Recyclable 1,2-bis[3,5-bis(trifluoromethyl)phenyl]diselane-catalyzed oxidation of cyclohexene with H2O2: A practical access to trans-1,2-cyclohexanediol

Article abstract of DOI:10.1002/aoc.3175

1,2-Bis[3,5-bis(trifluoromethyl)phenyl]diselane-catalyzed oxidation of cyclohexene by hydrogen peroxide affords a quick, clean and practical access to the important compound trans-1,2-cyclohexanediol under mild conditions. The highly atom-economic properties, clean procedures, high reaction concentration, short reaction time, mild conditions and eco-friendly, recyclable and low loading catalysts facilitate this methodology for possible future practical industrial production. Copyright

Full text of DOI:10.1002/aoc.3175

Full Paper
Received: 13 April 2014
Revised: 7 May 2014
Accepted: 11 May 2014
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/aoc.3175
Recyclable 1,2-bis[3,5-bis(trifluoromethyl)
phenyl]diselane-catalyzed oxidation of
cyclohexene with H2O2: a practical access to
trans-1,2-cyclohexanediol
Lei Yua,b*, Jun Wanga, Tian Chena, Yuguang Wanga,b,c* and Qing Xua,b
1,2-Bis[3,5-bis(trifluoromethyl)phenyl]diselane-catalyzed oxidation of cyclohexene by hydrogen peroxide affords a quick, clean
and practical access to the important compound trans-1,2-cyclohexanediol under mild conditions. The highly atom-economic
properties, clean procedures, high reaction concentration, short reaction time, mild conditions and eco-friendly, recyclable and
low loading catalysts facilitate this methodology for possible future practical industrial production. Copyright © 2014 John Wiley
& Sons, Ltd.
Additional supporting information may be found in the online version of this article at the publisher’s web-site.
Keywords: selenium; catalysis; trans-1,2-cyclohexanediol; oxidation
reported by Santi et al.[13] However, their studies did not involve
the synthesis of 1,2-cyclohexanediol and the methods always
Introduction
1,2-Cyclohexanediol is one of the most important chemicals,
widely employed in industrial production for the synthesis of
many significant products such as pyrocatechol, cyclohexane-
1,2-dione, 1,2-dichlorocyclohexane, adipaldehyde, 7-oxa-bicyclo
[4.1.0]heptanes, 2-halocyclohexanol, 2-halocyclohexanone, 2-hy-
droxycyclohexanone and 2-hydroxycyclohex-2-enone (Fig. 1).[1]
The preparation of 1,2-cyclohexanediol and its downstream
products involves many fields, such as agricultural chemistry,
food chemistry, medical chemistry, and polymer and material
science. Therefore, synthesis of 1,2-cyclohexanediol is a basic
and important topic in chemical industry research. Currently,
1,2-cyclohexanediol is synthesized through the oxidation of
cyclohexene, which is a cheap and abundant starting material. How-
ever, the present methodologies always require transition metal cat-
alysts, acidic intermediates and toxic oxidants that generate
hazardous wastes,[2] restraining further large-scale preparation. Thus
developing a clean oxidation procedure of cyclohexene to 1,2-
cyclohexanediol would be beneficial in applications.
required quite a long reaction time (≥24 h), and high catalyst
loading (≥10 mol%) but was performed at low reaction concentra-
tion (~0.1M). Thus there is still potential for the optimization of the
organoselenium-catalyzed dihydroxylation of olefins and for
expansion their application scope. Recently, we applied this clean
synthetic methodology to 1,2-cyclohexanediol synthesis and, by
carefully screening, the low loading and recyclable 1,2-bis[3,5-bis
(trifluoromethyl) phenyl]diselane was found to be a superior
catalyst, giving trans-1,2-cyclohexanediol rapidly in high yield. In
addition, the reaction concentration was enhanced to more than
3 M, affording more capability for possible industrial production.
All of these advantages will facilitate large-scale preparation. Herein,
we wish to report our findings.
Results and Discussion
Initially, we prepared a series of organoselenium compounds for
screening. Among these compounds, diphenyl diselenide [(PhSe)2]
Yet organoselenium-catalyzed reactions have attracted much
interest in synthetic chemistry in recent years and this field is still
in rapid progress. Since selenium is an eco-friendly metalloid that
can be metabolized in organisms,[3] organoselenium catalysts
might be potential alternatives to traditional transition metal
catalysts in synthesis of medicines. Currently, organoselenium-
catalyzed reactions include epoxidation,[4] halohydroxylation[5]
and haloamidation[6] of alkenes, or oxidation,[7] halogenation[8]
and amination[9] of sp2 and sp3 C–H bonds, as well as Baeyer–Villiger
oxidation of ketones and aldehydes[10] and oxidation of
amidogens.[11] Very recently, we reported organoselenium-catalyzed
dehydration of aldoximes to nitriles,[12] which should be the first
example of organoselenium-catalyzed dehydration. Organose-
lenium-catalyzed dihydroxylations of olefins have already been
* Correspondence to: Lei Yu and Yuguang Wang, Key Laboratory of Environmental
Materials and Engineering of Jiangsu Province, School of Chemistry and Chemical
Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, China. E-mail:
yulei@yzu.edu.cn; yuguangw@zjut.edu.cn
a Key Laboratory of Environmental Materials and Engineering of Jiangsu
Province, School of Chemistry and Chemical Engineering, Yangzhou University,
Yangzhou, Jiangsu, 225002, China
b Zhejiang Key Laboratory of Carbon Materials, College of Chemistry and
Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325035, China
c
College of Biological and Environmental Engineering, Zhejiang University of
Technology, Hangzhou, Zhejiang, 310014, China
Appl. Organometal. Chem. (2014)
Copyright © 2014 John Wiley & Sons, Ltd.

Lei Yu et al.
NH2
NH2
O
O
O
O
O
H, which is seldom used in organoselenium catal-
ysis, had good activity (run 9), while other dialkyl
diselenides, such as 1,2-diethyldiselane I, re-
sulted in quite low product yield (run 10). It was
also shown that only diselenides were efficient
catalysts for this reaction, while diphenyl sele-
nide J was almost inactive (run 11). Blank reac-
tion showed that a catalyst was essential for
this reaction, since no trans-1,2-cyclohexanediol
was generated without catalyst (run 12).
To gain more information on the relationship
between reaction time and product yield and
to obtain accurate reaction terminations, de-
tailed experiments were tested with the best five
organoselenium catalysts ((PhSe)2, B, C, E, H)
that had been screened out in Table 1. For each
catalyst, eight parallel experiments were taken
under standard conditions and terminated at 1,
3, 5, 8, 10, 20, 30 or 42 h respectively and then
subjected to GC analysis. The relationship
curves of reaction time with product yield are
shown in Fig. 2.[16] It was obvious that, although
simplest and most available. (PhSe)2 was a
good catalyst which afforded excellent trans-1,2-
cyclohexanediol yield after sufficient reaction
times; the reaction proceeded rather slowly and
the product yield rose gradually with reaction
time, even after 40 h. 2-Bis[3,5bis(trifluoromethyl)
phenyl]diselane E, which afforded trans-1,2-
cyclohexanediol in the highest (96%) yield, could
OH
OH
S
HOOC
S
C
O
O
l
P
COOH
Cl
b
d
c
e
a
OH
OH
OH
O
O
O
OHC
Se
O
CHO
O
f
g
j
h
i
n
Cl Cl
O
O
O
OH
OH
O
O
O
O
m
Cl Cl
k
p
q
r
s
o
Cl
Cl
O
O
O
CHO
OH
OH
u
w
v
x
t
OH
O
Br
O
X
O
N
H
OH
OH
X= (Br, Cl)
Figure 1. Commodity chemicals from 1,2-cyclohexanediol.
(1) Mg
(2) Se
O2
was commercially available, while the others (A–J) could be
obtained through known synthetic methodologies (Scheme 1).[14]
Diselenides A–I could be conveniently synthesized by the insertion
of selenium powder to Grignard reagents and the following acidifi-
cation and oxidation (equation (1)) while diphenyl selenide J could
be synthesized through the SN2 reaction of phenyl magnesium
bromide with phenyl selenium bromide, which was prepared by
the reaction of (PhSe)2 with equivalence bromine in CH2Cl2
(equation (2)). All of these organoselenium compounds were
prepared conveniently from available starting materials in moderate
to good yields (Scheme 1).
Then, with these organoselenium compounds as catalyst, a se-
ries of parallel experiments were tested for comparison. On the
basis of our experiences from previous studies in organoselenium
chemistry,[10a,12,15] including organoselenium catalysis,[10a,12] we
initially designed the experimental schemes involving stirring
20 mmol cyclohexene, 30 mmol H2O2 (30 w/w%, 1.5 equiv.) and
0.2 mmol (1%) of catalysts together in 2 ml CH3CN at 30°C for a
sufficient reaction time (42 h). The mixtures were then subjected
to GC analysis to calculate the yields of 1,2-cyclohexanediol.
Under these conditions, the simplest and most available catalyst
(PhSe)2 afforded trans-1,2-cyclohexanediol in excellent yield (run
1). Electron-deficient diaryl diselenides were much superior to
the electro-enriched ones (runs 3, 4, 5, 6 vs. 2) and, among these
catalysts, 2-bis[3,5bis(trifluoromethyl)phenyl]diselane E was found
to be the best one, giving 1,2-cyclohexanediol in even higher
yield than (PhSe)2 (run 6). Catalyst with large steric hindrance
groups resulted in rather low product yields (run 7 and 8). In ad-
dition, we were very surprised to find that dicyclohexyl diselenide
HCl
RSeMgBr
RSeH
R2Se2
F
(1)
RBr
R2Se2:
MeO
Se
2
Se
F
Se
2
2
2
A (72%)
B (85%)
C (81%)
Se
F3C
F
Se
Se
2
2
2
F3C
D (73%)
E (77%)
F (70%)
Se
Se
CH3CH2SeSeCH2CH3
2
I (67%)
G (85%)
H (88%)
Et2O
PhMgBr + PhSeBr
PhSePh
(2)
J (81%)
Scheme 1. Synthesis of the substituted diselenides and diphenylselenide.
catalyze the reaction rapidly and the reaction terminated in 3–5h,
where the curve became flat, as observed in Fig. 2. Dicyclohexyl
diselenide H also showed good catalytic activity. However, the prod-
uct yield reached its peak around 80% in 10–15 h and did not rise
any further after that, possibly due to the decomposition of catalyst
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Appl. Organometal. Chem. (2014)

Organoselenium-catalyzed dihydroxylation of cyclohexene
Table 1. Catalytic activities tests of diselenidesa
1 mmol E, CH3CN, 30°C, 5 h). After distillation under reduced
pressure (96–102°C/5 mmHg), 9.5 g trans-1,2-cyclohexanediol (82%
isolated yield) was obtained, clearly revealing the high scalability
and potential of the present method. During these processes, we
also noticed that a deep-yellow and oily residue remained at the
bottom of the flask after distillation. Considering that organo-
selenium catalysts were always stable[12] and the components of
this reaction were so simple that, theoretically, only catalytic
organoselenium compounds might be left over after distillation,
we collected and reused the residue as catalyst in the next turn. It
was shown that the organoselenium catalyst was so robust that
its catalytic activity did not reduce much even after recycling five
times (Fig. 3).[16]
The mechanism of this reaction was our next concern.
Fortunately, on the basis of the references[13] as well as our
previous 77Se NMR studies,[10a] there was no difficulty in under-
standing it, as depicted in Scheme 2. Diselenides, e.g. (PhSe)2,
were initially oxidized by H2O2 to benzeneseleninoperoxoic anhy-
dride 1, which hydrolyzed to benzeneseleninoperoxoic acid 2 as
the real activated catalytic species. Cyclohexene was then
oxidized by 2 to intermediate 7-oxa-bicyclo[4.1.0]heptane 4,
which hydrolyzed to produce trans-1,2-cyclohexanediol with the
assistance of acid (PhSe(O)OH, etc.).[13] Organoselenium species
3 was then reoxidized to 2 by H2O2 and restarted in the next
catalytic cycle. The intermediate organoselenium species in these
procedures have been confirmed by 77Se NMR in our previous
studies[10a] and the related references are given in Scheme 2.
Run
Catalystb
Yield (%)c
1
(PhSe)2
91
38
64
76
45
96
31
23
80
17
1
2
(p-MeOC6H4Se)2 (A)
(p-FC6H4Se)2 (B)
(m-FC6H4Se)2 (C)
(o-FC6H4Se)2 (D)
[3,5-(CF3)2C6H3Se] 2 (E)
(1-C10H7Se)2 (F)
(C6H5CH2Se)2 (G)
(c-C6H11Se)2 (H)
(C2H5Se)2 (I)
3
4
5
6
7
8
9
10
11
12
(C6H5)2Se (J)
—
0
aReaction conditions: 20 mmol cyclohexene, 30 mmol H2O2 (30 w/
w%), 1 mol% Se catalyst (based on cyclohexene) and 2 ml
CH3CN were stirred at 30 °C for 42 h.
bFor structural formula of catalyst see Scheme 1.
cGC yields based on cyclohexene with benzophenone as
internal standard.
Figure 3. Organoselenium catalyst recovery and reuse.[16]
Figure 2. The relationship of reaction time with product yield for the
reactions catalyzed by diselenides.[16]
through syn-selenoxide elimination of alkyl organoselenium
compounds.[14,17] The catalytic abilities of 1,2-bis(3-fluorophenyl)
diselane C and 1,2-bis(4-fluorophenyl) diselane B were weak and it
was interesting that there was a flat period of 1–3 h on the curve
of C, which might suggest the existence of a delayed process for
the generation of the real catalytic species aryl seleninic acid
derivatives, as supposed in our previous works.[10a]
Generally, the selectivity of this oragnoselenium-catalyzed
dihydroxylation was extremely high, while no other by-products
were observed in the GC spectra.[16] With the optimized reaction
conditions in hand, we then examined the scalability of the method
for large-scale preparation and a 100 mmol scale reaction of
cyclohexene under the optimized conditions was taken with
reduced H2O2 dosage, for safety reasons (100 mmol H2O2,
Scheme 2. Possible mechanisms.
Appl. Organometal. Chem. (2014)
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Lei Yu et al.
mixture was extracted with ether (50 mL × 3). The combined
organic layer was dried by anhydrous Na2SO4. After distillation of
the solvent, the residue was purified by column chromatography
(eluent: petroleum ether) to give 5.68 g PhSePh (81% yield).[21]
Conclusion
We have screened out a low-loading and recyclable organo-
selenium catalyst 1,2-bis[3,5-bis(trifluoromethyl)phenyl]diselane for
the oxidation of cyclohexene to trans-1,2-cyclohexanediol.
Compared with similar reports on organoselenium catalyzed
dihydroxylation of olefins with H2O2,[13] this accessible compound
could catalyze the reaction more rapidly with high product yield.
The mild conditions, high reaction concentration, clean procedure
and low loading but recyclable catalyst are all advantages that
might benefit from possible practical preparations in the future.
Procedure for Dihydroxylation of Cyclohexene in 20 mmol Scale
To a Schlenk tube, diselenide, cyclohexene, MeCN and H2O2 were
added (for the amount of reagents see Table 1 in the text). After
stirring at 30°C for a certain time, 20 mg internal standard
benzophenone was added. The mixture was diluted to 10 ml with
MeCN and subjected to GC for analysis.
Experimental
Procedure for Dihydroxylation of Cyclohexene in 100 mmol
Scale
General Methods
To a 50 mL round-bottom flask, 2-bis[3,5bis(trifluoromethyl)phe-
nyl]diselane E (0.58 g, 1 mmol, 1% loading), cyclohexene (10.1 ml,
8.2 g, 100 mmol), 10 ml MeCN and H2O2 (11.3g, 100 mmol) were
added. After stirring at 30°C for 5 h, MeCN was distilled by rotary
evaporator. The residue was transferred to a 25 ml flask and
distilled under vacuum (96–102°C/5 mmHg)[22] to give 9.5g trans-
1,2-cyclohexanediol (82%). The residue could be re-collected and
reused in the next cycle.
All of the chemicals used were analytical pure reagent grade.
H2O2 was an aqueous solution (30% weight concentration).
Diphenyl diselenide was commercially available and the other
organoselenium compounds were synthesized through known
methods (see below). Ether was dehydrated by sodium sand with
benzophenone as indicator. Selenium powder was baked at 100°
C for 1 h before use. All of the reactions were performed in a
fume hood. Dihydroxylation of cyclohexene was monitored by
GC, with a capillary DB1701 column and flame ionization
detector. The oven temperature was programmed at 70–260°C
(heating rate 30°C minÀ1). GC yields were confirmed with
benzophenone as the internal standard.
Acknowledgments
This work was supported by NNSFC (21202141, 21202151 and
20902070), Opening Foundation of the Key Laboratory of
Environmental Materials and Engineering of Jiangsu Province
(K11024), Priority Academic Program Development of Jiangsu
Higher Education Institutions and 580 Oversea Talents Program
of Wenzhou City. We thank enterprise employees Dr. Kehong
Ding, Shubin Yang and Genlin Wang for assistance in preliminary
work. We also thank Jiangsu Yangnong Chemical Group Co. Ltd
for financial support, and the analysis center of Yangzhou
University for assistance.
General Procedure for the Synthesis of diselenides
To a 100 ml three-necked flask, 30 mmol Mg powder (0.72 g), a
stirring bar and a small piece of I2 were added. The flask was then
equipped with a condenser and charged with N2. Under N2
protection, 20 ml anhydrous ether was injected by syringe. A small
amount of halogenated hydrocarbon was added and, after initia-
tion, the rest of the 30mmol halogenated hydrocarbon in 30ml
anhydrous ether was slowly injected with ice-water bath cooling.
After the preparation of Grignard reagent, 30 mmol dried selenium
powder (2.4g) was added slowly. After stirring for 1 h, the mixture
was dumped into 100 ml of 1 M HCl solution with ice cooling for
acidolysis. The mixture was extracted by ether (50 ml × 3) and the
combined organic layer was dehydrated by anhydrous Na2SO4.
The solution was charged with O2 for 24 h and turned orange.
Distillation of solvent afforded the crude diselenide, which could
be purified by recrystallization with EtOH–H2O or column
chromatography (eluent: petroleum ether).[20]
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Supporting Information
Additional supporting information may be found in the online
version of this article at the publisher’s web-site.
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