Selective catalytic oxidation of diglycerol

Article abstract of DOI:10.1039/d0gc03239e

The selective oxidation of α,α-diglycerol was studied using oxygen as a clean oxidant in the presence of a palladium/neocuproine complex. After optimization of the reaction parameters, the mono-oxidation product was obtained with 93% NMR yield (up to 76% isolated yield). The product was named “diglycerose” considering that it mainly exists as a cyclic hemi-ketal form.

Full text of DOI:10.1039/d0gc03239e

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Selective catalytic oxidation of diglycerol†
a
a
b
a
Cite this: Green Chem., 2021, 23,
154
Huan Wang, Nam Duc Vu, Guo-Rong Chen, Estelle Métay,
a
a
1
Nicolas Duguet * and Marc Lemaire
*
Received 24th September 2020,
Accepted 21st January 2021
DOI: 10.1039/d0gc03239e
rsc.li/greenchem
The selective oxidation of α,α-diglycerol was studied using oxygen
Diglycerol is a derivative of glycerol that is formally the
as a clean oxidant in the presence of a palladium/neocuproine result of the condensation of two molecules of glycerol. It is
1
9
complex. After optimization of the reaction parameters, the mono- mainly prepared by direct oligomerization of glycerol.
oxidation product was obtained with 93% NMR yield (up to 76% Diglycerol can be directly used as a monomer for the prepa-
2
0
isolated yield). The product was named “diglycerose” considering ration of polyesters. Moreover, it can be converted to digly-
2
1
that it mainly exists as a cyclic hemi-ketal form.
cerol dicarbonate (DGDC), that is further used as a building-
2
2
block for the synthesis of polyhydroxyurethanes (PHUs).
Diglycerol-based surfactants can be also produced such as
The transformation of renewable biomass to added-value com-
pounds is currently the subject of intense research efforts.
1
23
24
18
diglycerol esters, acetals, and ethers. Other ether deriva-
Biomass represents an important reservoir of polyols as it is
mainly composed of starch, cellulose, hemi-cellulose, sucrose,
25
tives can be also prepared by dehydrogenative arylation or
26
permethylation
respectively.
to give hydrotropes and solvents,
1
,2
and many more oxygenated compounds. Even triglycerides,
which exhibit a low oxygen content, are incorporating a polyol
as a linker of fatty chains. Transesterification of triglycerides,
extracted from vegetable oils, affords fatty acid methyl esters
The selective oxidation of polyols, especially those incorpor-
ating a 1,2-diol motif, provides α-hydroxyketones, that are
encountered in natural products and serve as useful synthetic
intermediates. The oxidation of 1,2-diols to α-hydroxyketones
is a challenging task considering that many byproducts (e.g.,
,2-diketones, aldehydes, carboxylic acids) could be formed by
over-oxidation and C–C cleavage. Some selective methods were
first reported using stoichiometric oxidants such as dioxiranes
3
that are used as either biodiesel, starting materials for oleo-
27
4
5
chemicals or biopolymers. Glycerol is obtained as the main
coproduct of the methanolysis of vegetable oils and is valor-
ized along its own value chain. It could be directly used as a
1
6
renewable solvent or as a monomer for the production of bio-
28
7
based polyesters. Glycerol is also an excellent platform mole-
29
30
2
or Br .
Catalytic methods were also developed based on Ru-
8
cule to prepare a wide range of biobased chemicals such as
31
and Ni-catalyzed dehydrogenation. Particularly, Waymouth
et al. have reported a highly selective catalytic method for the
oxidation of glycerol to dihydroxyacetone with a palladium/neo-
cuproine complex using hydroquinone as an oxidant. The
method was further developed using oxygen (or air) and applied
9
10
11
8
acrolein, glyceric acid, 1,2-propanediol, among others.
1
2
Moreover, it can be transformed to glycerol carbonate, solke-
1
3
14
tal and 1,2,3-trimethoxypropane, that serve as biobased sol-
32
1
5
vents. Glycerol can also be used as a polar head in the prepa-
1
6
17
ration of renewable surfactants based on esters, acetals or
33
34
35
to erythritol and other polyols, and even carbohydrates.
1
8
ethers. In contrast, the chemistry of diglycerol is compara-
tively under-developed.
However, to the best of our knowledge, the selective catalytic
oxidation of diglycerol has never been reported.
In this context, we report here a selective catalytic method
for the mono-oxidation of diglycerol using oxygen as a clean
oxidant.
a
Univ Lyon, Université Claude Bernard Lyon 1, CNRS, INSA-Lyon, CPE-Lyon, Institut
de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), UMR CNRS
5
246, Bâtiment Lederer, 1 rue Victor Grignard, F-69100 Villeurbanne, France.
Diglycerol is usually produced by oligomerization of gly-
19
E-mail: nicolas.duguet@univ-lyon1.fr
cerol, resulting in the formation of 3 main isomers. The pro-
portion of each isomer in commercially available diglycerol
was found to be ∼80% for α,α-isomer, ∼20% for α,β-isomer
b
East China University of Science and Technology, Key Laboratory for Advanced
Materials & Institute of Fine Chemicals, School of Chemistry and Molecular
Engineering, 130 Meilong Road, Shanghai 200237, P. R. China
1
3
and <1% for β,β-isomer, as determined by C NMR. The oxi-
dation of diglycerol already offers a great challenge in term of
†
Electronic supplementary information (ESI) available. See DOI: 10.1039/
d0gc03239e
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regioselectivity but also in term of mono- versus multiple oxi- dation product 6. Increasing the temperature to 80 °C did not
dations. So, in order to have a simpler model for oxidation of improve the results. On the contrary, very low yields were
diglycerol, the purification of the crude starting material was obtained under these conditions. This was attributed to the
carried out through the formation of α,α-diglycerol dicarbo- catalyst deactivation with the formation of Pd(0) aggregates,
3
6
38
nate 2 (Fig. S1 in ESI†).
i.e. “Pd black”.
1
The selective mono-oxidation of the α,α-isomer of diglycerol
From the H NMR spectrum, it was found that the expected
α,α-1 was performed with palladium-based catalysts using product 3 exists as an open and a cyclic form, representing 7
oxygen as a clean oxidant in acetonitrile/water (10 : 1) at 30 °C and 93%, respectively (Scheme 1). Indeed, compound 3
(
Table 1). First, no oxidation product was obtained when using cyclizes to form a six-membered ring as a single diastereo-
either a mixture of Pd(OAc) and neocuproine Pd-1 or a pre- isomer. The relative cis configuration between the two hydroxy-
formed Pd(OAc) /neocuproine complex Pd-2 (Table 1, entries methyl groups was determined by NMR analyses after derivati-
2
3
7
2
1
and 2). In these two cases, the starting material was recov- zation (see ESI†). The formation of a seven-membered ring
ered unaltered. system has not been detected, such product being usually
These results were somewhat surprising since the same cat- highly disfavored. Product 3 has been named “diglycerose”
alysts gave good results for the oxidation of glycerol 4 and the due to its structural similarities with ketoses.
corresponding dihydroxyacetone 5 was obtained with 41 and
Next, various solvents were screened. The temperature was
6
0% yield, respectively (Table 1, entries 1 and 2). With Pd-3 set at 50 °C to limit the formation of palladium black and the
3
8
complex, prepared following a reported method, only trace time was limited to 2 hours to avoid the formation of the bis-
amounts (<5%) of the mono-oxidation product of diglycerol oxidation product 6 (Table 2). First, repeating the reaction in
was observed (Table 1, entry 3). Once again, the same catalyst CH CN/H O (7 : 1) in 2 hours gave only 5% yield (Table 1, entry
3
2
performed very well for the oxidation of glycerol and dihydrox- 1). Protic polar solvents such as MeOH and EtOH did not lead
yacetone 5 was obtained with 90% yield (Table 1, entry 3). to any conversion of the starting material. Ethereal solvents
From these results, it is striking to see that the reported palla- were next screened. No reaction was obtained when using
dium-based catalysts exhibit good catalytic activities for the CPME and 2-MeTHF while the product was formed in THF
oxidation of glycerol while they are completely ineffective for and 1,4-dioxane with 31 and 43% yield, respectively (Table 1,
diglycerol. We hypothesized that the poor solubility of digly- entries 2–5). Then, fluorinated solvents were tested as they are
3
9
cerol under the chosen reaction conditions was responsible for known to well dissolve oxygen. (Trifluoromethyl)benzene was
the poor conversion. first used but no reaction was observed (Table 1, entry 6).
To solve this problem, the proportion of water was Satisfyingly, when using TFE and HFIP, diglycerose 3 was
increased to promote the dissolution of diglycerol and CH CN/ obtained with 54 and 74%, respectively (Table 1, entries 7 and
O (v/v 7 : 1) was selected as solvent system for further optim- 8). The success of HFIP has been reported in numerous
3
H
2
4
0
ization. Then, the temperature was gradually increased from occasions
in homogeneous catalysis using transition
4
1
42
3
7
0 to 80 °C (Fig. S2 in ESI†). The best result was obtained at metals, notably in CH activation. In our case, the use of
0 °C with an isolated yield of 27% for the mono-oxidation HFIP could increase the oxygen solubility but it could also
product 3, accompanied with about 11% yield of the bis-oxi- increase catalyst lifetime. Indeed, Waymouth has shown that
phenol derivatives can increase the lifetime of Pd/neocuproine
3
8
complexes. So, considering that HFIP exhibits a similar pK
a
a
Table 1 Oxidation of (di)glycerol with palladium-based catalysts
(9.3) as phenol, it is likely that it also helps to prevent the cata-
lyst degradation.
Consequently, HFIP was selected for further optimization
(
Table 3). Increasing the oxygen pressure to 3 and 6 bar, led to
a complete conversion and diglycerose 3 was obtained with 89
b
b
Entry
Catalyst
Yield of 3 (%)
Yield of 5 (%)
1
2
3
Pd-1
Pd-2
Pd-3
0
0
41
60
>90
Trace
a
Reaction conditions: α,α-Diglycerol or glycerol (0.45 mmol), palla-
(1 bar), CH CN/H O (v/v
0 : 1, 5.5 mL), 30 °C, 24 h. Yields were determined by H NMR.
dium-based catalyst Pd1–3 (10 mol%), O
1
2
3
2
b
1
Scheme 1 Mono-oxidation product of diglycerol.
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a
Table 2 Oxidation of α,α-diglycerol in different solvent systems
under 3 or 6 bar of oxygen. Under these conditions, compound
3
was obtained with 66 and 63% yield (Table 3, entries 3 and
4). Further decreasing the catalyst loading to 2.5 mol%, only
gave 33% yield (Table 3, entry 5). Recently, it was shown that
additives such as phenol or styrene have a beneficial impact
3
8
on the catalyst activity and lifetime. In our case, in the pres-
ence of styrene (5 equiv.) with 2.5 mol% catalyst loading, the
yield increased to 75% (Table 3, entry 6). Increasing the reac-
b
b
b
Conv.
(%)
Yield
(%)
Selec.
(%)
Cyclic
b
Entry Solvent
form (%) tion time to 18 hours allowed to reach full conversion and 3
was obtained with 93% yield (Table 3, entries 7 and 8). Further
1
2
3
4
5
6
CH
3
CN/H
2
O (7 : 1)
5
0
0
37
44
0
5
0
0
31
43
0
99
0
0
99
99
0
94
CPME
2-MeTHF
THF
1,4-Dioxane
(Trifluoromethyl)
benzene
—
—
98
98
—
decreasing the catalyst loading to 1 mol% did not allow to
reach high yield, even with extended reaction time (Table 3,
entries 9 and 10). Finally, the oxidation of diglycerol was
repeated using catalytic systems Pd-1 and Pd-2 under the opti-
mized conditions. In that case, diglycerose 3 was only formed
with 51 and 60% yield, respectively (Table 3, entries 11 and
7
8
TFE
HFIP
71
76
54
74
99
99
93
93
1
2). These experiments show that all catalytic systems are
a
Reaction conditions: α,α-Diglycerol (0.45 mmol), Pd-3 (10 mol%), O
2
active under the optimized conditions, which are found to be
crucial for the success of this reaction. The trend between the
b
(
1 bar), solvent (5.5 mL), 50 °C, 2 h. Conversion, yield, selectivity and
ratio of mono-oxidation product on cyclic form were determined by H
1
NMR using mesitylene as internal standard. CPME: cyclopentyl methyl three different catalytic systems is the same than the one
ether, 2-MeTHF: 2-methyl tetrahydrofuran, THF: tetrahydrofuran, TFE:
trifluoroethanol, HFIP: 1,1,1,3,3,3-hexafluoroisopropanol.
observed for the oxidation of glycerol (Table 1), with Pd-3
complex being the most active catalyst. The superiority of this
cationic palladium(II) complex in the oxidation of alcohols has
been previously attributed to the presence of both the acetate
a
Table 3 Diglycerol oxidation in HFIP
43
and triflate ions. While the non-coordinating triflate ion gen-
4
4
erates an open coordination site that allows fast initial rates,
the acetate ion acts as an internal base that facilitates the
4
5
intramolecular deprotonation.
A scale-up reaction was performed on a 10-fold scale under
optimized conditions and diglycerose 3 was obtained with
76% isolated yield (Scheme 2).
b
b
b
The oxidation method was found to be efficient and selec-
Catalyst
(mol%)
Time
(h)
Conv.
(%)
Yield
(%)
Selec.
(%)
tive on α,α-diglycerol. Therefore it could also be applied to
α,β-diglycerol. However, α,β-diglycerol recovered from the fil-
trate after hydrolysis of diglycerol dicarbonate was not pure
enough. Consequently, it was prepared in three steps from
Entry
O
2
(bar)
1
2
3
4
5
3
6
6
3
3
3
3
3
3
3
3
3
10
10
5
2
2
2
2
2
2
6
18
18
30
18
18
95
>99
69
69
34
79
79
>99
77
77
54
64
89
94
66
63
33
75
77
98
98
99
99
99
99
99
98
99
99
99
99
5
46
solketal following a reported procedure (see ESI† for details).
2.5
2.5
2.5
2.5
1
1
2.5
2.5
c
Selective oxidation of α,β-diglycerol was also carried out under
the optimized conditions. In that case, the mono-oxidation
product 7 was only obtained with 4% yield and bicylic ketal 8 –
formed by dehydration of 7 – was obtained with 76% yield
6
c
7
8
c
d
93 (61)
74
c
9
c
1
1
1
0
1
2
73
51
60
c,e
c, f
(Scheme 3). Satisfyingly, reducing the O
with 51% isolated yield. α,β-Diglycerose 7 also exists as a
cyclic hemi-ketal (no open formed detected) and was obtained
2
pressure to 1 bar gave
7
a
2
Reaction conditions: α,α-Diglycerol (0.45 mmol), Pd-3, O , HFIP
b
(
5.5 mL), 50 °C unless otherwise stated. Conversion, yield, selectivity with a dr of 88 : 12. In the major diastereoisomer, the hydroxy-
and ratio of mono-oxidation product (3 versus 6) were determined by
methyl groups adopt a relative trans configuration (determined
by NMR, see ESI†).
1
c
H NMR using mesitylene as internal standard. Styrene (2.25 mmol, 5
d
e
f
equiv.) was added. Isolated yield in brackets. Using Pd-1. Using Pd-
2.
and 94% yield, respectively (Table 3, entries 1 and 2).
Satisfyingly, the selectivity for the mono-oxidation product
remained high (around 98%), highlighting the high selectivity
of the catalytic system. Considering that palladium is an
expensive metal, the amount of catalyst should be reduced.
The reaction was first carried out with 5 mol% of catalyst Scheme 2 Scale-up reaction for α,α-diglycerol.
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Scheme 3 Scale-up reaction for α,β-diglycerol.
The difference of reactivity between α,α- and α,β-diglycerol
led us to investigate their oxidation rates under the optimized
conditions. The oxidation was first performed under 1 bar of
Fig. 2 Dehydration of α,α-diglycerose 3 and α,β-diglycerose 7. Reaction
conditions: α,α- or α,β-diglycerose 3 or 7 (0.45 mmol), A15 (10 mol%),
CH Cl , 30 °C, 2 hours. The conversions and yields were determined by
2 2
2
O for convenience in sampling the reaction mixture. The reac- GC after derivatization, using methyl oleate as an internal standard.
tion progress for each diglycerol isomer is plotted in Fig. 1.
From these experiments, it is clear that α,α-diglycerol α,α-1 is
more easily oxidized than α,β-diglycerol α,β-1, with their con- formed when the reaction was conducted at 50 °C under 3 bar
version reaching 59 and 39% after 24 hours, respectively. of oxygen from α,β-diglycerol, while almost no dehydration
Interestingly, an initiation period of about 2 hours was product 9 was detected when α,α-diglycerol was reacted under
observed for both isomers. When the reaction was performed the same conditions. To probe the synthetic utility of diglycer-
under 3 bar of oxygen, the conversion of α,α-1 reached 92% ose, some chemical transformations were next investigated
after 24 hours and no initiation period was observed.
(Scheme 4).
This result demonstrates that increasing the oxygen
First, α,α-diglycerose 3 was treated with Amberlyst 15 for
pressure has a positive outcome on the overall rate of the reac- 4 hours to give bicyclic ketal 9 with 48% isolated yield
tion. Indeed, increasing the pressure of oxygen increases its (Scheme 4, a). Then, benzoylation of α,α-diglycerose 3 was per-
concentration in HFIP. Considering that oxygen is necessary to formed using benzoyl chloride and provided the per-benzoy-
re-oxidize Pd(0) to Pd(II) and therefore to complete the catalytic lated products with 74% combined yield (Scheme 4, b). In that
cycle, increasing its concentration allows reaching higher turn- case, cyclic and linear products 10 and 11 can be separated
over frequencies.
and were isolated with 65 and 9% yield, respectively. Some
To further understand the formation of the dehydration traces (3%) of bis-benzoylated diglycerose 12 were also iso-
products, pure α,α-diglycerose 3 and α,β-diglycerose 7 were lated. In order to further confirm the structure of cyclic digly-
treated under acidic conditions (Fig. 2). After 1 hour at 30 °C, cerose, per-benzoylation was also carried out using 4-bromo-
the conversion of 3 and 7 reached 6 and 32%, respectively, benzoyl chloride (Scheme 4, c). Cyclic and linear products 13
while the yield of 9 and 8 reached 4 and 27%, respectively.
and 14 were obtained with 45 and 6% isolated yields, respect-
These results demonstrate that the dehydration of ively. Despite our efforts to obtain suitable crystals, no X-Ray
α,β-diglycerose 7 to 8 is easier than those of α,α-diglycerose 3
to 9. They could explain why a high proportion of 8 was
Fig. 1 Reaction progress of the oxidation of α,α-diglycerol (α,α-1) and
α,β-diglycerol (α,β-1). Reaction conditions: α,α- or α,β-diglycerol
(
2
0.45 mmol), Pd-3 (2.5 mol%), O (1 or 3 bar), HFIP (5.5 mL), 50 °C. The
conversions and yields were determined by GC after derivatization,
using methyl oleate as an internal standard.
Scheme 4 Chemical transformations of α,α-diglycerose.
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structure can be obtained for 13. Thereby, the structure of
compound 13 was determined by 1D and 2D NMR analyses
and the relative cis-configuration was assigned though a
NOESY experiment (see ESI†).
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dation of diglycerol using a palladium/neocuproine complex
and oxygen as a clean oxidant. After optimization of the reac-
tion parameters on α,α-diglycerol, the mono-oxidation product
was obtained with high selectivity (99%) and high yield (93%).
The product was isolated with up to 76% yield and was found
to mainly exist as a cyclic hemi-ketal form. Given its structural
similarities with ketoses, this original “ketose-like” compound
has been named “diglycerose”. The conditions were also
applied to α,β-diglycerol and the corresponding hemi-ketal was
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