Efficient Oxidation of Benzylic and Aliphatic Alcohols Using a Bioinspired Cross-Bridged Cyclam Manganese Complex with H2O2

Article abstract of DOI:10.1002/ejoc.201801140

The cross-bridged cyclam manganese complex Mn(Me₂EBC)Cl₂ efficiently catalyzes the oxidation of benzylic and aliphatic alcohols at pH 3 in a mixture of acetonitrile and water at room temperature. The environmentally benign and high oxygen content oxidant H₂O₂ was adopted. Conversions of the alcohols to the corresponding carbonyl compounds reached 98 % with good to excellent selectivity. In addition, several lignin model compounds were also catalytically oxidized under these conditions, with excellent conversion (up to 96 %) and selectivity (up to 99 %).

Full text of DOI:10.1002/ejoc.201801140

A Journal of
Accepted Article
Title: Efficient oxidation of benzylic and aliphatic alcohols using a
bioinspired, cross-bridged cyclam manganese complex with
H2O2
Authors: Zhan ZHANG, Lhoussain KHROUZ, Guochuan YIN, and
Bruno ANDRIOLETTI
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201801140
Link to VoR: http://dx.doi.org/10.1002/ejoc.201801140
Supported by

European Journal of Organic Chemistry
10.1002/ejoc.201801140
FULL PAPER
Efficient oxidation of benzylic and aliphatic alcohols using a
bioinspired, cross-bridged cyclam manganese complex with H
2
O
2
[a]
[b]
[c]
[a]
Zhan Zhang, Lhoussain Khrouz, Guochuan Yin, and Bruno Andrioletti *
Abstract: The cross-bridged cyclam manganese complex
Mn(Me EBC)Cl efficiently catalyzes the oxidation of benzylic and
proven very efficient for the catalytic oxidation of benzyl alcohols,
and for some lignin model compounds, in the presence of
(diacetoxyiodo)benzene.[7] With biomimetic manganese-based
catalysts, Shen et al. reported that the complex Mn(S-
2
2
aliphatic alcohols at pH 3 in a mixture of acetonitrile and water at room
temperature. The environmentally benign and high oxygen content
oxidant H O
2 2
was adopted. Conversions of the alcohols to the
3 3 2
PMB)(CF SO ) (Figure 1. e, S-PMB) efficiently oxidizes a large
corresponding carbonyl compounds reached 98% with good to
excellent selectivity. In addition, several lignin model compounds were
also catalytically oxidized under these conditions, with excellent
conversion (up to 96%) and selectivity (up to 99%).
range of secondary alcohols to the corresponding ketones with
hydrogen peroxide in the presence of acetic acid.[7] A manganese
complex based on the BQEN ligand (Figure 1. f), was also proven
to efficiently promote the oxidation of alcohols with peracetic acid
as the oxidant.[9] The catalytic oxidation of alcohols by other non-
haem complexes was also investigated.[10]
Introduction
The oxidation of alcohols is an important transformation in organic
synthesis that can be achieved by various methods such as
chromium-based oxidation, TPAP or Swern oxidations or using
periodiane derivatives as the resulting products (aldehydes,
carboxylic acids or ketones) are key intermediates for the
[1,2]
chemical industry.
However, most of the aforementioned
transformations display a very poor environmental impact
because heavy and toxic metals and/or multi component systems
are often used.
Conversely, metalloenzymes exhibit generally high efficiency and
selectivity for some specific substrates under very mild
conditions.[ As the development of sustainable oxidation
3]
[
4]
conditions remain highly challenging, substantial efforts have
been made to develop biomimetic oxidation reactions, using
environmentally benign metals (e.g. manganese and iron) and
oxidants (e.g. dioxygen and hydrogen peroxide). Consequently, a
large variety of bio-inspired catalysts have been synthesized and
applied for the catalytic oxidation of alcohols during the past
decades. Hence, Sekino et al.[5] reported that a µ-peroxo
Figure 1. Examples of bio-inspired ligands used for the catalytic oxidation of
alcohols.
During the course of our studies on the development of
environmentally benign oxidation of alcohols, we selected the
manganese(II) complex containing a cross-bridged cyclam ligand
Mn(Me
previously
transfer,
2
2
EBC)Cl (Figure 2), which had been fully characterized
diiron(IV)
Fe
(LPh4)(O
complex
)(Ph CCO
generated
in
situ
from
[11]
and used for hydrogen abstraction,[12] oxygen
[
2
2
3
2
)]2+ (Figure 1. a, LPh4
=
N,N,N',N'-
[13]
C-H bond activation[14] and some other applications.[15]
tetrakis(1-methyl-2-phenyl-4-imidazolyl)methyl-1,3-diamino-2-
propanolate) with a dinucleating ligand could catalyze the
oxidation of benzyl alcohol with dioxygen. Similarly, Nam et al.
investigated the oxidation of benzyl alcohol by oxoiron(IV)
Herein, we disclose that Mn(Me
oxidation of a series of benzylic and aliphatic alcohols (including
lignin model compounds) with 35% H 2(aq) as a green oxidant at
pH= 3 in a mixture of acetonitrile and water at room temperature.
2 2
EBC)Cl efficiently catalyzes the
2
O
4
complexes based on non-haem ligands such as N Py (Figure 1.
b) and TPA (Figure 1. c) and revealed detailed mechanistic
insights.[6] The Fe-TAML iron complex (Figure 1. d, TAML) was
[
a]
Univ Lyon, Université Claude Bernard Lyon 1, ICBMS-UMR 5246,
Campus Lyon-Tech la Doua, Bât. Curien/CPE, 43 Boulevard du 11
Novembre 1918, 69622 Villeurbanne, France. E-mail:
bruno.andrioletti@univ-lyon1.fr
2
Figure 2. Structure of cross-bridged cyclam Me EBC and the corresponding
manganese(II) complex.
http://www.icbms.fr/casyen/research/andrioletti
[
[
b]
c]
Univ Lyon, Ecole Normale Supérieure de Lyon, Laboratoire de
Chimie, UMR-CNRS 5182, 46 allée d'Italie, 69364 Lyon 07, France.
School of Chemistry and Chemical Engineering, Huazhong
University of Science and Technology, Wuhan 430074, PR China;
Key laboratory of Material Chemistry for Energy Conversion and
Storage (Huazhong University of Science and Technology), Ministry
of Education, PR China.
Results and Discussion
Veratryl alcohol being a common model substrate for studying the
[16]
oxidative degradation of lignin, it was chosen for determining
2 2
the optimal conditions, using Mn(Me EBC)Cl as the catalyst and
Supporting information for this article is given via a link at the end of
the document
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European Journal of Organic Chemistry
10.1002/ejoc.201801140
FULL PAPER
H
2
O
2
as the oxidant at different pH values (Table 1). In agreement
By taking into account the efficiency, the selectivity and the cost-
effectiveness of the transformation, we selected the conditions
used in the entry 4, namely 0.5 mol% of catalyst and 4 equivalents
of oxidant as the best compromise.
[
8-9, 17]
with preliminary observations,
we found that at pH 1, 2 or 3,
the conversion of veratryl alcohol was quantitative affording the
corresponding aldehyde and acid in up and to 80% and 12% yield,
respectively, in the presence of 1 mol% of catalyst and 4 eq. of
2 2
H O in 4 hours (Table 1, entries 1‒3). Conversely, at higher pH,
the conversion dropped significantly to 51% at pH 4 and 22% at
pH 5 (Table 1, entries 4-5). Therefore, we could infer that at pH >
Table 2. Oxidation of veratryl alcohol with different amounts of
II
2 2
Mn (Me EBC)Cl and oxidant.
3, the reactivity decreases. Due to the better selectivity observed
at pH 3 and relatively milder conditions, we fixed the working pH
at 3.
Entry
Amount of
catalyst
/mol%
Amount
of H O /
eq.
Conversion
/%
Yield of
aldehyde
/% [
Yield
of
2
2
a]
II
acid
Table 1. Oxidation of veratryl alcohol with Mn (Me
different pH.
2
EBC)Cl
2
and H
2
O
2
at
a]
/
%[
1
2
3
4
5
6
7
8
0
0.1
0.3
0.5
1
4
4
4
4
4
1
2
3
9
5
0
1
36
75
89
99
77
89
95
28
61
76
80
61
68
75
Entry
pH
Conversion
%)
Yield of
Yield of acid
(%)[
3
a]
(
aldehyde
a]
(
%)[
7
1[b]
2
1
2
3
4
5
3
3
99
98
99
51
22
98
99
72
70
80
47
19
83
81
11
12
12
0
12
1
1
3
1
3
4
1
9
5
0
[
3 2
a] GC yields. Conditions: solvent CH CN/ H O: 5 mL (4:1) substrate 100
II
6[c]
mM, Mn (Me
2
EBC)Cl
2
, H
O
2 2
, pH 3, 303 K, 4 h. pH adjusted with HCl.
9
7[d]
11
[
a] GC yields. Conditions: solvent CH
3
CN/ H
0.17 mL 4eq., 303 K, 4 h, pH: adjusted
with HCl. [b] 3 h; [c] pH adjusted with H SO ; [d] pH adjusted with HNO
2
O: 5 mL (4:1), substrate 100
II
2 2 2 2
mM, Mn (Me EBC)Cl 1 mol%, H O
2
4
3
.
1
00
9
8
0
0
In addition, we studied the influence of the chloride counter anion.
Hence, H SO and HNO were also investigated for adjusting the
working pH at 3. In the presence of H SO or HNO , both the
2
4
3
70
2
4
3
6
5
0
0
conversions and the yields were similar to that determined in the
presence of HCl (Table 1, entry 6 ‒ 7). Accordingly, contrary to
former reports from the literature revealing that the nature of the
counter-anion could accelerate the alcohol oxidation,[8,10e,18] in our
Conversion/%
Yield of a./%
Yield of b./%
40
30
20
10
0
-
-
conditions, the nature of the counter anion (i.e. Cl vs. HSO
4
or
-
NO
3
) did not affect significantly the outcome of the reaction.
Next, we investigated the effect of the catalytic charge and the
optimal amount of H at pH 3 at 30°C (Table 2). Firstly, a control
experiment carried out with H only confirmed that the
2
O
2
0
1
2
3
4
5
6
7
Time / h
2
O
2
manganese catalyst was crucial in the transformation (Table 2
entry 1). Entries 2 to 5 reveal that the conversions improve
dramatically from 36 to 99% when increasing the amount of
catalyst from 0.1 to 1 mol%. Hence, a minimum catalytic charge
of 0.5 mol% appeared necessary for ensuring the efficient
conversion of the substrate. On this basis, we also investigated
the effect of the amount of oxidant (Table 2, entries 5 ‒ 8). With 3
II
Figure 3. Kinetics of the oxidation of veratryl alcohol with Mn (Me
2 2
EBC)Cl in
the presence of H
2 2
O . Conditions: solvent CH
3 2
CN and H O 5 mL (4:1), substrate
EBC)Cl 0.5 mol%, H 0.17 mL, pH 3, 303 K, pH adjusted
II
100 mM, Mn (Me
with HCl.
2
2
2 2
O
The effect of the reaction time was also investigated (Figure 3).
When the reaction was run for 6 hours, the conversion went up to
2 2
or 4 equivalents of H O , conversions were excellent, up to 99%.
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European Journal of Organic Chemistry
10.1002/ejoc.201801140
FULL PAPER
9
9% but at the expense of the selectivity. Indeed, upon running
compound could not be transformed to the corresponding
aldehyde or acid in more than 86% conversion even after 18 h
(Table 3, entry 2). The relative position of the substituent did not
appear crucial either, as the ortho-methoxy benzyl alcohol
analogue produced the corresponding aldehyde and acid in
similar range (Table 3, entry 3). The benzyl alcohol was proven
even less reactive as after 6 h the conversion remained in the
40% range and reached 78% after 18 h (Table 3, entry 4).
However, this decent conversion was obtained at the expense
of the selectivity as benzoic acid was produced in substantial
amount.
the reaction for an additional 2 hours (from 4 to 6 h), the selectivity
went down from 9/1 to 5/1. Hence the quantity of aldehyde is
maximized after 5 h before slowly decreasing upon oxidation to
the corresponding acid.
In conclusion, this preliminary study reveals that the optimal
conditions for oxidizing veratryl alcohol to the corresponding
aldehyde involves the use of 0.5 mol% of catalyst, 4 equivalents
of H
2 2
O and a 5 h reaction at pH 3 and 303 K, knowing that the
maximum conversion is reached after 6 h.
II
2 2
Table 3. Oxidation of different types of alcohols with Mn (Me EBC)Cl and
H O .
2 2
When secondary benzylic alcohols were subjected to oxidation
(
Table 3, entries 5 ‒ 6), the corresponding ketone was isolated
in good yield (63%) in the case of the methyl ketone but a
relatively long reaction time was proven necessary. However,
the diphenylmethanol was more reluctant to oxidation, as the
expected ketone was isolated in 32% yield, even after a
prolonged reaction time (Table 3, entry 6). Similarly, aliphatic
alcohol displaying a long alkyl chain such as 1-octanol (Table 3,
entry 7) appeared little reactive under our conditions.
Interestingly, cyclohexanol was converted much more efficiently
and cyclohexanone was isolated in a decent 60% yield (Table
En
try
Substrate
Conv.
(%)
Aldehyde
or ketone
Y.
Acid
Y.
(%) [
a]
(%)
[
a]
1
2
98
69
77
15
(6)
68
79)
(
3, entry 8).
(86)
3
73
69
(81)
(6)
In contrast, very high conversions and selectivities were
obtained with 1,2-cyclohexanediol (Table 3, entry 9) and 1,2-
diphenyl-ethane-1,2-diol (Table 3, entry 10). In the latter cases,
the corresponding mono-ketones were obtained in quantitative
yields. Interestingly, even in the presence of a larger excess of
(89)
4
5
6
40
37
(59)
(11)
(78)
2 2
H O (8 equiv. vs. 4 equiv.) the mono-ketones were not oxidized
42
39
(63)
further. This observation is in agreement with the former
observation regarding the higher reactivity of electron rich
alcohols. Hence, an excellent selectivity can be reached in the
case of 1,2-diols. For this reason, we investigated the oxidation
of lignin model compounds that could be of prime interest for
understanding the reactivity of lignin. As in lignins, the 훽-O-4
moieties are the most abundant,[ we decided to investigate a
classical 훽-O-4 model (Table 3, entry 11). Using our optimized
conditions, the desired ketone was isolated in a moderate 56%
yield, but with an excellent selectivity. For this reason, we decide
to harden the reaction conditions by doubling the amount of
(63)
(32)
(32)
7
8
9
(24)
(60)
100/
(11)
(60)
99/
(12)
19]
b]
[b]
1
00[
99
1
0
1
95/
95/
[
b]
[b]
95
95
2 2
catalyst (1 mol%) and H O (8 equiv.). In these conditions, we
1
58/
56/
were delighted to observe that in these conditions the
conversion increased dramatically to 96% while maintaining an
excellent selectivity (99%). Using the same conditions, we
evaluated the reactivity of a 훽-1 lignin model compound (Table
9 [
b,c]
[b,c]
6
95
12
98
68
29
3, entry 12). After 6 h, the conversion of the starting material
was almost complete, but a mixture of mono-ketone and dione
was isolated. The mono- and diketone were isolated in 68 and
2
9% yield, respectively. Interestingly though, no C-C bond
[
a] GC yields. Conditions: solvent CH
3
CN/ H
0.17 mL 4eq., pH 3, 303 K, 6 h. [b] H
1 mol%; Data in brackets: 18 h.
2
O: 5 mL (4:1) substrate 100 mM,
II
cleavage was observed. These promising results suggest that
the combination of Mn (Me EBC)Cl and H O may constitute
Mn (Me
0
2
EBC)Cl
.34 mL 8 eq.; [c] Mn (Me
2
0.5 mol%, H
2
O
2
2 2
O
II
II
2
EBC)Cl
2
2
2
2
2
an alternative for the valorization of lignin, a bio-source of
aromatic compounds.[19b]
On the basis of these preliminary studies, we investigated the
effect of the substitution on the alcohol (Table 3). As expected,
the electron richness of the alcohol seems to be the major
parameter of the transformation. Indeed, if the veratryl alcohol
was converted to the corresponding aldehyde and acid in 98%
in 6 h (Table 3, entry 1), the para-methoxy benzyl alcohol
lacking one -OMe group in comparison with the parent
In order to gain some insights on the mechanism of the reaction,
we first investigated the possible presence of radical
intermediates. As t-BuOH is an acknowledged radical
scavenger,[20] we decided to perform the oxidation of veratryl
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European Journal of Organic Chemistry
10.1002/ejoc.201801140
FULL PAPER
alcohol in a t-BuOH/H
2
O (4:1) solvent mixture. In these solvent
Mn(Me
corresponding
Mn(Me EBC)(OH)
2
EBC)Cl
2
was kindly provided by Prof. Guochuan Yin. The
conditions, veratryl alcohol was converted in 67% and afforded
veratraldehyde in 65% yield. Hence, this result accounts for a
mechanism precluding the presence of hydroxyl radicals.[15, 20]
manganese(IV)
compound,
2
2
4
(PF )
2
was synthesized according to a known
10,22a
procedure from the literature.
All the chemical reagents used
were commercially available except for lignin model compounds,
which were synthesized and characterized before in our group.6
Alternatively, we confirmed the absence of hydroxyl radical
intermediates using EPR measurements (see Supporting
Information Section). Knowing that DMPO (5,5-dimethyl-1-
pyrroline-N-oxide) traps radicals affording a DMPO radical
General procedure for the oxidation of alcohols using
Mn(Me EBC)Cl in the presence of H O .
2 2 2 2
Under Ar, a 25 mL round bottom flask was charged with
acetonitrile (4 mL) and water (1 mL) before the pH was adjusted
at 3 with HCl. Next, the substrate (100 mM) and 0.5 mol% of
[12, 21]
adduct (that displays a typical four-line EPR spectra)
added DMPO to our experimental conditions and followed the
reaction using EPR. However, upon adding H to a solution
we
2
O
2
of Mn(Me
2
EBC)Cl
2
and DMPO at pH 3, only the EPR signal of
2 2 2 2
Mn(Me EBC)Cl , 0.17 mL or 0.34 mL of 35% of H O aqueous
residual Mn(II) (g~2 aMn~90G), was visible.[
22]
Hence, this
solution (35%) and diphenyl ether as the internal standard were
added. The reaction was kept under vigorous stirring for 6 h or 18
h at 303 K in a water bath. Next, the solution was extracted with
dichloromethane. After drying, the organic phase was analyzed
by GC/MS.
observation confirmed the absence of hydroxyl radicals in our
reaction conditions.
After excluding a radical-mediated oxidation, we investigated the
possibility that a highly oxidized Mn species was responsible for
The kinetic follow-up was carried out according to the same
protocol, but aliquots were taken every hour.
the catalytic performance. To this end we synthesized the pure
IV
Mn (Me
2
EBC)(OH)
2
(PF
6
)
2
metallocomplex from Mn(Me
2
EBC)Cl
2
Experiment protocol for hydroxyl radical trapping with t-
BuOH.
The protocol for this reaction was the same as the one described
above but MeCN (4 mL) was replaced by t-BuOH (4 mL).
[
23]
using a known procedure.
In the absence of any oxidant,
veratryl alcohol was oxidized rather efficiently by a stoichiometric
amount of the manganese(IV) complex as the expected aldehyde
and acid were isolated in 22 and 7% yield, respectively with a
conversion of 40%. This result demonstrates that
Stoichiometric oxygenation of veratryl alcohol with
manganese(IV) complexes.
IV
Mn (Me
2
EBC)(OH)
2
(PF
6
)
2
is able to oxidize veratryl alcohol even
at
2
EBC)Cl is oxidized generating the
2 2
in the absence of any oxidant. Hence, in the presence of H O
5
mL of the mix solvent containing acetonitrile (4 mL) and water
pH 3, Mn(Me
2
(
1 mL) at pH 3 (pH adjusted with HCl) was charged with 1 mM of
IV
2+
IV
Mn (Me
2
EBC)(OH)
2
. Next, the Mn intermediate can directly
substrate, 1 mM of Mn(IV) complex and diphenyl ether. The
reaction was kept stirring for 6 h at 303 K in a water bath. The
conversion and the yields were detected by GC/MS using the
internal standard method.
oxidize a molecule of alcohol through hydrogen atom abstraction
or through or the transfer of a hydroxyl as already observed in the
literature.[22a, 24]
.
Conclusions
In conclusion, we have developed an efficient catalytic system
Acknowledgements
from a bioinspired manganese(II) complex Mn(Me
2 2
EBC)Cl and
an environmentally benign oxidant H at pH 3. This new
2
O
2
The China Scholarship Council (CSC) is deeply acknowledged for
providing financial support to ZZ. The University Claude Bernard
Lyon 1 and the CNRS are also acknowledged for their support.
catalytic system displays a high efficiency for the oxidation of a
variety of benzylic alcohols and some aliphatic alcohols. More
interestingly, it was proven very powerful for the oxidation of lignin
model compounds. In particular, 훽-O-4 lignin model molecule was
converted almost quantitatively to the corresponding ketone
Keywords: Green oxidation • Manganese complex • cyclam •
lignin models • benzyl alcohols
without C-C bond cleavage. In addition, a mixture of H
MeCN was used at the expense of acetone and advantageously
precluded the possible oxidation of acetone with H . Substrates
2
O and
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O
2
displaying electron enriched alcohols were proven more reactive
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unsymmetrical 1,2-diols. At last, we have proven that the
oxidation process does not involve any radical and most likely
relies on a high valent manganese(IV) complex. Additional
investigations are currently underway in our Laboratory in order
to totally ascertain the mechanism of oxidation.
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European Journal of Organic Chemistry
10.1002/ejoc.201801140
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Sustainable oxidation of benzyl
alcohols
Zhan Zhang, Lhoussain Khrouz,
Guochuan Yin, and Bruno Andrioletti*
Page No. – Page No.
Efficient oxidation of benzylic and
aliphatic alcohols using a
bioinspired, cross-bridged cyclam
2 2
manganese complex with H O
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