Copper-catalyzed three-component ortho-selective selenation of phenols

Article abstract of DOI:10.1080/10426507.2021.1945600

An efficient and convenient copper-catalyzed three-component reaction has been developed for the arylselenation of phenols with Se powder and aryl iodides. This one-pot procedure provides a straightforward approach to the synthesis of ortho-arylselenylphenols with high regioselectivity. This practical process shows good functional group tolerance, providing the corresponding products in moderate to good yields.

Full text of DOI:10.1080/10426507.2021.1945600

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/gpss20
Copper-catalyzed three-component ortho-selective
selenation of phenols
Run Luo, Lina Guo, Meiyun Su, Wenjie Liu & Shaohua Wang
To cite this article: Run Luo, Lina Guo, Meiyun Su, Wenjie Liu & Shaohua Wang (2021): Copper-
catalyzed three-component ortho-selective selenation of phenols, Phosphorus, Sulfur, and Silicon
and the Related Elements, DOI: 10.1080/10426507.2021.1945600
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2021.1945600
SHORT COMMUNICATION
Copper-catalyzed three-component ortho-selective selenation of phenols
Run Luoa, Lina Guoa, Meiyun Sua, Wenjie Liua,b, and Shaohua Wanga,b
b
aSchool of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Guangzhou, P.R. China; Guangdong Cosmetics
Engineering and Technology Research Center, Guangzhou, P.R. China
ABSTRACT
ARTICLE HISTORY
Received 16 February 2021
Accepted 16 June 2021
An efficient and convenient copper-catalyzed three-component reaction has been developed for
the arylselenation of phenols with Se powder and aryl iodides. This one-pot procedure provides a
straightforward approach to the synthesis of ortho-arylselenylphenols with high regioselectivity.
This practical process shows good functional group tolerance, providing the corresponding prod-
ucts in moderate to good yields.
KEYWORDS
Selenation; phenols;
Se powder; copper;
regioselectivity
GRAPHICAL ABSTRACT
Introduction
phenylselenation of phenols catalyzed by ammonium salts
(Scheme 1, Eq. b).[12] More recently, Yang and coworkers
described a metal-free synthesis of phenol-aryl selenides via
coupling reaction of aryl selenoxides with phenols (Scheme
1, Eq. c).[13] Inspired by the above successful research on
the selenylation of phenols, we herein report the first
example of copper-catalyzed ortho arylselenation of phenols
via three-component coupling reaction of aryl iodides, Se
powder and phenols.
Here we began this study by choosing 4-methoxyphe-
nol 1a and iodobenzene 2a as model substrates in the
presence of elemental selenium (Table 1). The desired
ortho-selective arylselenation product 3a was obtained in
58% yield by using 10 mol% of CuO as catalyst, 3 equiv
of K3PO4 as base in DMSO at 120 ꢀC for 12 h (Table 1,
entry 1). Among other copper salts tested, Cu(OAc)2 dis-
played the best choice and afforded the desired product
3a in 81% yield (Table 1, entries 2–5). Next, we investi-
gated the influence of bases. The replacement of K3PO4
by K2CO3, KOH, and t-BuOK was ineffective (Table 1,
entries 6–8). The yield of corresponding product 3a
increased to 85% when Na3PO4Á12H2O was used as base
(Table 1, entry 9). The effect of solvents on this trans-
formation was also screened. The use of other solvents
(DMF, 1,4-Dioxane, CH3CN, DCE, and Toluene) led to
poor yields (Table 1, entries 10–14). An attempt to reduce
or increase the reaction temperature resulted in a lower
The construction of selenium-containing architectures has
already attracted increasing attention, due to the fact that
selenium-containing compounds are found in natural prod-
ucts, drugs, and active molecules.[1] In particular, organose-
lenium compounds exhibit a diverse of biological activities
such as lipoxygenase inhibitor, anti-Alzheimer, antimicro-
bial, antioxidant, antiproliferative functions, and antitumor
agent (Figure 1).[2] In recent decades, many selenium
reagents including selenol,[3] ArSeSnR3,[4] diselenide,[5]
SeO2,[6] KSeCN,[7] and NaO2SeR[8] have been successfully
used for building diaryl selenides. However, these selenium
reagents suffer from longer synthetic steps, relatively high
cost or environmental problems. Currently, the application
of selenium powder for C–Se bonds construction has
aroused the interest of organic chemists, which is stable,
cheap, and easy to handle.[7,9]
Phenols are often used as important intermediates and
exhibit higher reactivities in various chemical transforma-
tions.[10] Among them, selenium-containing phenol deriva-
tives have several pharmacological applications. But the
regioselective selenation of phenols is still challenging and
few practical methods have been reported. Recently, Takaki
and coworkers[11] reported the direct selenylation of phenols
using a stoichiometric amount of FeCl3 under an oxygen
atmosphere (Scheme 1, Eq. a). In other study, Yeung and
coworkers developed highly practical ortho-selective yield of the desired product 3a (Table 1, entries 15 and
CONTACT Wenjie Liu
wjliu1113@126.com; Shaohua Wang
wangshaohua108@163.com
School of Chemistry and Chemical Engineering, Guangdong
Pharmaceutical University, Guangzhou 510006, P.R. China.
Supplemental data for this article is available online at https://doi.org/10.1080/10426507.2021.1945600.
ß 2021 Taylor & Francis Group, LLC

2
R. LUO ET AL.
Figure 1. Organoselenium compounds with biological activity.
Scheme 1. Examples of direct arylselenation of phenols.
16). The reaction could not occur in the absence of cop- reacted smoothly with 4-methoxyphenol 1a and generated
per catalyst (Table 1, entry 17). Using bromobenzene
instead of iodobenzene afforded only a trace of 3a (Table
1, entry 18).
With the optimized conditions in hand, we next turned
our attention to the scope of aryl iodides and phenols. As
shown in Table 2, a variety of aryl iodides with either
electron-withdrawing or electron-donating groups in the
ortho, meta, or para position of benzene rings, were
the desired products 3a–3l in moderate to good yields. As
expected, methyl group and halogen atoms (F, Cl, Br)
were well-tolerated. Notably, this arylselenation was
slighted affected by the steric hindrance on the ortho-pos-
ition of aryl iodides (3b, 3e, 3g). The strong electron-with-
drawing group (–CF3) on the phenyl ring of aryl iodides
was compatible under this condition, and the desired
product 3k was isolated in 67% yield. Pleasing, this

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
Table 1. Optimization of the reaction conditions.
Table 2. Scope of the aryl iodides.
Entry
Catalyst
Base
Solvent
Yield (%)a
1
2
3
4
5
6
7
8
CuO
CuI
CuCl2
CuBr2
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K2CO3
KOH
t-BuOK
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
1,4-dioxane
CH3CN
DCE
Toluene
DMSO
DMSO
DMSO
DMSO
58
60
72
70
81
65
47
73
85
72
40
56
Trace
–
41
69
–
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
–
9
Na3PO4Á12H2O
Na3PO4Á12H2O
Na3PO4Á12H2O
Na3PO4Á12H2O
Na3PO4Á12H2O
Na3PO4Á12H2O
Na3PO4Á12H2O
Na3PO4Á12H2O
Na3PO4Á12H2O
Na3PO4Á12H2O
10
11
12
13
14
15b
16c
17
18d
Cu(OAc)2
Trace
Reaction conditions: 4-methoxyphenol 1a (0.5 mmol), iodobenzene 2a
(0.2 mmol), Se (0.6 mmol), catalyst (10 mol%), base (3 equiv) in 2 mL of solv-
ent at 120 ꢀC for 12 h, under air.
aIsolated yield.
b80 ꢀC.
c140 ꢀC.
dBromobenzene was used instead of iodobenzene.
All reaction were performed with 1a (0.5 mmol), 2 (0.2 mmol), Se (0.6 mmol),
Cu(OAc)2 (10 mol%) and Na3PO4Á12H2O (0.6 mmol) in 2 mL of DMSO at
120 ꢀC for 12 h, under air. Isolated yields.
arylselenation reaction was highly regioselective at ortho-
position on the phenol ring under our standard experi-
mental conditions.
obtained in 90% yield by treating iodobenzene 2a with Se
powder under the standard reaction conditions (Scheme 2,
Eq. 1). Next, the coupling reaction of diphenyl diselenide 4
with 4-methoxyphenol 1a generated the desired product 3a
in 80% yield, indicating that diselenide may be a key reac-
tion intermediate (Scheme 2, Eq. 2). Finally, by the addition
of radical scavenger 2,2,6,6-tetramethyl-1-piperidinyloxy
(TEMPO) under the optimized reaction conditions, the
desired product was smoothly produced; this results indi-
cated that radical pathway was not occurred in the arylsele-
nation reaction (Scheme 2, Eq. 3).
Furthermore, a variety of substituted phenols were
studied under optimized reaction conditions to explore the
scope and generality of this transformation (Table 3).
Phenols with different functional groups such as methyl,
ethyl, isopropyl, chloro, and phenyl groups at para-position
successfully afforded the desired products 3m–3q in good
yields. When carbomethoxy group was introduced at para-
position of phenol, the corresponding product 3r was
obtained in 78% yield. To investigate the regioselectivity of
this arylselenation reaction, meta and ortho-substituted phe-
nols bearing methyl, tert-butyl and methoxy groups were
tested and gave the arylselenation products 3s–3v with com-
plete ortho-selectivity. The above results highlight the gener-
ality of this new system. Complete experimental details,
7,
Based on the above results and previous reports,[5k,
9a–c] a plausible mechanism for the regioselective copper-
catalyzed selenation reaction is illustrated in Scheme 3.
Initially, the copper selenide intermediate A is formed by
the reaction of iodobenzene 2a with Se powder in the
presence of copper catalyst and base. The intermediate A
may oxidize to the key species diphenyl diselenide 4
under air atmosphere. The interaction of diphenyl disele-
nide 4 with CuI leads to a CuIII tetracoordinated square
1
characterization and sample H, 13C, and 19F NMR spectra
are
presented
in
the
Supplemental
Materials
(Figures S1–S46).
In an effort to gain more preliminary insight into the
reaction mechanism, several control experiments were car-
ried out as shown in Scheme 2. Diphenyl diselenide 4 was planar sulfate B. Phenol 1a would attack the intermediate

4
R. LUO ET AL.
Table 3. Scope of the phenols.
B at the ortho-position to generate intermediate C. A pro-
ton elimination from intermediate C gives target product
3a, releasing arylselenol species and copper catalyst for
next recycle.
Conclusion
In conclusion, a novel and facial method for synthesis of
arylselenylphenols via copper-catalyzed three-component
coupling reaction of phenols, Se powder, and aryl iodides
has been developed. This approach employs commercially
available elemental selenium as
a selenating reagent.
Importantly, the reaction proceeds with high ortho-selectiv-
ity and broad functional group tolerance. Due to the
importance of C–Se bonds formation, further studies to
All reaction were performed with 1 (0.5 mmol), 2a (0.2 mmol), Se (0.6 mmol),
Cu(OAc)2 (10 mol%) and Na3PO4Á12H2O (0.6 mmol) in 2 mL of DMSO at
120 ꢀC for 12 h, under air. Isolated yields.
p-Iodotoluene was used instead of iodobenzene.
Scheme 3. Proposed reaction mechanism.
Scheme 2. Control reactions.

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
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