A cost-effective shortcut to prepare organoselenium catalysts via decarboxylative coupling of phenylacetic acid with elemental selenium

Article abstract of DOI:10.1002/aoc.4599

An interesting decarboxylative coupling reaction of phenylacetic acid with elemental selenium was discovered and employed for the preparation efficient organoselenium catalysts for Baeyer–Villiger reaction and oxidative deoximation reaction. Compared with the traditionally used Grignard reagent method, the decarboxylative coupling reaction with selenium powders provides a shortcut for the preparation of organoselenium catalysts free of carcinogenic organohalide starting materials, toxic and odorous selenol intermediates and magnesium salt solid wastes. This may be helpful for reducing the cost of selenium catalysts to facilitate the application of organoselenium-catalyzed green reactions in large-scale production.

Full text of DOI:10.1002/aoc.4599

Received: 23 July 2018
DOI: 10.1002/aoc.4599
Revised: 24 August 2018
Accepted: 25 August 2018
F U L L P A P E R
A cost‐effective shortcut to prepare organoselenium
catalysts via decarboxylative coupling of phenylacetic acid
with elemental selenium
Hongen Cao1,2 | Mingxuan Liu1 | Rongrong Qian3 | Xu Zhang1 | Lei Yu1,2
1 Guangling College, School of Chemistry
An interesting decarboxylative coupling reaction of phenylacetic acid with
elemental selenium was discovered and employed for the preparation
efficient organoselenium catalysts for Baeyer–Villiger reaction and oxidative
deoximation reaction. Compared with the traditionally used Grignard reagent
method, the decarboxylative coupling reaction with selenium powders provides
a shortcut for the preparation of organoselenium catalysts free of carcinogenic
organohalide starting materials, toxic and odorous selenol intermediates and
magnesium salt solid wastes. This may be helpful for reducing the cost of sele-
nium catalysts to facilitate the application of organoselenium‐catalyzed green
reactions in large‐scale production.
and Chemical Engineering, and Institute
of Pesticide of School of Horticulture and
Plant Protection, Yangzhou University,
Yangzhou, Jiangsu 225002, China
2 Jiangsu Key Laboratory of Zoonosis,
Yangzhou University, Yangzhou 225009,
China
3 Jiangsu College of Tourism, Yangzhou
225009, China
Correspondence
Xu Zhang and Lei Yu, Guangling College,
School of Chemistry and Chemical
Engineering, Institute of Pesticide of
School of Horticulture and Plant
Protection, Yangzhou University,
Yangzhou, Jiangsu 225002, China.
Email: zhangxu@yzu.edu.cn; yulei@yzu.
edu.cn
KEYWORDS
Selenium, organoselenium catalysis, green chemistry, diselenide, decarboxylative coupling
Funding information
NNSFC, Grant/Award Number: 21202141;
Priority Academic Program Development
of Jiangsu Higher Education Institutions
(PAPD), Grant/Award Number: 21202141;
the Nature Science Foundation of
Guangling College, Grant/Award Num-
bers: ZKZD17005 and ZKZZ18001; the
Open Project Program of Jiangsu Key
Laboratory of Zoonosis, Grant/Award
Numbers: R1509 and R1609; Top‐notch
Academic Programs Project of Jiangsu
Higher Education Institutions (TAPP)
1 | INTRODUCTION
catalysis is one of the most important research directions
for its clean procedures, transition‐metal‐free reaction
Organoselenium compounds have been widely employed
in biochemistry, medicinal chemistry, organic synthesis
and materials science for their unique bioactivities
and chemical activities.[1] Recently, much attention has
been paid to the eco‐friendly aspects of organoselenium
chemistry[2] and among reported works, organoselenium
conditions and the metabolizable catalytic Se element
that affords a potential alternative to transition metal
catalysts.[3] Researchers have reported
a series of
organoselenium‐catalyzed reactions and this field has
seen rapid progress in recent years.[4,5] However, up to
the present, the frequently used method for introducing
Appl Organometal Chem. 2018;e4599.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4599

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CAO ET AL.
Se into molecules to synthesize Se catalysts is via the
Grignard reagent reaction, which is very tedious to oper-
ate and suffers from the use of carcinogenic organohalide
starting materials that are hazardous to the environment
(Scheme 1). The method inevitably generates toxic and
odorous selenol intermediates and magnesium salts as
solid wastes (Scheme 1). Therefore, developing a more
direct and environment‐friendly method for the synthesis
of Se catalysts is an inescapable step before any applica-
tion of the organoselenium catalysis techniques in large‐
scale production.
protection, but, unfortunately, no desired product was
observed after 20 h of reaction (Table 1, entry 1). Tertiary
amines, such as tri‐n‐butylamine, tri‐n‐octylamine, N,N‐
diisopropylethylamine (DIEA) and 1‐methylpiperidine,
were comprehensively introduced as additives to improve
the reaction and it was found that DIEA was the most
favorable base, affording dibenzyl diselenide in 26%
yield, while dibenzyl selenide was also obtained in 37%
yield as the co‐product. The Se content index (n) of mix-
1
ture 2 was calculated to be 1.41 according to H NMR
analysis (Table 1, entry 2).[10] Secondary amines, such as
diethylamine, di‐n‐butylamine (DNBA), pyridine, piperi-
dine, pyrrolidine, 1‐methylpiperazine and morpholine,
were examined, and DNBA was found to be the favorable
base, affording 2 in 59% yield, while n was also calculated
to be 1.41 (Table 1, entry 3).[10] Other bases, including
aniline derivatives or inorganic bases such as NaOH,
KOH, Na2CO3 and K2CO3, were all unfavorable additives
for the reaction (Table 1, entries 4 and 5).[10] A series of
parallel experiments were then performed to determine
the preferable amount of base for the reaction. Using
100 mol% of DIEA (versus substrate 1) as the base addi-
tive, the reaction led to 2 in 29% yield, with n = 1.34
(Table 1, entry 6) and it was contrarily restrained with
further increase of DIEA amount over 200 mol%
(Table 2, entries 7 and 8 versus 2). Similar trends were
also observed in the reactions with DNBA as the base,
and using 200 mol% of DNBA was also found to be the
preferable amount (Table 1, entry 3).[10] Effects of the
amount of Se on the reaction were then examined.
The reaction of 1 with 50 mol% of Se afforded 2 in 29%
yield, with n = 1.30 (Table 1, entry 9). With 100 mol%
of Se, the reaction afforded 2 in 34% yield (Table 1, entry
10). The product yield could be further enhanced by using
an increased amount of Se powders, and 400 mol% of Se
was found to be the better amount (Table 1, entries 2
versus 9–13). Interestingly, the values of n for products
2 were almost invariable, regardless of the amount of Se
used (Table 1, entries 2, 10–13).
Decarboxylative coupling reactions[6] are promising
because of the solid‐waste‐free procedures and the eas-
ily accessible and halogen‐free starting materials.
Releasing harmless CO2 gas provides strong driving
forces for these transformations. The decarboxylative
coupling reactions may proceed via free radical mecha-
nisms.[7] During our continuing investigations of green
synthesis,[5,8,9] it was found that heating elemental Se
could lead to Se8 bi‐radicals, which were efficient
selenylation reagents for the preparation of cyclic
diselenides.[9] Thus, we considered that catalytically
active Se compounds might also be synthesized
through the direct decarboxylative coupling reactions
of carboxylic acids with Se powders via thermo‐
initiated free radical mechanisms. Efforts were made
to achieve this objective and it was found that benzyl
Se catalysts for Baeyer–Villiger reactions and oxidative
deoximation reactions could be easily synthesized via
an interesting transition‐metal‐free decarboxylative
coupling reaction of phenylacetic acid with elemental
Se. Herein we report the details of this work.
2 | RESULTS AND DISCUSSION
Phenylacetic acid (1) was initially heated with Se powders
in dimethylformamide (DMF) at 150°C under N2
We then tried to improve the reaction conditions by
screening the reaction solvent and temperature. No prod-
uct was obtained under solvent‐free reaction conditions
or in a low‐polarity solvent such as CHCl3 or CH2Cl2
(Table 2, entries 1 and 2). In MeCN, the product 2
(n = 1.45) was obtained in 22% yield (Table 2, entry 3).
The reactions in EtOH or EtOH–H2O both led to poor
product yields (Table 2, entries 4 and 5). It was then
found that the high‐polarity solvents dimethylsulfoxide
(DMSO) and DMF were favorable for the reaction,
affording 2 in 53–63% yields (n = 1.41–1.42; Table 2,
entries 6 and 7). A series of reactions at various tempera-
tures were conducted. The results demonstrated that
140–160°C was the favorable reaction temperature range,
SCHEME 1 Introduction of Se into molecules through the
Grignard reagent method

CAO ET AL.
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TABLE 1 Screening of bases and amount of Se for decarboxylative coupling of phenylacetic acid with Sea
Entry
Base (amount, %)b
Se amount (%)b
nc
Yield (%)d
1
—
400
400
400
400
400
400
400
400
50
—
0
2
DIEA (200)
DNBA (200)
Anilines (200)
Inorganic bases (200)
DIEA (100)
DIEA (300)
DIEA (400)
DIEA (200)
DIEA (200)
DIEA (200)
DIEA (200)
DIEA (200)
1.41
1.41
—
63
59
0–24
0
3
4
5
—
6
1.34
1.33
—
29
30
0
7
8
9
1.30
1.44
1.41
1.43
1.40
29
34
59
44
25
10
11
12
13
100
200
600
800
a1 mmol of 1, 4 mmol of Se and 1 ml of DMF solvent were employed.
bMolar ratio versus substrate 1.
cValues of Se content index (n) were calculated from the molar ratios of diselenide versus selenide determined by 1H NMR analysis (for details, see supporting
information).
dIsolated yields.
TABLE 2 Optimization of reaction conditionsaa
Entry
Solvent
T (°C)
n
Yield (%)b
1
No solvent
CHCl3 or CH2Cl2
MeCN
150
—
0
0
2
150c
150c
150c
150c
150
—
3
1.45
1.43
1.40
1.42
1.41
—
22
23
10
53
63
0
4
EtOH
5
EtOH–H2O (1/1)
DMSO
6
7
DMF
150
8
DMF
120
9
DMF
130
1.33
1.41
1.42
1.33
—
33
59
55
27
0
10
11
12
13
DMF
140
DMF
160c
170c
180c
DMF
DMF
a1 mmol of 1, 4 mmol of Se, 2 mmol of DIEA and 1 ml of solvent were employed.
bIsolated yields.
cReaction performed in a sealed tube.

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CAO ET AL.
affording 2 in 55–63% yields (Table 2, entries 7, 10, 11
versus 8, 9, 12, 13). No desired product was obtained at
a temperature lower than 120°C or exceeding 180°C
(Table 2, entries 8 and 13). In the former reaction, much
unconverted 1 was observed using TLC (Table 2, entry 8),
while in the latter one, a series of complex by‐products
were generated (Table 2, entry 13). The values of n were
generally invariable in the reactions at the preferable
reaction temperatures (Table 2, entries 7, 10 and 11).
Mechanisms of this interesting reaction were our next
concern, and metal catalysts were introduced into the
reaction to investigate their catalytic activities. The stan-
dard reaction (Table 1, entry 2) with 10 mol% of CuI,
CuBr, Cu(OAc)2, FeCl3 or FeCl2 generated no desired
diselenide or selenide product, while much unconverted
1 was observed using TLC, indicating that the metal salts
actually restrained the reactions. Reactions with 10 mol%
of ZnI2 or ZnCl2 as catalyst produced 2 in 26 and 17%
yields with n = 1.42 and 1.35, respectively. These results
demonstrated that, different from previous report,[7] this
decarboxylative coupling reaction proceeded through a
non‐metal‐catalyzed mechanism. In order to gain essen-
tial information for the mechanism study, a control
reaction with 1 eq. of hydroquinone as a free radical scav-
enger was performed. It was found that the reaction was
completely prohibited (Scheme 2), indicating that this
decarboxylative coupling reaction with Se occurs via a
free radical mechanism as in previous reports.[6,7] More-
over, since it was found that a white precipitate was
produced on mixing the reaction liquid with lime water,
it was corroborated that carbon dioxide was generated
during the processes.
Thus, based on these experimental results as well as
literature reports,[7,9] a plausible mechanism of this inter-
esting transition‐metal‐free decarboxylative coupling
reaction is proposed. As shown in Scheme 3, Se powders
(Se8) might first generate the Se bi‐radical 3 under ther-
mal conditions.[9] Capturing a hydrogen from substrate
1, 3 is transformed into intermediate 4 and the carboxyl
radical 5 is generated. Decarboxylation of 5 produces
the benzyl free radical 6,[7] which is thermodynamically
stabilized by the p–π conjugation of the adjacent phenyl
ring. The reaction of 6 with Se8 leads to intermediate 7,
which might produce 8 via a deselenization reaction.[9]
Dimerization of 8 leads to dibenzyl diselenide (n = 2),
while the possible reaction of 8 with benzyl radical 6
produces dibenzyl selenide (n = 1). Although this mech-
anism remains to be fully clarified and alternative pro-
cesses might also occur due to the complexity of the free
radical reactions, Scheme 3 should be the most likely
mechanism on the basis of the experimental results and
literature reports.[7,9]
Because of the complex free radical mechanism,
it was difficult to control the reaction selectivities
between diselenide and selenide. Worse yet, due to the
similar polarities of the diselenide and selenide, it was
also difficult to separate them via regular chromatogra-
phy methods such as the flash column chromatography
or preparative TLC. Therefore, this decarboxylative
coupling method is of less utility for the purposes of
SCHEME 2 Control reaction with
hydroquinone as free radical scavenger
SCHEME 3 Possible mechanisms for
the decarboxylative coupling reaction

CAO ET AL.
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synthesizing pure dibenzyl diselenide or dibenzyl sele-
nide. Fortunately, since the literature demonstrates that
both diselenides and selenides are efficient catalysts in
oxidation reactions,[4,5] their mixtures may also be effec-
tive catalysts in related reactions. For this reason, we
investigated the catalytic activities of mixtures 2 in the
useful Baeyer–Villiger oxidation reaction of (E)‐4‐
phenylbut‐3‐en‐2‐one (9) with H2O2 to produce vinyl
ester 10 (Scheme 4).[11]
As shown in Figure 1, the oxidation reaction of 9 cat-
alyzed by pure dibenzyl diselenide (n = 2) led to 10 in
82% yield; whereas, the same reaction with pure dibenzyl
selenide (n = 1) as the catalyst resulted in a decreased
yield of 42%. Using mixture 2 with n = 1.69 as the catalyst
(prepared by the reaction of Table S1, entry 15), the
Baeyer–Villiger reaction of 9 afforded 10 in 73% yield,
while the reaction in the presence of catalytic mixture 2
with n = 1.41 (prepared by the reaction of Table 1, entry
2) could still produce 10 in an acceptable yield of 60%.
The same oxidation reactions of 9 catalyzed by electron‐
enriched Se catalysts (4‐MeOC6H4Se)2/(4‐MeOC6H4)2Se
or electron‐deficient Se catalysts (4‐FC6H4Se)2/(4‐
FC6H4)2Se were also examined and they all led to
decreased yields of 10 (Figure 1). Thus, considering the
catalyst cost and catalytic performances, the mixtures of
dibenzyl diselenide and dibenzyl selenide, prepared via
the decarboxylative coupling reaction of phenylacetic
acid with elemental Se reported in this work, should be
preferable catalysts.
Oxidative deoximation reactions are also very impor-
tant in synthetic organic chemistry[12] because oximes
are easily prepared and stable compounds that allow the
utilization of oximation–deoximation strategies in protec-
tion and purification of carbonyl compounds in total syn-
thesis.[13] They are also widely employed in the
preparation of ketones from non‐carbonyl starting mate-
rials, such as in the production of the spice carvone from
limonene.[14] Therefore, we then evaluated the catalytic
performances of mixtures 2 in oxidative deoximation
reaction, with the reaction of diphenylmethanone oxime
(11) being chosen as the model reaction (Scheme 5).
As shown in Figure 2, catalyzed by pure dibenzyl
diselenide (n
= 2), the reaction of 11 afforded
diphenylmethanone (12) in 89% yield, while the pure
dibenzyl selenide (n = 1)‐catalyzed reaction led to a
moderate product yield of 63%. Using mixtures 2 with
n = 1.69 and 1.41 as the catalysts (prepared by the reac-
tion of Table S1, entry 15 and Table 1 entry 2), the
reactions afforded 12 in 88 and 84% yields, respectively,
which showed that mixtures 2 were almost as active
as pure diselenide (n = 2) in a much broader range
of n in this deoximation reaction than that in the
previously investigated Baeyer–Villiger reaction (light
blue symbols in Figure 2 versus Figure 1). The catalytic
SCHEME 4 Baeyer–Villiger reaction of 9 catalyzed by 2
SCHEME 5 Oxidative deoximation reaction of 11 catalyzed by 2
FIGURE 1 Baeyer–Villiger oxidation
reactions of 9 catalyzed by diselenide/
selenide mixtures

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CAO ET AL.
FIGURE 2 Oxidative deoximation
reactions of 11 catalyzed by diselenide/
selenide mixtures
performances of electron‐enriched and electron‐deficient
diselenides/selenides were also evaluated in the
deoximation reaction (red and black diamonds in
Figure 2), and they were found to be less reactive than
mixtures 2 (blue diamonds in Figure 2), which were even
cheaper for being prepared using unsubstituted 1 as the
more accessible and inexpensive starting material.
method and their catalytic activities were investigated in
the oxidative deoximation reactions of 11 (Figure 3).
Introducing an electron‐donating group into the substrate
did not affect the reaction (Figure 3, black bars, entries 2
versus 1), while electron‐deficient substrates were prefer-
able, affording elevated product yields (Figure 3, black
bars, entries 3–5 versus 1 and 2). The method was also
applicable for the preparation of branched or cyclic
aliphatic organoselenium compounds (Figure 3, black
Moreover, a series of organoselenium compounds
were synthesized through the decarboxylative coupling
FIGURE 3 Synthesis and evaluation of diselenide/selenide mixtures

CAO ET AL.
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bars, entries 6–8). Chained aliphatic organoselenium
compounds were also accessible (Figure 3, black bars,
entries 9 and 10) and showed higher catalytic activities
in the oxidative deoximation reactions (Figure 3, blue
bars, entries 9 and 10 versus 6–8). Electron‐enriched or
electron‐deficient diselenide/selenide mixtures were less
catalytically active than the dibenzyl diselenide/selenide
mixture (Figure 3, blue bars, entries 2–10 versus 1), albeit
their higher n values (Figure 3, red bars, entries 2–10 ver-
sus 1). The decarboxylative coupling reaction of benzoic
acid could not occur, possibly due to the good stability
of the substrate as well as the instability of the phenyl free
radical intermediate (Figure 3, black bar, entry 11).
20 h. After cooling to room temperature, the produced
mixtures 2 containing dibenzyl diselenide and dibenzyl
selenide could be isolated by flash column chromatogra-
phy (eluent: petroleum ether). They were subjected to
1H NMR analysis to calculate the Se content indexes n
(for details, see the supporting information). The molar
ratio of diselenide versus selenide could be calculated by
the equation: diselenide/selenide = (n − 1)/(2 − n).
4.3 | Details of Baeyer–Villiger oxidation
of (E)‐4‐phenylbut‐3‐en‐2‐one with H2O2
To a reaction tube, 1 mmol of (E)‐4‐phenylbut‐3‐en‐2‐
one, 0.05 mmol of 2, 4 mmol of H2O2 and 2 ml of MeCN
were added. The mixture was then stirred at room tem-
perature for 24 h. An amount of 5 ml of water was added
and the liquid was extracted with EtOAc (5 ml × 3). The
combined organic layers were dried with anhydrous
Na2SO4 and the organic solvent was evaporated using a
rotary evaporator. The residue was separated by flash
column chromatography (eluent: petroleum ether–
EtOAc = 8/1) to afford the vinyl ester product 10.
3 | CONCLUSIONS
We have found an interesting transition‐metal‐free
decarboxylative coupling reaction of phenylacetic acid
with elemental Se. Compared with traditional methods
to introduce Se into molecules, this reaction employs
cheap Se powders as the Se source and the generation
of toxic and odorous selenol intermediates and solid
wastes such as magnesium salts can be avoided, affording
a more direct and relatively green access to dibenzyl
diselenide/selenide mixtures, which are found to be good
catalysts in Baeyer–Villiger reactions and oxidative
deoximation reactions. The idea of using easily accessible
organoselenium compound mixtures as catalysts is novel
and will be helpful for reducing catalyst costs, so that the
application of organoselenium catalysis in large‐scale pro-
duction may be realized in not far distant future.
4.4 | Details of oxidative deoximation of
diphenylmethanone oxime
To a reaction tube, 1 mmol of diphenylmethanone
oxime, 0.05 mmol of 2, 0.3 mmol of H2O2 and 2 ml of
MeCN were added. The mixture was then stirred in open
air at 60°C for 24 h. An amount of 5 ml of water
was added and the liquid was extracted with EtOAc
(5 ml × 3). The combined organic layers were dried
with anhydrous Na2SO4 and the organic solvent was
evaporated using a rotary evaporator. The residue
was separated by flash column chromatography (eluent:
4 | EXPERIMENTAL PROCEDURES
4.1 | General methods
petroleum ether–EtOAc
=
10/1) to afford the
diphenylmethanone product 12.
Chemicals were purchased from a commercial source
with purities of more than 98%. Solvents were analytically
pure (AR) and were directly used without any special
treatment. NMR spectra were recorded with a Bruker
Avance 400 instrument (400 MHz for 1H NMR,
ACKNOWLEDGMENTS
We thank NNSFC (21202141), Priority Academic Pro-
gram Development of Jiangsu Higher Education Institu-
tions (PAPD), Top‐notch Academic Programs Project of
Jiangsu Higher Education Institutions (TAPP), the
Nature Science Foundation of Guangling College
(ZKZD17005, ZKZZ18001) and the Open Project Program
of Jiangsu Key Laboratory of Zoonosis (R1509, R1609) for
financial support.
1
100 MHz for 13C NMR). Chemical shifts for H NMR
were referred to internal Me4Si (0 ppm).
4.2 | Typical procedure for
decarboxylative coupling of phenylacetic
acid with elemental Se
To a reaction tube, 1 mmol of 1, 4 mmol of Se powders,
2 mmol of DIEA and 1 ml of DMF were added. The tube
was then charged with N2 and was heated at 150°C for
ORCID
Lei Yu https://orcid.org/0000-0001-5659-7289

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CAO ET AL.
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Additional supporting information may be found online
in the Supporting Information section at the end of the
article.
How to cite this article: Cao H, Liu M, Qian R,
Zhang X, Yu L. A cost‐effective shortcut to prepare
organoselenium catalysts via decarboxylative
coupling of phenylacetic acid with elemental
selenium. Appl Organometal Chem. 2018;e4599.
https://doi.org/10.1002/aoc.4599
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