Cyclohexene Promoted Efficient Biomimetic Oxidation of Alcohols to Carbonyl Compounds Catalyzed by Manganese Porphyrin under Mild Conditions?

Article abstract of DOI:10.1002/cjoc.201900426

Selective oxidation of alcohols to corresponding carbonyl compounds is one of the most important processes both in academic and application research. As a kind of biomimetic catalyst, metalloporphyrins-catalyzed aerobic oxidation of alcohols with aldehyde as hydrogen donator is gathering much attention. However, using olefins as another kind hydrogen donator for aerobic oxidation of alcohols has not been reported. In this study, a system comprising managenese porphyrin and cyclohexene for biomimetic aerobic oxidation of alcohols to carbonyl compounds was developed. The catalytic system exhibited excellent catalytic performance and selectivity towards the corresponding products for most primary and secondary alcohols under mild conditions. Based on the results obtained from experiments as well as in situ EPR (electron paramagnetic resonance) and UV-vis spectroscopy, the role of cyclohexene was demonstrated.

Full text of DOI:10.1002/cjoc.201900426

Chinese Journal
of Chemistry
CJC
中 国 化 学 - An International Journal
Accepted Article
Title: Cyclohexene Promoted the Efficient Biomimetic Oxidation of Alcohols to
Carbonyl Compounds Catalyzed by Manganese Porphyrin under Mild Conditions
Authors: Xiao-Hui Liu, Hai-Yang Yu, Can Xue, Xian-Tai Zhou* and Hong-Bing Ji*
This manuscript has been accepted and appears as an Accepted Article online.
This work may now be cited as: Chin. J. Chem. 2020, 38, 10.1002/cjoc.201900426.
The final Version of Record (VoR) of it with formal page numbers will soon be
published online in Early View: http://dx.doi.org/10.1002/cjoc.201900426.
ISSN 1001-604X • CN 31-1547/O6
mc.manuscriptcentral.com/cjoc
www.cjc.wiley-vch.de

Cyclohexene Promoted the Efficient Biomimetic Oxidation of Alcohols to
Carbonyl Compounds Catalyzed by Manganese Porphyrin under Mild
Conditions
Xiao-Hui Liu,a Hai-Yang Yu,a Can Xue,a Xian-Tai Zhou*, a and Hong-Bing Ji*b,c
a School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai 519082, P. R.China
b Fine Chemical Industry Research Institute, the Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province, School of Chemistry,
Sun Yat-sen University, Guangzhou 510275, P. R. China
c School of Chemical Engineering, Guangdong University of Petrochemical Technology, Maoming 525000, P. R.China
Cite this paper: Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX
Summary of main observation and conclusion Selective oxidation of alcohols to corresponding carbonyl compounds is one of the most important
processes both in academic and application research. As one kind of biomimetic catalysts, metalloporphyrins-catalyzed aerobic oxidation of alcohols with
aldehyde as hydrogen donator is gathering much attention. However, using olefins as another kind hydrogen donator for the aerobic oxidation of alcohols
has not been reported. In this study, a system comprising managenese porphyrin and cyclohexene for the biomimetic aerobic oxidation of alcohols to
carbonyl compounds was developed. The catalytic system exhibited excellent catalytic performance and selectivity towards the corresponding products for
most primary and secondary alcohols under mild conditions. Based on the results obtained from experiments as well as in situ EPR (Electron Paramagnetic
Resonance) and UV–vis spectroscopy, the role of cyclohexene was demonstrated.
in the aerobic catalytic oxidation reaction. This is mainly due to the
Background and Originality Content
harsh conditions for activating molecular oxygen in the oxidation
The selective oxidation of alcohols to carbonyl compounds is
one of the most important processes because the products are
valuable in organic synthesis1. Numerous methods for the oxidation
of alcohols have been developed involve the use of stochiometric
oxidants such as chromium oxides2, TBHP (tert-butyl hydrogen
peroxide)3, hydrogen peroxide4 etc., which causes environmental
and high cost problems. From the viewpoints of enviroment and
cost, selective oxidation of alcohols with molecular oxygen is
extremely valuable and particularly attractive. The aerobic
oxidation of alcohols catalyzed by TEMPO (2,2,6,6-tetra-
methylpiperidyl-l-oxy) or its derivatives in absence of transition
metal is gathering much attention5. And variety of methods were
reported on the aerobic oxidation of alcohols catalyzed by metal
catalysts like ruthenium6, manganese7, cobalt8, and Au-Pd alloy
nanoparticles9 or vanadium oxide10 presented excellent activity.
Particularly, most common transition metals like iron and
copper are also efficient for the aerobic oxidation of alcohols11. Ma
group reported a general an practical catalytic protocol of
Fe(NO3)3·9H2O/TEMPO/NaCl to accomplish the selective aerobic
oxidation of alcohols to aldehydes or ketones at room
temperature12. Copper complexes bearing redox-active ligands
catalyzed the aerobic oxidation of alcohols to aldehydes efficiently
without using any additives at room temperature13. Most recently,
Cu(NO3)3·3H2O/TEMPO or (4-HO) TEMPO catalyst presented
excellent performance in the selective aerobic oxidation of alcohols
to corresponding aldehydes using readily available reagents, at
room temperature with O2 or ambient air as the oxidant14.
process15. Therefore, it is of great concern to achieve the activation
of dioxygen under mild conditions. Metalloporphyrins-mediated
biomimetic catalytic system is the promising approach due to the
similar reactivity as enzyme-catalyzed oxidation, which has been
gathering much attention in recent years16.
In bio-oxidation mediated by cytochrome P450 enzymes,
hydroxylation can be achieved by utilizing NAD(P)H (nicotinamide
adenine dinucleotide (phosphate)) as the hydrogen donator for
activating molecular oxygen17. Therefore, aldehydes acts as
NAD(P)H-like hydrogen donator are widely used to activate
dioxygen in metalloporphyrins-catalyzed oxidation system18. Other
compounds that containing active α-hydrogen are desired to have
the efficiency of molecular oxygen activation. Recently, our group
reported the biomimetic aerobic epoxidation of olefins with
isopropylbenzene as hydrogen donator, with excellent conversion
and selectivity up to 94%19. The biomimetic aerobic oxidation of
cyclohexane and diphenylmethane in the presence of cyclohexene
as hydrogen donator were also reported recently20.
However, the selective aerobic oxidation of alcohols in
presence of cyclohexene as hydrogen donator catalyzed by
metalloporphyrins with molecular oxygen as oxidant is still limited.
As part of our ongoing interests in biomimetic catalytic oxidations
process with dioxygen, the aerobic oxidation of alcohols to carbonyl
compounds catalyzed by manganese porphyrin in the presence of
cyclohexene has been developed in this work (Scheme 1). The
catalytic system exhibited excellent catalytic performance and
selectivity towards the corresponding products for most primary
and secondary alcohols under mild conditions. Based on the results
There is always imbalance between conversion and selectivity
This article has been accepted for publication and undergone full peer review but has not been through
the copyediting, typesetting, pagination and proofreading process which may lead to differences between
this version and the Version of Record. Please cite this article as doi: 10.1002/cjoc.201900426
This article is protected by copyright. All rights reserved.

First author et al.
Report
obtained from experiments as well as in situ EPR and UV–vis
spectroscopy, a plausible mechanism for the alcohol aerobic
oxidation catalyzed by MnTPPCl (meso-triphenylporphyrin
manganese chloride) in presence of cyclohexene was proposed.
same ligand but different metal ions were tested. Comparison
among the tested catalysts revealed that manganese porphyrins
(MnTPPCl) exhibited higher catalytic activity than iron, copper,
cobalt and zinc porphyrins (entries 1-5, Table 1). These catalytic
performance differences could be ascribed to the stability of high-
valent species during the oxidation21. Manganese complexes have
been reported to be efficient for alcohols oxidation due to its
various multiple valence22. Meng group also reported the aerobic
oxidation of benzyl alcohol to benzaldehyde with 95% yield by using
decacarbonyldimanganese [Mn2(CO)2] as catalyst at 120oC23.
Interestingly, the selectivity of benzaldehyde was excellent
whatever metalloporphyrins catalyst was used in this biomimetic
oxidation system.
Scheme 1 Aerobic oxidation of alcohols catalyzed by manganese porphyrins
in presence of cyclohexene
O
OH
MnTPPCl
benzotrifluoride, cyclohexene, 60oC, O2(1 atm)
R1
R2
R1
R2
N
N
N
N
Mn
Cl
The selective oxidation of benzyl alcohol with different amount
of cyclohexene were examined. The conversion of benzyl alcohol
increased as cyclohexene amount rose (entries 6 and 7, Table 1).
But the large excess amount of cyclohexene could promote over-
oxidation of benzaldehyde to benzoic acid (entry 7, Table 1). The
effect of solvent on the aerobic oxidation of benzyl alcohol with
MnTPPCl catalyst and cyclohexene was also examined. As shown in
Table 1, the efficiency of alcohol oxidation is closely related with the
polarity of the used solvents (entries 8~10, Table 1). The strong
electrophilic effect of benzotrifluoride was most favorable to the
alcohol oxidation. Moderate yield of benzaldehyde was obtained
using ethyl acetate and acetonitrile (entries 9 and 10, Table 1). The
remarkable differences could be attributed to two aspects. Beside
the solvation effect, benzotrifluoride is favorable to improve the
stability of free radicals24.
The oxidation was greatly influenced by the reaction
temperature (entries 11 and 12, Table 1). With increasing
temperature, benzyl alcohol conversion increased as temperature
rose. But the selectivity towards the over-oxidation product
(benzoic acid) increased when the oxidation was conducted at 70
oC (entry 12, Table 1).
MnTPPCl
Results and Discussion
Catalytic performance
Using benzyl alcohol as testing substrate, the reactivity and
selectivity of catalytic system involved metalloporphyrins and
cyclohexene were explored (Figure 1). In the control experiments,
that is the reaction was conducted in absence of either MnTPPCl or
cyclohexene, almost no oxidation occurred after 60 min stirring.
Then, about 25% benzyl alcohol was converted to corrresponding
aldehyde in excellent selectivity when the oxidation was carried out
with either MnTPPCl or cyclohexene alone. However, the
simultaneous presence of MnTPPCl and cyclohexene could make
the oxidation exhaustivity. This result indicates that the synergistic
action plays significant role in the biomimetic catalytic oxidation of
alcohols.
Table 1. Optimization of reaction conditions for the oxidation of benzyl
alcohol by MnTPPCl and cyclohexenea
Amount of
Conv.
(%)
Select.
(%)
Entry
Catalyst
cyclohexene
(mmol)
1.0
Solvent
1
2
FeTPPCl
MnTPPCl
CuTPP
Benzotrifluoride
Benzotrifluoride
Benzotrifluoride
Benzotrifluoride
Benzotrifluoride
Benzotrifluoride
Benzotrifluoride
Toluene
80
97
72
82
83
62
98
76
45
>99
>99
>99
>99
>99
>99
92(8)
>99
>99
1.0
1.0
1.0
1.0
0.5
1.5
1.0
1.0
3
4
CoTPP
5
ZnTPP
6
MnTPPCl
MnTPPCl
MnTPPCl
MnTPPCl
Figure 1. Aerobic oxidation of benzyl alcohol. Benzyl alcohol (2.0 mmol),
MnTPPCl (0.1 mol%), benzotrifluoride (5 mL), O2 bubbling, 60oC, 60 min. A:
in absence of catalyst and cyclohexene; B: MnTPPCl (0.1 mol%); C:
cyclohexene (1.0 mmol); D: in presence of MnTPPCl (0.1 mol%) and
cyclohexene (1.0 mmol).
7b
8
9
Ethyl acetate
Followed, the activities of different metalloporphyrins that have
www.cjc.wiley-vch.de
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

Running title
Chin. J. Chem.
10
11c
12d
MnTPPCl
1.0
1.0
1.0
Acetonitrile
52
69
99
>99
>99
O
H
O
O2N
2
3
90
90
90
92
>99
>99
MnTPPCl
MnTPPCl
Benzotrifluoride
Benzotrifluoride
N
O2
81(19)
O
OH
a Benzyl alcohol (2.0 mmol), solvent (5 mL), catalyst (0.1 mol%), O2 bubbling,
60 oC, 60 min.
Cl
Cl
b The numbers in parentheses indicate the selectivity of benzoic acid.
c 50 oC.
H
O
O
d 70 oC, the numbers in parentheses indicate the selectivity of benzoic acid.
4
5
60
60
99
99
>99
>99
e
e
O
M
O
M
To further identify the scope of alcohol reactions in presence of
MnTPPCl and cyclohexene, the study was extended to include
various benzylic alcohols, primary and secondary alcohols and the
results are summarized in Table 2.
OH
O
The catalytic system appeared efficient towards most benzylic
primary alcohols, in which alcohols were smoothly converted to
corresponding aldehydes with high yields (entries 1~6, Table 2). The
efficiency for the oxidation of benzylic primary alcohols in this
catalytic system was dependent on the electronic property of the
para substituents of the substrate. Compared to benzylic alcohols
with electron-donating groups, electron-withdrawing groups
seemed unfavorable for forming carbonyl compounds, in which
longer reaction time was necessary. It could be attributed to the
electronic effect promoting β-hydride elimination. The catalytic
system showed also excellent efficiency towards the oxidation of
saturated primary aliphatic alcohols, such as 3-phenylpropanol and
1-hexanol (entries 6 and 7, Table 2). The present catalyticic system
was also efficient for basic substrates like 4-pyridinemethanol. It
was converted with high conversion (87%) within 90 min (entry 8,
Table 2). Furthermore, MnTPPCl with cyclohexene system was
found to be efficient for the oxidation of most secondary to the
corresponding ketones (entries 9-12, Table 3). Even sterically
hindered 2-adamantanol could smoothly be converted into
corresponding ketone with yield of 92% (entry 12, Table 2).
O
O
OH
OH
6
60
96
>99
7
8
60
90
95
87
>99
>99
OH
O
N
N
O
OH
9
60
96
>99
O
OH
10
11
60
60
97
93
>99
>99
O
OH
Plausible mechansim
The profile of benzyl alcohol oxidation catalyzed by MnTPPCl
and cyclohexene in presence of molecular oxygen is shown in Figure
2. The conversion of benzyl alcohol slowly increased within the first
10 min. Then, the reaction rate rapidly increased. It is clear that
there is an induction period during the catalytic oxidaiton process,
which exihibited the features of the radical reaction. For verifying
the free-radical mechanism, 2,6-di-tert-butylphenol (1 mmol),
serving as the free-radical inhibitor, was used. After the addition of
this inhibitor, the oxidation was subsequently quenched.
O
OH
12
90
92
>99
aSubstrate (2.0 mmol), MnTPPCl (0.1 mol%), benzotrifluoride (5 mL),
cyclohexene (1.0 mmol), O2 bubbling, 60 oC.
As has been previously reported, high-valent species was
generally produced in the oxidation catalyzed by
metalloporphyrins25. The in situ UV–vis spectra were recorded on a
spectrophotometer connected to an AvaSpec-2048 spectrometer
under the given reaction conditions, and the obtained spectra were
presented in Figure 3.
Table 2. Oxidation of various alcohols catalyzed by MnTPPCl with
cyclohexenea
Time Conv. Select.
Entry
1
Substrate
Product
/min
/%
/%
H
O
O
60
97
>99
Chin. J. Chem. 2019, 37, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
This article is protected by copyright. All rights reserved.

First author et al.
Report
Wilmad WG-810-A quartz-flat cell. A mixture of benzotrifluoride
solution comprised MnTPPCl, cyclohexene, and PBN (free-radical
spin-trapping agent). The cell was sealed after filling dioxygen. EPR
analyses were performed under a microwave frequency of 9.05 GHz
at 333 K. The results were showed in Figure 4.
According to previous reports, the α-hydrogen atom of
cyclohexene was easily abstracted under high temperature,
affording an allylic radical27. As shown in Figure 4A, two stable PBN
radical adducts were obtained when the oxidation of cyclohexene
was carried out in molecular oxygen without MnTPPCl (Figure 4A,
a). Adduct 1 was characterized by hyperfine splitting constant (aN1
= 15.2 G, aH1 = 3.6 G, g = 2.0033), adduct 2 was characterized by
hyperfine splitting constants, (aN2 = 14.0 G, aH2 = 2.3 G, g = 2.0033).
Allylic radical can combine with dioxygen quickly to generate allylic
peroxyl radical. According to our previous works, adduct 1 should
be assigned to carbon-centred cyclohexenyl radical (C6H9•), adduct
2 is assigned to cyclohexenyl peroxyl radical (C6H9OO•)20a
.
Figure 2. Reaction profile of benzyl alcohol aerobic oxidation catalyzed by
MnTPPCl in presence of cyclohexene. Benzyl alcohol
(2.0 mmol),
benzotrifluoride (5 mL), MnTPPCl (0.1 mol%), cyclohexene (1.0 mmol), O2
bubbling, 60 oC.
The spectrophotometer was programmed for acquiring UV–vis
spectrum every 5 min. As shown in Figure 3, as the reaction
proceeded, the Soret band gradually decreased at 477 nm.
Meanwhile, a red shift with 5 nm in the Soret band from 477 nm to
482 nm was observed. The color bleach of mixture solution from
dark green to yellow was also observed. Such changes in the in situ
UV–vis spectra have been reported to be attributed to the
generation of the oxidize active species (PorMnV=O) during
oxidation26.
Figure 4. A: in situ EPR spectra of cyclohexene aerobic oxidation at 333K, (a)
without MnTPPCl, (b) catalyzed by MnTPPCl; B: in situ EPR spectra of benzyl
alcohol oxidation catalyzed by MnTPPCl and cyclohexene at 333K.
When MnTPPCl catalyst was added in the mixture, the signal
of adduct 1 disappeared gradually, while another radical signal
constantly increased (adduct 3). Adduct 3 was characterized by
hyperfine splitting constant (aN3 = 15.5 G, aH3 = 3.4 G, g = 2.0031).
Therefore, the manganese porphyrin catalyst has been suggested
to be favorable for the transfer of radical 2 to radical 3. The radical
transfer involves the participation of manganese porphyrins
catalyst. High-valent Mn species and cyclohexenyl alkoxyl radical
could be generated from the heterolysis of O-O bond in
cyclohexenyl peroxyl radical (C6H9OO•). Hence, the radical should
be assigned to cyclohexenyl alkoxyl radical (C6H9O•)20b
.
Figure 4B shows time courses of in situ EPR spectra towards
benzyl alcohol oxidation catalyzed by MnTPPCl and cyclohexene. As
reaction progresses, the radical transformation of radical 2 to
radical 3 was further confirmed. The active cyclohexenyl alkoxyl
radical can react with one cyclohexene molecule to produce
cyclohexen-1-ol and one cyclohexenyl radical (C6H9•).
Based on the above discussions, a plausible mechanism was
proposed for the aerobic oxidation of alcohols to carbonyl
compounds in the presence of MnTPPCl and cyclohexene, as shown
in Scheme 2.
Figure 3. In situ UV-vis spectra for benzyl alcohol aerobic oxidation catalyzed
by MnTPPCl in presence of cyclohexene (interval 5 min). Benzyl alcohol
(2.0 mmol), benzotrifluoride (5 mL), MnTPPCl (0.1 mol%), cyclohexene (1.0
mmol), O2 bubbling, 60 oC.
To obtain more insights into the role of cyclohexene in the
oxidation of alcohols catalyzed by manganese porphyrins, in situ
EPR spectra was used to record the signal changes of free radicals.
The catalytic oxidation in benzotrifluoride was carried out in a
The reaction initiated from the generation of cyclohexenyl
radical (1, C6H9•), which is derived from the abstraction of hydrogen
www.cjc.wiley-vch.de
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

Running title
Chin. J. Chem.
at the allylic position under reaction temperature conditions.
Cyclohexenyl peroxyl radical (2, C6H9OO•) is rapidly formed by the
insertion of oxygen. Subsequently, cyclohexenyl alkoxyl radical (3,
C6H9O•) and PorMn(V)=O were generated from the O-O bond
cleavage of cyclohexenyl peroxyl radical (2, C6H9OO•). Cyclohexenyl
alkoxyl radical is an active oxy radical, which can react with another
cyclohexene molecule to produce 2-cyclohexen-ol and cyclohexenyl
radical. The formation of benzaldehyde is attibuted to the reaction
of benzyl alcohol with Mn-oxo species, followed by the β-hydride
elimination.
spectroscopy measurements were performed on a JESFA-200 (JEOL,
Japan) spectrometer using PBN as a free-radical spin-trapping agent.
General procedures for the biomimetic catalytic oxidation of
alcohols
The catalytic oxidation of alcohols were carried out in a
magnetically stirred glass reaction tube fitted with a reflux
condenser. Using benzyl alcohol as a model substrate, a typical
procedure was as follows: A solution of benzotrifluoride (5 mL),
benzyl alcohol (2 mmol), cyclohexene (2.0 mmol), MnTPPCl (2×10-3
mmol, 0.1mol% based substrate) and 0.5 mmol naphthalene (inert
internal standard) were added in the tube. Then the mixture was
stirred at 60°C for 60 min with the bubbled molecular oxygen. The
consumption of benzyl alcohol and formation of benzaldehyde
were monitored by GC (Shimadzu GC-2010 plus) and GC-MS
(Shimadzu GCMS-QP2010). Each catalytic reaction was repeated
three times.
Conclusions
In this study, a system comprising managenese porphyrin and
cyclohexene for the biomimetic aerobic oxidation of alcohols to
carbonyl compounds was developed. The catalytic system exhibited
excellent catalytic performance and selectivity towards the
corresponding products for most primary and secondary alcohols
under mild conditions. Based on the results obtained from
experiments as well as in situ EPR and UV–vis spectroscopy, a
plausible mechanism for the alcohol oxidation catalyzed by
managenese porphyrin in presence of cyclohexene was presented.
The role of cyclohexene was to generate Mn-oxo species through
the propagation of free radical that generated from cyclohexene.
Oxidation of alcohol monitored by in situ UV–vis
spectroscopy
Catalytic oxidation was carried out in the stainless-steel reactor
(Parr 5510) equiped with a reflux condenser. The reaction mixture
contained solvent (benzotrifluoride), catalyst (MnTPPCl), alcohol
and cyclohexene were added into the reactor. The reactor sealed
and dioxygen bubbled through the mixture. The reaction mixture
was heated to 60 °C. The in situ UV–vis spectra of MnTPPCl were
recorded on the AvaSpec-2048 spectrometer, which was equipped
with a high-pressure, high-temperature probe and connected to the
stainless-steel reactor. The spectrophotometer was programmed at
5 min intervals.
Scheme 2 Plausible mechanism for the aerobic oxidation of benzyl alcohol
catalyzed by MnTPPCl in presence of cyclohexene
O
OH
O
H
Ph
PorMn(V)
PorMn(III)
Oxidation of alcohol monitored by in situ EPR spectroscopy
OH
O
O
V
Aerobic catalytic oxidation in benzotrifluoride was performed in
a Wilmad WG-810-A quartz-flat cell with a mixture of the solution
of MnTPPCl as well as cyclohexene, alcohol and PBN. A JESFA-200
(JEOL, Japan) spectrometer was utilized to record in situ EPR spectra.
The cell was sealed after filling dioxygen. EPR analyses were
performed at a microwave frequency of 9.05 GHz at 333K.
Instrument conditions for all analyses were as follows: microwave
frequency, 9.05 GHz; modulation amplitude, 2 mT; modulation
frequency, 100 kHz; power, 0.998 mW; and time constant, 0.03 s. All
spectra represent the signal-averaged sum of six scans unless
otherwise noted.
P
o
rM
n
H
3
O
O
O2
O
1
2
Experimental
Materials and methods
Alcohols and the corresponding carbonyl comppounds,
cyclohexene, N-tert-butyl-alpha-phenylnitrone (PBN) were
purchased from J&K Scientific Ltd. Other reagents were of analytical
grade and used without further purification unless indicated.
Metalloporphyrin catalysts were prepared according to previous
procedures28.
Acknowledgement
This work was financially supported by the National Key
Research and Development Program of China (2016YFA0602900),
the National Natural Science Foundation of China (No. 21425627,
21576302, 21878344 and 21938001) , the National Natural Science
Foundation of China-SINOPEC Joint Fund (No. U1663220),
Guangdong Provincial Key R&D Programme(2019B110206002) and
the Local Innovative and Research Teams Project of Guangdong
Pearl River Talents Program (2017BT01C102).
FT-IR spectra were obtained on a Bruker 550 spectrometer.
The UV–vis spectra were recorded on a Shimadzu UV-2450
1
spectrophotometer. H NMR and 13C NMR spectra were recorded
on a Bruker Avance III 400 M spectrometer. Elemental analysis data
were received on a Vario EL III system. Mass spectra were obtained
on a Shimadzu LCMS-2010A. The in situ UV–vis spectra were
recorded on a spectrophotometer connected to an AvaSpec-2048 References
spectrometer. The in situ EPR (Electron Paramagnetic Resonance)
Badalyan, A.; Stahl, S. S., Cooperative electrocatalytic alcohol oxidation
Chin. J. Chem. 2019, 37, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
This article is protected by copyright. All rights reserved.

First author et al.
Report
with electron-proton-transfer mediators. Nature 2016, 535 (7612),
28 (12), 1025-1027; (b) Sun, H. Y.; Hua, Q.; Guo, F. F.; Wang, Z. Y.;
Huang, W. X., Selective Aerobic Oxidation of Alcohols by Using
Manganese Oxide Nanoparticles as an Efficient Heterogeneous
Catalyst. Adv. Synth. Catal. 2012, 354 (4), 569-573; (c) Su, Y.; Wang, L.
C.; Liu, Y. M.; Cao, Y.; He, H. Y.; Fan, K. N., Microwave-accelerated
solvent-free aerobic oxidation of benzyl alcohol over efficient and
reusable manganese oxides. Catal. Commun. 2007, 8 (12), 2181-2185.
(a) Su, H.; Zhang, K. X.; Zhang, B.; Wang, H. H.; Yu, Q. Y.; Li, X. H.;
Antonietti, M.; Chen, J. S., Activating Cobalt Nanoparticles via the
Mott-Schottky Effect in Nitrogen-Rich Carbon Shells for Base-Free
Aerobic Oxidation of Alcohols to Esters. J. Am. Chem. Soc. 2017, 139
(2), 811-818; (b) Zhao, X.; Zhou, Y.; Huang, K.; Li, C. Z.; Tao, D. J.,
Ultralow Loading Cobalt-Based Nanocatalyst for Benign and Efficient
Aerobic Oxidation of Allylic Alcohols and Biobased Olefins. ACS Sustain.
Chem. Eng. 2019, 7 (2), 1901-1908; (c) Albadi, J.; Alihosseinzadeh, A.;
Jalali, M.; Shahrezaei, M.; Mansournezhad, A., Highly dispersed cobalt
nanoparticles supported on a mesoporous Al2O3: An efficient and
recyclable catalyst for aerobic oxidation of alcohols in aqueous media.
Mol. Catal. 2017, 440, 133-139.
Zhang, W.; Xiao, Z. A.; Wang, J. J.; Fu, W. Q.; Tan, R.; Yin, D. H., Selective
Aerobic Oxidation of Alcohols over Gold-Palladium Alloy Catalysts
Using Air at Atmospheric Pressure in Water. ChemCatChem 2019, 11
(6), 1779-1788.
Zavahir, S.; Xiao, Q.; Sarina, S.; Zhao, J.; Bottle, S.; Wellard, M.; Jia, J. F.;
Jing, L. Q.; Huang, Y. M.; Blinco, J. P.; Wu, H. S.; Zhu, H. Y., Selective
Oxidation of Aliphatic Alcohols using Molecular Oxygen at Ambient
Temperature: Mixed-Valence Vanadium Oxide Photocatalysts. ACS
Catal. 2016, 6 (6), 3580-3588.
(a) Jiang, X. G.; Liu, J. X.; Ma, S. M., Iron-Catalyzed Aerobic Oxidation of
Alcohols: Lower Cost and Improved Selectivity. Org. Process Res. Dev.
2019, 23 (5), 825-835; (b) Wei, Z. Y.; Ru, S.; Zhao, Q. X.; Yu, H.; Zhang,
G.; Wei, Y. G., Highly efficient and practical aerobic oxidation of
alcohols by inorganic-ligand supported copper catalysis. Green. Chem.
2019, 21 (15), 4069-4075; (c) Wang, L. Y.; Shang, S. S.; Li, G. S.; Ren, L.
H.; Lv, Y.; Gao, S., Iron/ABNO-Catalyzed Aerobic Oxidation of Alcohols
and Ketones under Ambient Atmosphere. J. Org. Chem. 2016, 81 (5),
2189-2193. (d) Zhao, G.; Yang, F.; Chen, Z.; Liu, Q.; Ji, Y.; Zhang, Y.,
Metal/oxide interfacial effects on the selective oxidation of primary
alcohols. Nat. Commun. 2017, 8, 14039; (e) Liu, Y.; Ma, S. M., CuCl-
Catalyzed Aerobic Oxidation of Allylic and Propargylic Alcohols to
Aldehydes or Ketones with 1:1 Combination of Phenanthroline and
Bipyridine as the Ligands. Chin. J. Chem. 2012, 30 (1), 29-34; (f) Hoover,
J. M.; Stahl, S. S., Highly practical copper (I)/TEMPO catalyst system for
chemoselective aerobic oxidation of primary alcohols. J. Am. Chem.
Soc. 2011, 133(42), 16901-16910; (g) Wu, J. L.; Liu, Y.; Ma, X. W.; Liu,
P.; Gu, C. Z.; Dai, B., Cu(II)-Catalyzed Ligand-Free Oxidation of
Diarylmethanes and Second Alcohols in Water. Chin. J. Chem. 2017, 35
(9), 1391-1395.
406-410; (b) Crabtree, R. H., Homogeneous Transition Metal Catalysis
of Acceptorless Dehydrogenative Alcohol Oxidation: Applications in
Hydrogen Storage and to Heterocycle Synthesis. Chem. Rev. 2017, 117
(13), 9228-9246; (c) Koh, M. J.; Khan, R. K. M.; Torker, S.; Yu, M.; Mikus,
M. S.; Hoveyda, A. H., High-value alcohols and higher-oxidation-state
compounds by catalytic Z-selective cross-metathesis. Nature 2015,
517 (7533), 181-186; (d) Mallat, T.; Baiker, A., Oxidation of alcohols
with molecular oxygen on solid catalysts. Chem. Rev. 2004, 104 (6),
3037-3058. (e) Sheldon, R. A.; Arends, I. W. C. E.; Ten Brink, G. J.;
Dijksman, A., Green, catalytic oxidations of alcohols. Acc. Chem. Res.
2002, 35 (9), 774-781; (f) Sigman, M. S.; Jensen, D. R., Ligand-
modulated palladium-catalyzed aerobic alcohol oxidations. Acc. Chem.
Res. 2006, 39 (3), 221-229.
(a) Heidarnezhad, A.; Zamani, F., Chromium containing
Fe3O4/polyacrylonitrile-ethylenediamine
as
a
magnetically
recoverable catalyst for alcohol oxidation. Catal. Commun. 2015, 60,
105-109; (b) Thao, N. T.; Nhu, N. T.; Lin, K. S., Liquid phase oxidation of
benzyl alcohol to benzaldehyde over sepiolite loaded chromium oxide
catalysts. J. Taiwan Inst. Chem. Eng. 2018, 83, 10-22.
(a) Kani, I.; Bolat, S., Effective catalytic oxidation of alcohols and
alkenes with monomeric versus dimeric manganese(II) catalysts and t-
BuOOH. Appl. Organomet. Chem. 2016, 30 (8), 713-721; (b) Gogoi, N.;
Begum, T.; Dutta, S.; Bora, U.; Gogoi, P. K., Rice husk derived nanosilica
supported Cu(II) complex: an efficient heterogeneous catalyst for
oxidation of alcohols using TBHP. RSC Adv. 2015, 5 (115), 95344-95352.
(a) Zhang, Z.; Khrouz, L.; Yin, G. C.; Andrioletti, B., Efficient Oxidation
of Benzylic and Aliphatic Alcohols Using a Bioinspired Cross-Bridged
Cyclam Manganese Complex with H2O2. Eur. J. Org. Chem. 2019, (2-3),
323-327; (b) Wagh, R. B.; Nagarkar, J. M., An efficient and sustainable
protocol for oxidation of alcohols to carbonyl compounds.
Tetrahedron Lett. 2018, 59 (37), 3443-3447.
(a) Dong, Y. L.; Zhao, X. M.; Liu, R. H., 4-OH-TEMPO/TCQ/TBN/HCl: A
Metal-Free Catalytic System for Aerobic Oxidation of Alcohols under
Mild Conditions. Chin. J. Chem. 2015, 33 (9), 1019-1023; (b) Shen, J. X.;
Sun, J. K.; Qin, S. S.; Chu, C. H.; Liu, R. H., 4-Benzamido-TEMPO
Catalyzed Oxidation of a Broad Range of Alcohols to the Carbonyl
Compounds with NaBrO3 under Mild Conditions. Chin. J. Chem. 2014,
32 (5), 405-409; (c) Zhang, J.; Jiang, Z. Q.; Zhao, D.; He, G. Z.; Zhou, S.
L.; Han, S. Q., Transition-Metal-Free TEMPO Catalyzed Aerobic
Oxidation of Alcohols to Carbonyls Using an Efficient Br2 Equivalent
under Mild Conditions. Chin. J. Chem. 2013, 31 (6), 794-798.
(a) Isaka, Y.; Kondo, Y.; Kuwahara, Y.; Mori, K.; Yamashita, H.,
Incorporation of a Ru complex into an amine-functionalized metal-
organic framework for enhanced activity in photocatalytic aerobic
benzyl alcohol oxidation. Catal. Sci. Technol. 2019, 9 (6), 1511-1517; (b)
Patil, M. R.; Kapdi, A. R.; Kumar, A. V., Recyclable Supramolecular
Ruthenium Catalyst for the Selective Aerobic Oxidation of Alcohols on
Water: Application to Total Synthesis of Brittonin A. ACS Sustain. Chem.
Eng. 2018, 6 (3), 3264-3278; (c) Hao, Z. Q.; Li, N.; Yan, X. L.; Li, Y.; Zong,
S. Q.; Liu, H. T.; Han, Z. G.; Lin, J., Ruthenium carbonyl complexes with
pyridylalkanol ligands: synthesis, characterization and catalytic
properties for aerobic oxidation of secondary alcohols. New J. Chem.
2018, 42 (9), 6968-6975.
Ma, S. M.; Liu, J. X.; Li, S. H.; Chen, B.; Cheng, J. J.; Kuang, J. Q.; Liu, Y.;
Wan, B. Q.; Wang, Y. L.; Ye, J. T.; Yu, Q.; Yuan, W. M.; Yu, S. C.,
Development of a General and Practical Iron Nitrate/TEMPO-
Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones:
Catalysis with Table Salt. Adv. Synth. Catal. 2011, 353 (6), 1005-1017.
Rajabimoghadam, K.; Darwish, Y.; Bashir, U.; Pitman, D.; Eichelberger,
S.; Siegler, M. A.; Swart, M.; Garcia-Bosch, I., Catalytic Aerobic
Oxidation of Alcohols by Copper Complexes Bearing Redox-Active
(a) Jing, H.; Sun, K. Q.; He, D. P.; Xu, B. Q., Amorphous manganese oxide
for catalytic aerobic oxidation of benzyl alcohol. Chin. J. Catal. 2007,
www.cjc.wiley-vch.de
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

Running title
Chin. J. Chem.
Ligands with Tunable H-Bonding Groups. J. Am. Chem. Soc. 2018, 140
(48), 16625-16634.
comprising metalloporphyrins and cyclohexene for the biomimetic
aerobic oxidation of toluene. Catal. Commun. 2018, 109, 76-79.
Hong, S.; Lee, Y. M.; Sankaralingam, M.; Vardhaman, A. K.; Park, Y. J.;
Cho, K. B.; Ogura, T.; Sarangi, R.; Fukuzumi, S.; Nam, W., A
Manganese(V)-Oxo Complex: Synthesis by Dioxygen Activation and
Enhancement of Its Oxidizing Power by Binding Scandium Ion. J. Am.
Chem. Soc. 2016, 138 (27), 8523-8532.
(a) Shaabani, A.; Boroujeni, M. B.; Laeini, M. S., Porous chitosan-MnO2
nanohybrid: a green and biodegradable heterogeneous catalyst for
aerobic oxidation of alkylarenes and alcohols. Appl. Organomet. Chem.
2016, 30 (3), 154-159; (b) Elmaci, G.; Ozer, D.; Zumreoglu-Karan, B.,
Liquid phase aerobic oxidation of benzyl alcohol by using manganese
ferrite supported-manganese oxide nanocomposite catalyst. Catal.
Commun. 2017, 89, 56-59.
Meng, S. S.; Lin, L. R.; Luo, X.; Lv, H. J.; Zhao, J. L.; Chan, A. S. C., Aerobic
oxidation of alcohols with air catalyzed by decacarbonyldimanganese.
Green. Chem. 2019, 21 (22), 6187-6193.
Hasegawa, E.; Ogawa, Y.; Kakinuma, K.; Tsuchida, H.; Tosaka, E.;
Takizawa, S.; Muraoka, H.; Saikawa, T., Tris(trimethylsilyl)silane
promoted radical reaction and electron-transfer reaction in
benzotrifluoride. Tetrahedron 2008, 64 (33), 7724-7728.
Zhai, D.; Ma, S. M., Copper catalysis for highly selective aerobic
oxidation of alcohols to aldehydes/ketones. Org. Chem. Front. 2019, 6
(17), 3101-3106.
(a) Marimuthu, A.; Zhang, J. W.; Linic, S., Tuning Selectivity in
Propylene Epoxidation by Plasmon Mediated Photo-Switching of Cu
Oxidation State. Science 2013, 339 (6127), 1590-1593; (b)
Punniyamurthy, T.; Velusamy, S.; Iqbal, J., Recent advances in
transition metal catalyzed oxidation of organic substrates with
molecular oxygen. Chem. Rev. 2005, 105 (6), 2329-2363.
(a) Zhou, X. T.; Ji, H. B., Cobalt Porphyrin Immobilized on
Montmorillonite: A Highly Efficient and Reusable Catalyst for Aerobic
Oxidation of Alcohols to Carbonyl Compounds. Chin. J. Catal. 2012, 33
(12), 1906-1912; (b) Saha, B.; Gupta, D.; Abu-Omar, M. M.; Modak, A.;
Bhaumik, A., Porphyrin-based porous organic polymer-supported
iron(III) catalyst for efficient aerobic oxidation of 5-hydroxymethyl-
furfural into 2,5-furandicarboxylic acid. J. Catal. 2013, 299, 316-320; (c)
Yazdely, T. M.; Ghorbanloo, M.; Hosseini-Monfared, H., Polymeric
ionic liquid material-anchored Mn-porphyrin anion: Heterogeneous
catalyst for aerobic oxidation of olefins. Appl. Organomet. Chem. 2018,
32 (8); (d) Rayati, S.; Nejabat, F., The catalytic efficiency of Fe-
porphyrins supported on multi-walled carbon nanotubes in the
oxidation of olefins and sulfides with molecular oxygen. New J. Chem.
2017, 41 (16), 7987-7991; (e) Huang, G.; Yuan, R. X.; Peng, Y.; Chen, X.
F.; Zhao, S. K.; Wei, S. J.; Guo, W. X.; Chen, X., Oxygen oxidation of
ethylbenzene over manganese porphyrin is promoted by the axial
nitrogen coordination in powdered chitosan. RSC Adv. 2016, 6 (54),
48571-48579; (f) Zhou, X. T.; Ji, H. B., Highly Efficient Oxidative
Cleavage of Carbon-Carbon Double Bond over meso-Tetraphenyl
Cobalt Porphyrin Catalyst in the Presence of Molecular Oxygen. Chin.
J. Chem. 2012, 30 (9), 2103-2108.
(a) Nam, W.; Kim, I.; Lim, M. H.; Choi, H. J.; Lee, J. S.; Jang, H. G.,
Isolation of an oxomanganese(V) porphyrin intermediate in the
reaction of a manganese(III) porphyrin complex and H2O2 in aqueous
solution. Chem. Eur. J. 2002, 8 (9), 2067-2071; (b) Fukuzumi, S.; Fujioka,
N.; Kotani, H.; Ohkubo, K.; Lee, Y. M.; Nam, W., Mechanistic Insights
into Hydride-Transfer and Electron-Transfer Reactions by
a
Manganese(IV)-Oxo Porphyrin Complex. J. Am. Chem. Soc. 2009, 131
(47), 17127-17134.
(a) Sharma, N.; Jung, J.; Ohkubo, K.; Lee, Y. M.; El-Khouly, M. E.; Nam,
W.; Fukuzumi, S., Long-Lived Photoexcited State of a Mn(IV)-Oxo
Complex Binding Scandium Ions That is Capable of Hydroxylating
Benzene. J. Am. Chem. Soc. 2018, 140 (27), 8405-8409; (b) Cho, K. B.;
Hirao, H.; Shaik, S.; Nam, W., To rebound or dissociate? This is the
mechanistic question in C-H hydroxylation by heme and nonheme
metal-oxo complexes. Chem. Soc. Rev. 2016, 45 (5), 1197-1210; (c) Li,
Y.; Zhou, X. T.; Chen, S. Y.; Luo, R. C.; Jiang, J.; Liang, Z. X.; Ji, H. B., Direct
aerobic liquid phase epoxidation of propylene catalyzed by Mn(III)
porphyrin under mild conditions: evidence for the existence of both
peroxide and Mn(IV)-oxo species from in situ characterizations. RSC
Adv. 2015, 5 (38), 30014-30020.
(a) Song, Y. X.; Xin, F.; Zhang, L. X.; Wang, Y., Oxidation of Cyclohexene
in the Presence of Transition-Metal-Substituted Phosphotungstates
and Hydrogen Peroxide: Catalysis and Reaction Pathways.
ChemCatChem 2017, 9 (21), 4139-4147; (b) Gupta, R.; Li, X. X.; Cho, K.
B.; Guo, M.; Lee, Y. M.; Wang, Y.; Fukuzumi, S.; Nam, W., Tunneling
Effect That Changes the Reaction Pathway from Epoxidation to
Hydroxylation in the Oxidation of Cyclohexene by a Compound I Model
of Cytochrome P450. J. Phys. Chem. Lett. 2017, 8 (7), 1557-1561.
Zhou, X. T.; Ji, H. B., Biomimetic kinetics and mechanism of
cyclohexene epoxidation catalyzed by metalloporphyrins. Chem. Eng.
J. 2010, 156 (2), 411-417.
Fukuzumi, S.; Lee, Y. M.; Nam, W., Catalytic recycling of NAD(P)H. J.
Inorg. Biochem. 2019, 199.
(a) Berijani, K.; Farokhi, A.; Hosseini-Monfared, H.; Janiak, C., Enhanced
enantioselective oxidation of olefins catalyzed by Mn-porphyrin
immobilized on graphene oxide. Tetrahedron 2018, 74 (18), 2202-2210;
(b) Chen, S. Y.; Zhou, X. T.; Ji, H. B., Insight into the cocatalyst effect of
4A molecular sieve on Sn(II) porphyrin-catalyzed B-V oxidation of
cyclohexanone. Catal. Today 2016, 264, 191-197; (c) Kameyama, H.;
Narumi, F.; Hattori, T.; Kameyama, H., Oxidation of cyclohexene with
molecular oxygen catalyzed by cobalt porphyrin complexes
immobilized on montmorillonite. J. Mol. Catal. A 2006, 258 (1-2), 172-
177; (d) Panwar, V.; Kumar, P.; Ray, S. S.; Jain, S. L., Organic inorganic
hybrid cobalt phthalocyanine/polyaniline as efficient catalyst for
aerobic oxidation of alcohols in liquid phase. Tetrahedron Lett. 2015,
56 (25), 3948-3953.
Jiang, J.; Luo, R. C.; Zhou, X. T.; Wang, F. F.; Ji, H. B., Metalloporphyrin-
mediated aerobic oxidation of hydrocarbons in cumene: Co-substrate
specificity and mechanistic consideration. Mol. Catal. 2017, 440, 36-
42.
(a) Jiang, J.; Wang, J. X.; Zhou, X. T.; Chen, H. Y.; Ji, H. B., Mechanistic
Understanding towards the Role of Cyclohexene in Enhancing the
Efficiency of Manganese Porphyrin-Catalyzed Aerobic Oxidation of
Diphenylmethane. Eur. J. Inorg. Chem. 2018, (23), 2666-2674; (b) Chen,
H. Y.; Lv, M.; Zhou, X. T.; Wang, J. X.; Han, Q.; Ji, H. B., A novel system
(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
Chin. J. Chem. 2019, 37, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
This article is protected by copyright. All rights reserved.

First author et al.
Report
Accepted manuscript online: XXXX, 2019
Version of record online: XXXX, 2019
www.cjc.wiley-vch.de
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

Entry for the Table of Contents
Page No.
Cyclohexene Promoted the Efficient Biomimetic
Oxidation of Alcohols to Carbonyl Compounds
Catalyzed by Manganese Porphyrin under Mild
Conditions
Xiao-Hui Liu, Hai-Yang Yu, Can Xue, Xian-Tai
Zhou,* Hong-Bing Ji*
A system comprising managenese porphyrin and cyclohexene for the biomimetic aerobic
oxidation of alcohols to carbonyl compounds was developed.
a Department, Institution, Address 1
E-mail:
c Department, Institution, Address 3
E-mail:
b Department, Institution, Address 2
E-mail:
Chin. J. Chem. 2018, template© 2018 SIOC, CAS, Shanghai,
&
WILEY-VCH Verlag GmbH
&
Co. KGaA,
Weinheim
This article is protected by copyright. All rights reserved.