Heterogeneous Sodium-Manganese Oxide Catalyzed Aerobic Oxidative Cleavage of 1,2-Diols

Article abstract of DOI:10.1002/anie.201705934

The aerobic oxidative cleavage of 1,2-diols using a heterogeneous catalyst only based on earth-abundant metals manganese and sodium is reported for the first time. This reusable catalyst cleaves a variety of substrates into aldehydes or ketones with high selectivity. The reaction requires small catalytic loadings and is performed under mild conditions using ambient pressure O₂ or air as the oxidant while producing water as the only by-product. Mechanistic investigations reveal a monodentate, two-electron oxidative fragmentation process involving a Mn^IV species. The eco-friendly, innocuous catalyst is compatible with a wide range of functional groups and conditions, making it highly competitive with classical reagents, such as periodic acid or lead tetraacetate, as a preferred method for activated 1,2-diols.

Full text of DOI:10.1002/anie.201705934

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Accepted Article
Title: Heterogeneous Sodium-Manganese Oxide Catalyzed Aerobic
Oxidative Cleavage of 1,2-diols
Authors: Vincent Escande, Chun Ho Lam, Philip Coish, and Paul T.
Anastas
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201705934
Angew. Chem. 10.1002/ange.201705934
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Heterogeneous Sodium-Manganese Oxide Catalyzed Aerobic
Oxidative Cleavage of 1,2-diols
Vincent Escande,*†[a,b] Chun Ho Lam†[a], Philip Coish[a], and Paul T. Anastas*[a][c]
Abstract: The aerobic oxidative cleavage of 1,2-diols using a
heterogeneous catalyst only based on earth abundant metals
manganese and sodium is reported for the first time. This reusable
catalyst cleaves a variety of substrates into aldehydes or ketones with
high selectivity. The reaction requires small catalytic loadings and is
performed under mild conditions using ambient pressure O2 or air as
the oxidant while producing water as by-product. Mechanistic
investigations reveal
a
monodentate, two-electron oxidative
fragmentation process involving a MnIV species. The eco-friendly,
innocuous catalyst is compatible with a wide range of functional
groups and conditions, making it highly competitive with classical
reagents such as periodic acid or lead tetraacetate as a preferred
method for activated 1,2-diols.
The oxidative cleavage of 1,2-diols to produce aldehydes or
ketones is an important transformation in synthetic organic
chemistry. Since its discovery in the early 20th century,[1] this
reaction has been employed in numerous applications ranging
from organic syntheses[2] to analytical studies in biochemistry.[3]
Recently, the oxidative cleavage of 1,2-diols has been employed
in biomass valorization for renewable feedstock production.[4]
However, despite human health and environmental concerns, the
reaction conditions continue to use the same archetypal reagents,
periodic acid and its salts, and lead tetraacetate. While these
reagents are known to be selective and efficient, their intrinsic
toxicities and safe disposal are non-trivial consequences,
questioned by sustainability standards.[5] Although several
protocols have been developed to address the aforementioned
challenges using chemically benign oxidant such as O2 or
hydrogen peroxide,[2a, 6] they either require toxic reagents or high
loadings of precious metals for the transformation. Driven by the
need for sustainable catalysts, metal-free protocols have been
reported recently,[7] as well as catalysts based on more abundant
metals, such as complexes of Fe,[8] Mn,[9] Ti,[10] and V.[11] However,
in addition to a frequent lack of selectivity, a critical drawback
persists as most of these catalysts are homogeneous and non-
recyclable. Therefore, development of a cost-effective, innocuous,
heterogeneous catalyst that enables a highly selective aerobic
oxidative cleavage of 1,2-diols is imperative.
Scheme 1. Comparing previous protocols with this work.
Our recent reports using catalysts prepared from Mn-rich plant
extracts[12] prompted us to investigate the utilization of a well-
defined heterogeneous Mn oxide catalyst for the oxidative
cleavage of 1,2-diols. Transition metal oxides have attracted
growing interest for the synthesis of small molecules. They
represent a major class of heterogeneous catalysts used in
industry.[13] Among them, manganese oxides are particularly
attractive for its abundance and low toxicity.[14] These materials
exist as a variety of structures, with unique catalytic properties in
a number of reactions.[15] In particular, in layered oxides such as
birnessite, edge-shared MnO6 units form
a lattice with
exchangeable oxygen molecules. Mn species exist in the lattice
as the mixed oxidation states MnII, MnIII and MnIV.[16] We
envisaged the coexistence of these different oxidation states and
the possibility of redox cycling with O2 would make Mn layered
mixed oxide a good candidate for the aerobic oxidative cleavage
of 1,2-diols as a heterogeneous catalyst. It is worth noting that
activated manganese dioxide has been described as an efficient
reagent for 1,2-diol oxidation but only with the use of a large
excess of reagent [40:1 ratio of reagent : substrate].[17] While this
amount of reagent has presumably disqualified the method as a
feasible protocol for large scale reactions, no catalytic version has
been proposed so far.
Herein, we describe an unprecedented protocol for aerobic
oxidative cleavage of 1,2-diols into aldehydes or ketones using
Mn layered mixed oxide (Mn LMO) as the catalyst (Scheme 1).
The absence of toxic solvents or reagents, the use of mild reaction
conditions and the ability to cleave a variety of 1,2-diols within
short reaction times by using O2 or air as oxidants are significant
advantages of the method. Most importantly, the catalyst is easily
[a]
[b]
[c]
Dr. V. Escande, Dr. C. H. Lam, Dr. P. Coish, Prof. Dr. P. T. Anastas
Center for Green Chemistry & Green Engineering, Yale University
New Haven, CT 06520 (USA)
E-mail: vincent.escande@yale.edu
Dr. V. Escande
Laboratory of Bio-Inspired Chemistry and Ecological Innovations
ChimEco, UMR 5021 CNRS-UM
34790 Grabels (France)
Prof. Dr. P. T. Anastas
School of Forestry and Environmental Studies, and Department of
Chemistry, Yale University
New Haven, CT 06511 (USA)
E-mail: paul.anastas@yale.edu
[†]
These authors contributed equally to this work.
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10.1002/anie.201705934
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prepared from inexpensive reagents and can be recycled multiple
times without losing activity which makes this approach
competitive with previous systems.
We prepared Mn LMO under mild conditions, adapted from a
previous protocol.[18] Oxidation of Mn2+ ions from MnCl2.4H2O with
hydrogen peroxide in presence of sodium hydroxide afforded the
corresponding catalyst which was isolated by filtration. Energy-
dispersive X-ray (EDX; Figure S1) spectroscopy revealed the
oxide nature of the material, and presence of Na along with Mn.
Further characterization by inductively coupled plasma atomic
Only 5% yield was obtained with commercial MnO2 and activated
MnO2, supporting the notion that the unique layered structure of
Na-Mn LMO was critical to catalytic activity (Table 1, entries 4-5).
Interestingly, a Na-birnessite similar to Na-Mn LMO but prepared
in less basic conditions gave a lower conversion (33%) than Na-
Mn LMO (Table 1, entry 6). While this result confirmed that a
layered structure was a key parameter for catalysis, it also
highlighted the importance of basicity during catalyst preparation.
The base influence on catalyst morphology and activity was
assessed by the preparation of catalysts within a range of NaOH
concentrations (in excess relative to the amount required for
oxidation of Mn2+ by H2O2). The resulting catalysts displayed
increasing activity with increasing NaOH concentration up to an
optimal concentration of 1.8 M (Table S3) while average size of
particles as measured by scanning electron microscopy (SEM)
decreased to 4.9 µm. However, when the concentration of NaOH
reached beyond this limit, average particle size increased
dramatically to over 30 µm along with an apparent decline in
catalytic activity (Figure 1a).
emission
spectroscopy
(ICP-AES;
Table
S1)
and
thermogravimetric analysis (TGA; Figure S2) indicated that the
material can be formulated as Na0.274MnO2∙6H2O, hereafter
referred to as Na-Mn LMO. Based on this composition, Mn is
present with an average oxidation state of ca. +3.7,[19] which was
confirmed by X-ray photoelectron spectroscopy (XPS; Figures S3
and S4). Whereas Na-Mn LMO appeared to be of low crystallinity,
its X-ray powder diffraction (XRPD; Figure S5) pattern showed
prominent (001) peaks suggesting that Mn oxide layers are
uniformly stacked in the birnessite phase with interlayered Na+
ions.[20] This is confirmed by Fourier transform infrared (FTIR;
Figure S6) spectroscopy which displayed a strong band at 400
cm-1, characteristic of layered Mn oxides.[21]
We evaluated the performance of our Na-Mn LMO material as a
catalyst for oxidative cleavage using meso-hydrobenzoin under
the atmospheric pressure of O2 in a model reaction. The
exploratory conditions and results are presented as
supplementary material in Table S2. The optimized reaction
conditions afforded the desired product, benzaldehyde, in high
yield. At 100 °C in 1-butanol, a 99% conversion with complete
selectivity toward benzaldehyde was obtained in 1 h, with only 1
mol% of Mn (Table 1, entry 1). A high turnover frequency (TOF)
of 180 h-1 at 100 °C was achieved in the initial hour (see SI). While
O2 gave the shortest reaction times, the same conversion was
obtained in air, in 4 h (Table 1, entry 2). Control experiment under
N2 confirmed the critical role of oxygen for the reaction (Table 1,
entry 3).
Figure 1. a) Influence of NaOH concentration used for Na-Mn LMO preparation
on its catalytic efficiency and on particles size. b) Influence of bases of different
strength on catalytic efficiency and on particles size. Reaction conditions for a)
and b) are the same than for Table 1, entry 1.
These observations are consistent with the known influence of
basicity on the crystallization of birnessite-materials.[22] Indeed,
when we examined a weaker base, tetramethylammonium
hydroxide (TMA∙OH) and stronger base, cesium hydroxide, we
observed an optimal yield with NaOH (Figure 1b). Here again,
SEM measurements showed that excessively high basicity
caused the crystallization of the material, resulting in the formation
of large particles (> 30 µm) with low catalytic activity (Figure S7).
Table 1. Oxidative cleavage of meso-hydrobenzoin catalyzed by Na-Mn LMO
and other Mn oxides.[a]
Using the most active form of Na-Mn LMO catalyst, a variety of
1,2-diols were readily cleaved under the optimized conditions
(Table 2). Although 1 mol% of Mn was sufficient to cleave these
substrates, we selected 10 mol% since it provided shorter
reaction times. Both cis and trans as well as symmetrical and
asymmetrical benzylic diols were cleaved efficiently (Table 2,
entries 1-5). The applicability of the method was illustrated by high,
isolated yields (up to 96%), after simple filtration then evaporation
of the solvent (Table 2, entries 1,3). Benzylic or allylic 1,2-diols
were the most reactive, but the method was also efficient on less
activated benzylic-aliphatic diols (Table 2, entries 5-6). In the
particular case of a non-substituted 1,2-diol such as 1f, the
reaction was slower and some degradation occurred after long
heating. However, addition of a base made the oxidative cleavage
possible. A screening of bases (Figure S8) revealed that the mild
base Na2CO3 was most effective. However, no reaction occurred
on diols substituted by two aliphatic moieties (Table 2, entries 13-
14), showing the catalyst was selective toward diols with a least
Entry
Catalyst
Atmosphere
t
Conversion
Selectivity
[%][b,c]
>99
>99
-
[h]
1
4
1
1
1
[%][b]
99
99
<1
5
1
2
3
4
5
Na-Mn LMO
Na-Mn LMO
Na-Mn LMO
MnO2
O2
air
N2
O2
O2
>99
>99
MnO2
5
(activated)
Na-
6
O2
1
33
>99
birnessite[d]
[a] Reaction conditions: meso-hydrobenzoin (42.9 mg, 0.2 mmol), catalyst
(1 mol% Mn), 1-butanol (1 mL), gas balloon, 100 °C. [b] Conversion and
selectivity were determined by GC using dodecane as internal standard.
Remaining mass balance is recovered starting materials. [c] Ratio of
benzaldehyde yield to conversion as a percentage. [d] Na-birnessite
prepared according to ref [18].
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10.1002/anie.201705934
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one activating substituent. The Na-Mn LMO catalyst cleaved
heterocyclic 1,2-diols with high efficiency (Table 2, entries 8-9),
sometimes with only 1 mol% of Mn, without any poisoning effect
of the heterocyclic atom. Moreover, reactions were unaffected by
the presence of electron- donating and withdrawing aromatic
substituents, consistently achieving complete conversion with
>99% selectivity (Table 2, entries 10-12). Interestingly, a test on
(S)-mandelic acid showed that the oxidative cleavage was also
possible on this -hydroxy acid, here again with a beneficial effect
of additional Na2CO3 (Table S4).
12
1
98
98
13
14
18
15
0
0
-
-
Table 2. Aerobic oxidative cleavage of 1,2-diols catalyzed by Na-Mn LMO.[a]
Substrate[b]
t
[h]
Product
Conv.
Yield
[a] Reaction conditions: substrate (0.2 mmol), Na-Mn LMO (10 mol% Mn), 1-
butanol (1 mL), O2 balloon, 100 °C. [b] Unless specified, the starting diols
bearing two stereogenic centers were used as variable mixtures of
diastereoisomers. [c] Determined by GC using dodecane as internal
standard, values between brackets correspond to isolated yields. Unless
specified, remaining mass balance is recovered starting materials. [d]
Reaction performed with 1 mol% Mn from Na-Mn LMO. [e] Remaining mass
balance was unidentified degradation products. [f] Reaction performed in
presence of Na2CO3 (0.4 mmol).
Entry
(%)[c]
(%)[c]
99
[96]
1[d]
1
1
99
93
2
93
In addition to substrate surveying, kinetic experiments were
devised to gain mechanistic insight. Interestingly, kinetic
comparison of meso- and (R,R)-hydrobenzoin cleavage revealed
the trans isomer, meso-hydrobenzoin, was cleaved faster than
the cis isomer, (R,R)-hydrobenzoin (Figure S9). Such observation
99
[92]
3[d]
1
100
disapproved the cyclic type I mechanism,[2a] where the opposite
trend would be expected.[17,
Moreover, in a cyclic type I
23]
mechanism, the reaction has usually second order (with order one
with respect to the substrate and one to the oxidant).[2a] However,
our initial rate kinetic study revealed the order with respect to
meso-hydrobenzoin to be zero (Figure S10), and displayed a
fractional order with respect to the oxidant (Figure S11). We
therefore postulate the cleavage proceeded through a type II
mechanism wherein an acyclic monodentate complex
intermediate was formed as shown in Scheme 2. In this
mechanism, the trans-diol would go through an antiperiplanar
geometry intermediate (see Scheme 2, A’) which would line up
both C-O sigma orbitals to facilitate the cleavage transition while
minimizing the steric hindrance from the phenyl groups.[24]
Although less common, the higher reaction rate of trans-diol
cleavage compared to its cis isomer has been observed and
accounted for with the mechanism described.[25] Based on this
monodentate type II mechanism, two scenarios were possible:
either a radical or a two-electron oxidative fragmentation.[2a] Such
mechanistic investigations were previously performed on CeIV
reagents with the same substrate, and the two mechanisms were
distinguished by addition of acrylamide for radical trapping.[26]
Since our experiments showed no difference in the presence or
absence of acrylamide (Figure S12), we therefore conclude that
the reaction catalyzed by Na-Mn LMO followed a type II
mechanism via two-electron oxidative fragmentation as proposed
in Scheme 2. This monodentate mechanism also supports the
beneficial role of Na2CO3 observed for less reactive substrates
(Table 2, entry 6), which fosters deprotonation of the A’
intermediate, as mentioned by Criegee et al for this pathway.[27]
The proposed catalytic cycle involves MnIV and MnII species, the
latter reoxidized by O2, forming H2O. The fractional order of O2
suggests reoxidation of MnII was part of the rate-determining step,
and also indicates a sequence of elementary steps, possibly
4
5
6
4
92
94
92
94
6
29
15[e]
19
83[f]
53[e,f]
7
1
97
97
8
4
1
94
99
94
99
9[d]
10
11
1
1
100
100
99
99
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10.1002/anie.201705934
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involving dissociation processes on the catalyst surface.[28] Thus,
current effort is devoted to investigate the reoxidation of MnII into
MnIV, on the catalyst surface.[29] Such understanding would
enable us to design the next generation of catalyst that could yield
comparable performance using air, which displays a lower rate
than pure O2 with our current Na-Mn oxide catalyst, as Table 1
shown.
easily prepared from inexpensive and abundant metals. This
catalyst affords the products in short reaction times, under mild
conditions and with facile work-up, and can be reused several
times without loss of activity. The absence of precious metals,
toxic solvents and reagents, the use of O2 or air in atmospheric
conditions with H2O as only by-product, make this catalyst more
appealing for the cleavage of activated 1,2 diols to any previously
reported systems. This method excels at handling benzylic 1,2-
diols, cleaved in excellent yields (92-99%), with high selectivity
(>99%). Mechanistic investigations revealed a monodentate, two-
electron oxidative fragmentation, involving MnIV as the oxidizing
species. Finally, we applied this system in several domino
reactions, showing the compatibility of the catalyst with different
conditions to demonstrate its value as a powerful synthetic tool.
Acknowledgements
V.E. is grateful for support from French National Center for
Scientific Research (CNRS). C.H.L would like to thank the
Donnelley Environmental Foundation for his fellowship support.
Dr. Stephen Golledge from University of Oregon and Jinyang Li,
from Prof. Dr. André Taylor’s group at Yale University, are
acknowledged for assistance with XPS and TG analysis,
respectively. Dr. Sara Hashmi at the Facility for Light Scattering
at Yale University is acknowledged for her assistance and
instrumentation support.
Scheme 2. Proposed mechanism for the reaction.
As the heterogeneous nature of the catalyst was a key attribute,
it was assessed by the removal of the catalyst before the reaction
was complete by simple filtration. Analysis of the reaction mixture
showed no further conversion after removal of the catalyst (Figure
S13). The recyclability of Na-Mn LMO catalyst was also confirmed.
It was isolated, washed with ethanol and dried at 105 °C for 2 h
before being reused (Figure S14). The catalyst was employed in
6 successive runs without any loss of activity.
Keywords: aerobic oxidation • cleavage reactions • diol •
heterogeneous catalysis • manganese
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Entry for the Table of Contents
COMMUNICATION
V. Escande,* C.H. Lam, P. Coish,
P.T. Anastas*
Catalytic scissors: A reusable
heterogeneous catalyst, easily
prepared from earth abundant
elements Na and Mn, cleaved 1,2-
diols by using atmospheric O2 as
sole oxidant and forming only water
as by-product. Aldehydes or
ketones are formed with high yield
and selectivity, making this eco-
friendly method a competitive
alternative to classical reagents.
Page No. – Page No.
Heterogeneous Sodium-
Manganese Oxide Catalyzed
Aerobic Oxidative Cleavage of 1,2-
diols
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