical deborylative selenocyanation
using increased operating current and prolonged reaction time,
whereas trace amounts of products were detected for electron-
deficient substrates (13-16), thus, the results further suggested
remarkable electronic effect on the reaction efficiency. Notably,
ring-fused
naphthylboronic
acids
(17-18)
and
4-
(dibenzofuranyl)boronic acid (19) were suitable coupling partners to
deliver target products. Furthermore, moderate to good yields were
observed for heteroarylboronic acids substrates (20-23),
significantly, benzo[b]thien-3-ylboronic acid (20) and 3-
benzofuranboronic acid (22) formed the desired products in higher
yield than their isomers (21) and (23), respectively.
a Conditions: 9 (0.2 mmol), KSeCN (4.0 equiv, 0.8 mmol), anhydrous
CH3CN/H2O (10:0.05, 10.05 mL) in an undivided cell with two
graphite felts (each 15 x 15 x 0.4 mm3), air, rt, 10 mA, 5 h. b Yield of
isolated product.
Encouraged by the feasibility of electrochemical deborylative
selenocyanation transformation, we further explored deborylative
thiocyanation of arylboronic acids to create corresponding aryl
thiocyanates. To our delight, the desired aryl thiocyanates bearing
electronically diverse groups were obtained in moderate to good
yields with TMSNCS as a thiocyanation reagent in the presence of
KF. During protocol processing, Goossen and co-workers have
recently reported an electrochemical method for ipso-thiocyanation
of aryl boronic acids and trifluoroborates with NH4SCN.17 As
outlined in Table 2, electron-rich (hetero)arylboronic acids
substrates (1-12 and 17-23) well participated in transformation with
TMSNCS/KF to provide aryl thiocyanates under electrochemical
conditions. Fortunately, electron-deficient phenylboronic acid
derivatives (13-16) bearing bromo, chloro, methyl formate and
cyano group were able to undergo electrochemical deborylative
thiocyanation, albeit in moderate yields. It's noteworthy that halo-
moieties in substrates (13-14) were well tolerated in the
conversion, which offered the possibility for late-stage
functionalization via classical activation of C-halo bond. Finally, one
of the desired products (23b) was crystallized and X-ray analysis
unequivocally validated the product structure, which was in
agreement with the NMR spectrum.
outcome, thus, the clue implied a trace of water in mixed solvents
had an influence on the transformation (entries 2-3). Furthermore,
the transformation gave a decreased yield with the introduction of
quaternary ammonium salt as electrolyte, thus, KSeCN played a
dual role as both the coupling partner and supporting electrolyte in
this reaction system (entries 4-5). In terms of electrode selection,
the effect of C(+)/C(-) electrode pairs on the transformation was
better than that of Pt plate as anode or cathode under otherwise
identical conditions (entries 6-7). Both increase and decrease of
reaction time or operating current cut down the reaction yield, thus,
the reaction parameters (5 h and 10 mA) were the best for the
transformation (entries 8-11). It’s noteworthy that raising the
reaction temperature or switching the reaction atmosphere to
nitrogen did not improve conversion efficiency (entries 12-13).
Finally, no reaction took place without the electric current under
otherwise equal conditions, thus, the conversion could be precisely
controlled by switching the electric current on or off (entry 14).
With the optimized reaction conditions established, we next
examined the scope of arylboronic acids substrates to evaluate
generality of the methodology (Table 2). Similarly to our recent
observation,12 this novel transition metal-free electrochemical
deborylative selenocyanation transformation worked well for a
series of arylboronic acids (1-23) with various substituents. As
previously described,12 no matter where the methoxy substituent
located on phenylboronic acid core, 4-methoxyphenylboronic acid
(1) and its isomer 2-methoxyphenylboronic acid (2) well
participated in this electro-organic system to afford desired
deborylative selenocyanation products, moreover, for the case of 4-
methoxyphenylboronic acid bearing another methoxy or formyl
group, moderate to good yields were furnished for substrates 2,4-
Scheme
1 Gram-scale synthesis of product p-hydroxyphenyl
selenocyanate 5a.
To demonstrate the synthetic application of this methodology, a
20-fold scale-up of deborylative selenocyanation of 4-
hydroxyphenylboronic acid 5 with KSeCN was performed using the
same electrosynthetic apparatus. As exhibited in Scheme 1, the
desired product 5a was obtained in 84% yield after 23 hours under
constant current electrolysis in air atmosphere, which afforded the
outcome at a close level with that on a 0.2 mmol scale (see SI for
dimethoxyphenylboronic
acid
(3)
and
3-formyl-4-
methoxybenzeneboronic acid (4) with long reaction time, indicative
of the influence of the electronic effect on transformation.
Interestingly, 4-(dimethylamino)benzeneboronic acid (7) exhibited
better
performance
than
that
of
unprotected
4-
hydroxyphenylboronic acid (5) and 2-aminophenylboronic acid (6).
2 | J. Name., 2012, 00, 1-3
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Table 2 Substrate scope of arylboronic acids in the deborylative
seleno/thiocyanation reactionsa
transformation (entry 10, Table 1). Secondly,
the
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electrochemical
DOI: 10.1039/dCe9bGoCr0y3la79ti7vGe
seleno/thiocyanation
methoxyphenylboronic
of
acid
4-
gave
1
corresponding aryl seleno/thiocyanates in
85% and 83% yields under standard
conditions respectively, however, trace of
the desired product suggested a possible
radical process when 4 equiv of 2,2,6,6-
tetramethylpiperidine 1-oxyl (TEMPO) was
added as radical scavenger into deborylative
selenocyanation transformation, (Scheme
2A), and the evidence of DPE-SCN adduct
further confirmed the presence of a free
radical intermediate during electrolysis when
introducing 2.0 equiv of radical capture 1,1-
diphenylethylene (DPE) into deborylative
thiocyanation conversion (Scheme 2B).
Thirdly, as shown in Figure 1, cyclic
voltammetry
(CV)
of
4-
methoxyphenylboronic acid
1
(curve b)
exhibited an oxidation peak at 2.37 V (vs.
Ag/AgCl), which was higher than that of
KSeCN and TMSNCS (curves c-d), thus, the
comparison substantiated that KSeCN and
TMSNCS could be oxidized more easily than
arylboronic acid substrate under this
galvanostatic mode. Since free radical
intermediates were involved in electrolysis
process, therefore, dual oxidation peaks
which corresponded to the oxidation of
SeCN- to ·SeCN and ·SeCN to SeCN+
respectively were observed in the CV of
KSeCN (curve c), whereas
potential of 1.27 V probably referred to the
oxidation of SCN- to ·SCN (curve d).
a recorded
a
Arylboronic acid (0.2 mmol), KSeCN (4.0 equiv, 0.8 mmol),
anhydrous CH3CN/H2O (10:0.05, 10.05 mL) in an undivided cell with
two graphite felts (each 15 x 15 x 0.4 mm3), air, rt, 10 mA, 80 min. b
Arylboronic acid (0.2 mmol), TMSNCS (3.0 equiv, 0.6 mmol), KF (5.0
equiv), anhydrous CH3CN/H2O (10:0.03, 10.03 mL) in an undivided
cell with two graphite felts (each 15 x 15 x 0.4 mm3), air, rt, 10 mA,
3 h. 3 h. 5 h. anhydrous CH3CN/H2O (10:0.01, 10.01 mL), 5 h.
15 mA, 5 h. anhydrous CH3CN/H2O (10:0.03, 10.03 mL), 3 h. 80
min.
On the basis of above experimental
evidence and literature precedents,9,17-18
plausible mechanism was proposed as
shown in Scheme 3. In Scheme 3A, a
selenocyanate radical intermediate was
a
c
d
e
f
g
h
firstly formed on the anodic electrode by
a single-electron-transfer (SET) process,
followed by the formation of (SeCN)2 via
the details). Therefore, the result declared a great potential of the
method on practical synthesis.
radical coupling and generation of electrophile SeCN+ through
heterolytic bond-cleavage of (SeCN)2. Subsequently,
arylboronic acid I underwent electrophilic attack by SeCN+ to
form active adduct II, which ultimately gave rise to desired
+
product aryl selenocyanate with the release of B(OH)2. In the
case of deborylative thiocyanation transformation, an
alternative process of free-radical addition and then re-
aromatization could be envisioned. In Scheme 3B, since
thiocyanate anion can be generated from the conversion
between TMSNCS and KF,[18b] thus, a thiocyanate radical
intermediate ·SCN was formed by a SET process. After that, the
addition of radical ·SCN to arylboronic acid I and then following
Scheme 2 Radical trapping experiments.
In order to understand the reaction mechanism, some
experiments were carried out to elucidate transformation process.
Firstly, control experiment indicated electricity was essential for the
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Acknowledgements
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DOI: 10.1039/C9GC03797G
Financial support from the National Natural Science
Foundation of China (NSFC) (21761021, 21571094 and
21861026), Natural Science Foundation of Jiangxi Province
(20181BAB204003) and Scientific research and training
program of Nanchang University (3663) is gratefully
acknowledged.
Conflicts of interest
There are no conflicts to declare.
Notes and references
1
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Figure 1 Cyclic voltammograms of substrates: (a) background (KF
0.25 mol/L in MeCN/H2O); (b) p-methoxyphenylboronic acid 1 (0.05
mmol/L); (c) KSeCN (0.08 mol/L); (d) TMSNCS (0.06 mol/L).
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Scheme 3 Proposed mechanism.
oxidation to furnish aryl cation IV through intermediate III at
the anode, re-aromatization of the intermediate IV by losing
+B(OH)2 afforded the final aryl thiocyanate product. At the
cathode,
electro-reduction
of
+B(OH)2
generated
tetrahydroxydiboron detected by LC-MS,
concomitant
production of H2 and OH- via degradation process of H2O in
mixed solvents, while the observation of H2 gas liberation on
cathode was confirmed via GC during electrolysis.
6
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In summary, an operationally simple electrochemical method
for deborylative seleno/thiocyanation of arylboronic acids has
been developed under mild conditions. The feasibility of this
concept provides a straightforward and green method to
synthesize a collection of aryl seleno/thiocyanates in the
absence of transition-metal catalyst and exogenous oxidant.
Gram-scale reaction was performed to assess the advantage
and practicability of the methodology. Further investigation
into mechanism and applications of the approach are
underway in our group, and the results will be reported in due
course.
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Green Chemistry
Page 6 of 6
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DOI: 10.1039/C9GC03797G
Various aryl seleno/thiocyanates have been synthesized from
electrochemical deborylative seleno/thiocyanation of arylboronic acids
under ambient conditions.