Allylic oxidation of cyclic alkenes with molecular oxygen and tert-butyl hydroperoxide over copper-manganese oxides

Article abstract of DOI:10.1007/s00706-016-1742-6

Abstract: An efficient and mild method for the allylic oxidation of cyclic alkenes employing molecular oxygen and tert-butyl hydroperoxide as the oxidant, copper-manganese oxides as heterogeneous catalyst under ambient temperature is proposed. The catalyst, which was prepared by co-precipitation and characterized, was evaluated oxidation of isolongifolene as a typical mode substrate. The catalyst showed a good catalytic activity and remained nearly the same after four cycles. The scope of the reaction was investigated with a variety of cyclic alkenes compounds. Graphical abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s00706-016-1742-6

Monatsh Chem
DOI 10.1007/s00706-016-1742-6
ORIGINAL PAPER
Allylic oxidation of cyclic alkenes with molecular oxygen and tert-
butyl hydroperoxide over copper-manganese oxides
1
1
1
1
3
1,2
Wu Zhang
•
Qiuyu Wei
•
Lingling Lan
•
Aiqun Wu
•
Xiuju Yin
•
Liqun Shen
Received: 12 January 2016 / Accepted: 15 March 2016
Ó Springer-Verlag Wien 2016
Abstract An efficient and mild method for the allylic
oxidation of cyclic alkenes employing molecular oxygen
and tert-butyl hydroperoxide as the oxidant, copper-man-
ganese oxides as heterogeneous catalyst under ambient
temperature is proposed. The catalyst, which was prepared
by co-precipitation and characterized, was evaluated oxi-
dation of isolongifolene as a typical mode substrate. The
catalyst showed a good catalytic activity and remained
nearly the same after four cycles. The scope of the reaction
was investigated with a variety of cyclic alkenes
compounds.
Introduction
The allylic oxidation of olefins into value-added a,b-un-
saturated carbonyl compounds or alkenyl alcohol
compounds are a fundamental transformation in organic
synthesis and industrial chemistry [1]. Allylic oxidation of
1,3,4,5,6,7-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-meth-
anonaphthalene(isolongifolene) to 1,2,3,4,5,6-hexa-
hydro-1,1,5,5-tetramethyl-7H-2,4a-methanonaphthalen-7-
one (isolongifolenone) is of interest because isolongi-
folenone and its derivatives have been found to be active
against tyrosinase and antimalarial. In addition, iso-
longifolenone also be found more effective than Deet in
repelling ticks [2] and deterring feeding mosquitoes [3, 4].
Classically, allylic oxidation mainly with SeO2 [5–7],
Graphical abstract
O
Cu-Mn oxides, TBHP
O , 20-24 h
MnO [8], potassium permanganate [9], chromium hex-
2
2
acarbonyl [10], and Pd compounds [11–14] frequently
encounters problems such as toxicity, high cost, and low
regioselectivity.
The use of tert-butyl hydroperoxide (TBHP) in combi-
nation with some of the reagents such as inorganic metal
Keywords Oxidation Á Heterogeneous catalysis Á
TBHP Á Isolongifolene Á Chemoselectivity
[
15–17], diacetoxyiodobenzene [18], Schiff base com-
plexes [19–21], metal organic frameworks (MOFs) [22, 23]
has afforded allylically oxidized products but the reaction
still utilizes the toxic compound, and the process produces
hazardous waste making the process eco unfriendly.
Cu-based oxide catalysts [24–27] that are highly desirable
objects for the allylic oxidation due to their good catalytic
performances and low fabrication costs could become an
alternative to the precious metal catalysts. Manganese(III)
acetate catalyzed [28] allylic oxidation of alkenes to the
corresponding enones also showed appreciable regioselec-
tivity and chemoselectivity. Against this background, it is
interesting to consider the influence of copper-manganese
oxides catalysts for allylic oxidation of alkenes.
W. Zhang, Q. Wei contributed equally to this work.
&
Liqun Shen
shenliqun@gxun.edu.cn
1
2
3
College of Chemistry and Chemical Engineering, Guangxi
University for Nationalities, Nanning 530006, China
Key Laboratory of Development and Application of Forest
Chemicals of Guangxi, Nanning 530006, China
School of Chemistry and Biological Engineering, Hechi
University, Yizhou, Guangxi 546300, China
123

W. Zhang et al.
Scheme 1
evaluated from low temperature (77 K) static nitrogen
physisorption–desorption isotherms by a volume method
using a Micromeritics ASAP2020 M surface/porosity
analyzer. The surface area and pore volume of fresh and
recycled Cu–Mn Ox (673 K) were determined by the BET
method (Table 1). The fresh Cu–Mn Ox shows a lager
O
Cu-Mn oxides, TBHP
O , 20-24 h
2
1
a
2
specific surface area (59.69 m /g) and total pore volume
3
0.45 cm /g) followed by the recycled Cu–Mn Ox
(
(
2
33.38 m /g and 0.23 cm /g). Average pore diameters of
3
fresh and recycled catalysts are 27.86 and 28.21 nm,
respectively. The results obtained show that samples pos-
sess a larger specific surface area and narrow pore volume
compared with the reports by Ivanets [34].
Mixed manganese-copper oxides are well known as
active catalyst for the oxidation of CO to CO [29]. Mixed
2
copper-manganese oxides as catalyst have also been stud-
ied for the oxidation toluene [30], for the oxidation of
benzyl alcohol to benzaldehyde with molecular oxygen
Fourier transform infrared
[
31], for ozone decomposition [32], NO reduction [33], and
other redox processes. However, to date, mixed copper-
manganese oxides (here after called Cu–Mn Ox) catalysts
have not been studied for allylic oxidation of alkenes.
In this work, we have synthesized mixed copper-man-
ganese oxides catalyst by simple co-precipitation method
and have examined its catalytic property for allylic oxi-
dation of alkenes with molecular oxygen and TBHP as the
oxidant (Scheme 1).
The FT-IR spectra of fresh and recycled Cu–Mn mixed
oxides are shown in Fig. 1. We can see that the IR spec-
trums of fresh and recycled Cu–Mn mixed oxides look
nearly the same, but there still exists differences among
them. The broad and intense absorption peak at
-
1
3300–3500 cm considers being the stretching vibration
of the internal hydroxyl groups for all samples. The broad
-
1
absorption peak at 1500–1600 cm corresponding to the
bending vibration of the internal OH groups from water
molecules are observed. It is apparent to recognize that the
Results and discussion
-
1
sharp and intense absorption peak at 1363 cm attributes
2
-
to the bending vibration of the internal CO3 for the
samples of fresh and recycled Cu–Mn mixed oxides. The
characteristic absorption peak of the stretching vibration
and framework vibration of M–O–M can be found at
Element, surface area, and porosity measurements
analysis
The results of the ICP analysis of the prepared Cu–Mn Ox
in Table 1 show that a content of the Cu–Mn Ox was close
to that of the molar ratio is approximately 0.40. While there
still exists in slight differences, it could be possibly that
some part of the ions are not precipitated, and remain in
solution. In addition, [Mn]/([Cu] ? [Mn]) mole ratios of
recycled Cu–Mn solids material decline to 0.39 from 0.41
in fresh Cu–Mn Ox. It may be mainly due to the amount of
copper loss in catalytic oxidation reaction. The adsorptive
and microstructural properties of the Cu–Mn Ox were
-
1
400–700 cm . The IR spectra of fresh and recycled Cu–
Mn mixed oxides, suggesting that Cu–Mn mixed oxides are
of structural stability.
Powder X-ray diffraction
The XRD patterns of fresh, recycled Cu–Mn mixed
oxides and various Cu–Mn oxides at different tempera-
ture are presented in Figs. 2 and 3. The data were
treated with Jade (Version 6.0) software and
Table 1 The content of Cu–Mn Ox catalysts measured by ICP and BET methods
2
-1
3
Pore volume/cm g
-1
Sample
[Mn]/([Cu] ? [Mn])
S
BET/m g
Pore diameter/nm
Initial solution
Solids material
0.41
Fresh
0.40
–
59.69
33.38
0.45
0.23
27.86
28.21
Cu–Mn
Recycle
Cu–Mn
0.39
1
23

Allylic oxidation of cyclic alkenes with molecular oxygen and tert-butyl hydroperoxide over…
Figs. 2 and 3. Though it was hard to distinguish the
XRD patterns of the single and mixed manganese and
copper oxide catalysts for the diffraction peaks which
were broad and weak, we were able to identify,
including those with the spinel structure. The catalysts
prepared from mixed solutions of manganese(II) and
copper nitrate contained not only individual copper(II)
and manganese(IV) oxides but also the mixed oxides
Cu1.5Mn1.5O , Cu1.4Mn1.6O , CuMn O , and etc. Sur-
e
d
c
b
a
4
4
2 4
prisingly, calcination at 573 K or higher temperatures,
there was no substantive change in composition com-
pared with the temperatures of 378 K, showing the
catalyst has a good thermal stability. The results indi-
cated that Cu–Mn mixed oxides may be responsible for
recycled, at least, four times without loss of the activity
ꢀ
ꢁꢁꢁ
ꢂꢃꢁꢁ
ꢂꢁꢁꢁ
ꢄꢃꢁꢁ
ꢄꢁꢁꢁ
ꢅꢃꢁꢁ
ꢅꢁꢁꢁ
ꢃꢁꢁ
Wavenumber/cm-1
Fig. 1 The FT-IR spectra: a, fresh Cu–Mn Ox; b, c, d and e orderly
from the second to the fifth, recycled Cu–Mn Ox
(
Fig. 3). The XRD data attributes to Cu–Mn due to the
identification of the crystalline phases was made by
comparison with the ICDD (2004) files. As it can be
seen, there are a few differences in feature between
report of Ivanets [34], suggesting the formation of a well
structural hopcalite (copper-manganese oxide).
Fig. 2 The XRD patterns of
Cu–Mn Ox: filled square,
Cu1.5Mn1.5
O
4
; filled circle,
CuO; filled upright triangle,
Mn ; calcined temperature:
3 4
O
a 378 K; b 573 K; c 673 K
Fig. 3 The XRD patterns of
Cu–Mn Ox: filled square,
Cu1.5Mn1.5
O
4
; filled circle,
CuO; filled upright triangle,
Mn ; d, fresh Cu–Mn Ox; e,
3 4
O
f, and g orderly from the second
to the fourth, recycled Cu–Mn
Ox
123

W. Zhang et al.
Thermo gravimetry and differential thermal
analyses
total weight loss was about 12 %. The weight loss in
temperature range of 423–573 K accounts for about
8–9 %, which is attributed to the removal of internal and
TG/DTA analysis of Cu–Mn Ox was measured by syn-
chronous thermal analyzer to study the course of the
thermal decomposition. The consequence of Cu–Mn Ox
was exhibited as a mode sample in Fig. 4. As it can be
seen, the curves of TG/DTA has two stages of weight over
the temperature range of 423–573 and 573–873 K and the
weakly adsorbed water molecules. The second weight loss
accounts for 3–4 %, which is due to the decomposition of
carbonate anions from the internal causing the break of the
structure. The whole curve of DTA was shown that the
material was exothermic except that at the temperature of
423–523 K which was endothermic.
Scanning electron microscope
The scanning electron micrographs (SEM) of fresh and
recycled Cu–Mn Ox are displayed in Fig. 5. It is clear to
see that the materials are made up of aggregate of regular
morphology and the particle size is homogeneous and tiny;
after the oxidation reaction, the particle size of Cu–Mn Ox
slightly change and become uneven and loose.
Effect of calcined temperature on the reaction
The catalytic performances of different calcined tempera-
ture catalysts in the oxidation of isolongifolene by
molecular oxygen and TBHP are compared in Table 2. We
Fig. 4 TG/DTA curves of Cu–Mn Ox
Fig. 5 The SEM micrographs: a, fresh Cu–Mn Ox; b, c, and d orderly from the second to the fourth, recycled Cu–Mn Ox
1
23

Allylic oxidation of cyclic alkenes with molecular oxygen and tert-butyl hydroperoxide over…
Table 2 The different calcined temperature catalysts oxidation of isolongifolene
Calcined temp./K
Solvent
TBHP/mmol
Time/h
Conversion/%
Selectivity/%
3
5
6
78
73
73
CH
CH
CH
3
3
3
CN
CN
CN
3
3
3
24
24
24
100
100
100
3
89.5
93.4
95.2
All reactions were carried out using isolongifolene (1 mmol), Cu–Mn Ox (100 mg), TBHP (3 mmol), and 4 cm CH
3
CN, purged with molecular
oxygen, A.T, 24 h. Selectivity (%) = yield (%)/conversion (%), determined by GC and GC–MS
can find that the Cu–Mn Ox (673 K) exhibits a maximum
conversion (100 %) and selectivity (95.2 %) to isolongi-
folenone, and then followed by Cu–Mn Ox (573 K)
conversion (100 %) and selectivity (93.4 %). Cu–Mn Ox
acid (44.5 % conversion, 47.2 % selectivity) and methanol
(55.7 % conversion, 32.8 % selectivity).The results are
conformed to the recent studies of the Cu-catalyzed allylic
oxidation of alkenes performed in acetonitrile or acetone
[35].
(
378 K) shows an inferior selectivity (89.5 %). The results
indicate that oxides calcined at a temperature of 673 K lead
to formation of highly active species on the surface of Cu–
Mn Ox for the oxidation, so we chose it as catalyst of all
experiments we had done.
The blank experiment among catalyst, TBHP
and O2
As we known, these factors including Cu–Mn Ox, TBHP,
Effect of solvent on the reaction
and O have much effect on the reaction. So, to clarify the
2
relations, the blank experiments were carried out. From the
Table 3, it can be seen clearly that both the conversion and
the selectivity were poor when lack one of them. Therefore,
to complete this reaction efficiently, Cu–Mn Ox, TBHP,
The rates, equilibria, the selectivity and the products of
chemical reactions can be strongly influenced by the solvent.
Therefore, the effect of organic solvents on the oxidation of
isolongifolene using Cu–Mn Ox catalysts was studied and
the results were illustrated in Fig. 6. Among the solvents
studied, acetonitrile shows excellent conversion (100 %)
and selectivity (95.2 %) to isolongifolenone, and then fol-
lowed by acetone (97.7 % conversion, 88.3 % selectivity),
tetrahydrofuran (84.1 % conversion, 79.1 % selectivity),
chloroform (79.2 % conversion, 66.8 % selectivity),
dichloromethane (61.7 % conversion, 57.0 % selectivity),
ethylacetate (45.4 % conversion, 54.8 % selectivity), acetic
and O are indispensable.
2
Designs of experiments for isolongifolene
to isolongifolenone
To seek for an optimal reaction condition, we design DoE
experiments using statistical methods, which is a statistical
approach that defines a domain for every variable involved
in a reaction [36]. We investigated two variables, the
equivalents of TBHP and the amount of Cu–Mn Ox. We
2
adopted a 3 full factorial design to carry out 11 experi-
AConversion
BSelectivity
ments (Table 4). The curved shape of the obtained
response surface (Fig. 8) showed that higher amounts of
Cu–Mn Ox and TBHP would not proceed in significant
higher yields for the allylic oxidation. The vertical line in
2
Table 3 The blank experiment among catalyst, TBHP, and O on
isolongifolene to isolongifolenone (the ‘‘?’’ or ‘‘-’’ stands for add or
none)
Entry Cu–Mn Ox TBHP
O
2
Conversion/% Selectivity/%
1
2
3
4
?
?
-
?
?
-
?
?
-
?
?
?
44.7
27.6
39.5
100
39.9
34.0
37.3
95.2
Acetonitrile Acetone
THF Chloroform
CH2Cl2 Ethylacetate Acetic acid Methanol
Fig. 6 The influence of solvents on the reaction. Conditions: 1 mmol
3
isolongifolene, 100 mg Cu–Mn Ox, 3 mmol TBHP, 4 cm solvent,
Conditions: isolongifolene (1 mmol), TBHP (3 mmol), Cu–Mn Ox
3
(100 mg), O
a
, A.T, 24 h. Selectivity (%) = yield (%)/conversion
and 1 atm O
(
2
2 3
(1 atm), and 4 cm CH CN, A.T, 24 h. Selectivity
a
%), determined by GC
(%) = yield (%)/conversion (%), determined by GC
123

W. Zhang et al.
Table 4 Factors and levels of three full factorial design for
isolongifolenone
Factor
High level
Low level
Units
Cu–Mn Ox
TBHP
150
5
50
mg
0.5
equiv
the Pareto plot (Fig. 7) indicates a level of 95 % confi-
dence, representing the TBHP has a great influence on the
reaction. The statistical analysis of the model obtained
(
Tables 4, 5) displayed that the main factor involved was
Fig. 8 Response surface for the synthesis of isolongifolenone (1a)
Table 6 Reused of catalyst
the amount of TBHP employed in the reaction. The
response surface is displayed in Fig. 8. The excellent result
attributes to 100 mg/mmol Cu–Mn Ox and 3 equiv TBHP,
which led to 95.2 % yield of isolongifolenone analyzed by
GC.
Cycles (n)
Conversion/%
Selectivity/%
1
2
3
4
100
100
100
100
95.2
91.1
89.3
87.0
Reused of catalyst
To evaluate the reusability of Cu–Mn mixed oxide catalyst, a
recycling test was carried out using the recovered catalysts for
oxidation isolongifolene (Table 6). The reaction was carried
Conditions: 1 mmol isolongifolene, 100 mg catalysts, 3.0 mmol
3
TBHP, and 4 cm CH CN, purged with molecular oxygen, A.T, 24 h.
3
Selectivity (%) = yield (%)/conversion (%), determined by GC
out with molecular oxygen and TBHP as the oxidant under
ambient temperature. Upon completion of the reaction, prod-
ucts were extracted with dichloromethane and the yields were
determined by GC. The resulting Cu–Mn Ox catalyst with
A:TBHP
+
-
B:Mn-Cu Ox
AA
BB
AB
96.5 % yield was collected and activated in the oven at 378 K
for 10 h. Therecycled experiment was carried out with 100 mg
recycled Cu–Mn Ox under the same condition. As can be seen
from Table 6, the Cu–Mn Ox catalyst could be used four times
with no significant decrease in the yields. Consistent with these
results, no apparent changes could be discovered between the
FT-IR spectra and XRD patterns of the fresh and recycled
catalysts. Those mean Cu–Mn mixed oxide was a stable,
heterogeneous catalyst for allylic oxidation.
1
2
3
4
5
Standard effect
Fig. 7 Pareto plot for the oxidation of isolongifolene
Table 5 Three-level full factorial design for isolongifolenone 1a
a
Yield /%
Run
Cu–Mn Ox/mg
TBHP/equiv
Oxidation of different cyclic olefins catalyzed by Cu–
Mn Ox
1
2
3
4
5
6
7
8
9
100
100
100
150
150
50
3
5
3
1
3
3
5
1
1
3
5
95.2
93.4
95.1
55.4
93.0
76.3
60.1
38.1
54.7
94.9
89.4
To further probe the generality of this catalytic system,
various cyclic olefins were investigated under the optimal
condition and the results are summarized in Table 7.
Cyclohexene was oxidized with 100 % conversion and
50
9
3.9 % selectivity for 2-cyclohexene-1-one (1b). Interest-
ingly, 2-cyclohexene-1-one undergoes epoxidation with
00 % conversion and 92.8 % selectivity for 7-oxabicy-
50
100
100
150
1
1
1
0
1
clo[4.1.0]heptan-2-one (2a) and no cyclohex-2-ene-1,4-
dione. Meanwhile, when indane was oxidized, 93.1 %
conversion 81.6 % selectivity for 1-indanone (3a) was
obtained. When oxidation of a-pinene and b-pinene was
performed, 85.2 % conversion was obtain with 85.1 %
All reactions were carried out using isolongifolene (1 mmol), TBHP,
3
Cu–Mn Ox, 4 cm CH CN, and O (1 atm), A.T, 24 h
3 2
a
Determined by GC
1
23

Allylic oxidation of cyclic alkenes with molecular oxygen and tert-butyl hydroperoxide over…
Table 7 Results of oxidation of
cyclic olefins over Cu–Mn Ox
Entry
Substrate
Product
Conversion / % Selectivity / %
1
b
1
100
100
93.9
92.8
O
O
2
3
4
5
O
2a
O
O
3a
93.1
85.2
90.2
81.6
85.1
98.5
4
a
O
O
5
a
6a
6
87.8
89.2
HO
3
All reactions were done using alkene (1.0 mmol), Cu–Mn Ox (100 mg), TBHP (3 mmol), 4 cm
CH
GC
3 2
CN, and O (1 atm), A.T, 24 h. Selectivity (%) = yield (%)/conversion (%), determined by
selectivity of 4,6,6-trimethyl-bicyclo[3.1.1]hept-3-en-2-one
4a) and 90.2 % conversion was afforded 98.5 % selectivity
of 6,6-dimethyl-2-methylenebicyclo[3.1.1]heptan-3-one
5a), respectively. Surprisingly, when terpinolene was oxi-
dized, only gave corresponding rearrangement product,
7.8 % conversion and 89.2 % selectivity for 2-(4-methyl-
good yields without using excesses of the alkene. Fur-
thermore, DoE was designed to confirm the best conditions
of allylic oxidation. Besides, the catalyst was identified to
be stable and reusable without substantial loss of activity.
(
(
8
phenyl)propan-2-ol (6a) was obtained.
Experimental
All the reagents in the experiment were of analytical grade
except industrial grade isolongifolene, terpinolene, and
molecular oxygen, which were used without further dis-
posal, if not mentioned. Deionized water was used
throughout this experiment. Each of reaction was per-
formed with magnetic stirrers under an ambient
Conclusion
In using a catalytic amount of mixed copper-manganese
oxide, the allylic oxidation of cycloolefins in the presence
of 1 atm O and TBHP has been efficiently carried out in
2
123

W. Zhang et al.
temperature. ICP were measured with Optima 5300 DV,
FT-IR spectra were determined on a MAGNA-1R550 using
Initially, stir vigorously for 30 min to form a subtly dis-
persed heterogeneous system. 70 % aqueous solution of
TBHP was added to the system and then purged with
oxygen. The reaction mixture was stirred for the required
time (about 20–24 h). Reactions were measured by gas
chromatography (GC) using naphthaline as an internal
standard. To take the small portion for the GC analysis at
appropriate time intervals, the small portions were diluted
-
1
KBr discs in the 400–4000 cm region under atmospheric
conditions. The specific surface areas were determined
using the BET equation and the microspore volumes by the
de Boer’s t-method on ASAP2020M. Powder XRD were
performed on a XD-3 diffractometer with CuKa radiation
(
k = 1.5406 nm) scanning from 10 to 70° (2h) at a scan
-1
rate of 0.5 min and using silicon as an external standard.
The working voltage and the current were 36 kV and
20-fold with CH CN before the analysis. Saturated aqueous
3
3
Na S O solution (10 cm ) was added to remove any
2
2 3
2
5 mA. TG/DTA measurements of the samples were
redundant TBHP after filtered out the residue, and the
solution was extracted with dichloromethane
measured with STA instruments STA449 F3 Jupiter ther-
3
(3 9 50 cm ), washed with 10 cm saturated aqueous
3
mal analyzer used a-Al O crucible in the temperature
range of 303–1173 K at a heating rate of 283 K min
2
3
-
1
EDTA solution, and dried over anhydrous Na SO . The
2
4
under nitrogen conditions. SEM images were obtained with
a SUPRA 55 Sapphire microscope operating at accelera-
tion voltages 10 kV, and magnification values up to 50 KX.
The reaction products of oxidation were analyzed using
GC-7890A gas chromatograph with a HP-5 column
solvent was then evaporated to dryness. The resulting oily
residue was purified by silica gel column chromatography
1
(petroleum ether/EtoAc = 20:1) and analyzed by H NMR,
X-ray single crystal diffraction, or GC and GC–MS.
The recovery of this black powder by filtration, drying
and its submission to X-ray diffraction analysis, allowed us
to know that catalytic capacity of Cu–Mn Ox whether there
is a change or not after the reaction. The recycling exper-
iments were carried out as follows: After the completion,
the catalyst was filtered out and washed with warm water
for more than three times. Then, it was activated by dryness
in the oven at 378 K for 10 h. The structures of the prod-
ucts were confirmed by GC–MS (Perkin Elmer Instruments
Clarus500, 70 eV) by comparison with authentic samples.
Product isolongifolenone (GC yield 95.2 %) was isolated
by column chromatography (silica) using mixtures of pet-
(30 m 9 0.32 mm 9 0.25 lm) in flame ionization detec-
tor (FID) and were confirmed by gas chromatograph–mass
spectra (GC–MS) on Perkin Elmer Instruments (Clarus500)
1
with ionization energy of 70 eV. H NMR spectra were
recorded on 600 MHz NMR spectrometer (Bruker
AV600), using tetramethylsilane (TMS) as the internal
standard and CDCl as the solvent. X-ray single crystal
3
diffraction experiments were carried out on with MoKa
˚
radiation (k = 0.71073 A) using a bruker SMART APEX
CCD diffractometer at 296 K.
Catalyst preparation
roleum ether and EtOAc (20:1) as eluents (isolated yield
1
2.6 %) and identified by H NMR, IR, and X-ray crystal
8
Catalyst was prepared by co-precipitation method based on
the paper which was reported by Jonesa C [29]. An alkaline
solution containing 1270 mg Na CO (12 mmol) and
diffraction (Fig. 9).
2
3
3
5
200 mg NaOH (130 mmol) in 100 cm deionized water
was added dropwise over 1.5 h to another solution con-
taining Cu (NO ) Á3H O and 50 % Mn(NO ) aquatic
3
2
2
3 2
3
solution in 50 cm deionized water. The molar ratio [Mn]/
(
[Cu] ? [Mn]) is 0.40. The suspension solution was then
stirred at 343 K for 22 h, and was gradually changed in
color from blue to black during the course of reaction. The
black precipitate was filtered and the residue was washed
with warm deionized water. The solid was then dried in the
oven at 378 K for 10 h and then calcined in muffle furnace
at different temperature 573 or 673 K for 10 h. In the finial,
it was left exposed to air 3 days before use.
General procedure for the allylic oxidation
Alkene (1 mmol), Cu–Mn Ox (100 mg), and amount of
3
3
TBHP were stirred in 4 cm of acetonitrile in a 50 cm
round-bottom flask equipped with a magnetic stirrer.
Fig. 9 ORTEP view of isolongifolenone
1
23

Allylic oxidation of cyclic alkenes with molecular oxygen and tert-butyl hydroperoxide over…
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33; or e-mail:deposit@ccdc.cam.ac.uk.
Acknowledgments We are Grateful to colleges and universities in
Guangxi Science and Technology Research projects (ZD2014046,
YB2014331), Natural Science Foundation of Guangxi Zhuang
Autonomous Region (No. 2014GXNSFAA118032) and Graduate
education innovation project of Guangxi University for nationalities
2
2
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gxun-chxs2015087) for financial support.
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