Low-Temperature Reductive Aminolysis of Carbohydrates to Diamines and Aminoalcohols by Heterogeneous Catalysis

Article abstract of DOI:10.1002/anie.201708216

Short amines, such as ethanolamines and ethylenediamines, are important compounds in today's bulk and fine chemicals industry. Unfortunately, current industrial manufacture of these chemicals relies on fossil resources and requires rigorous safety measures when handling explosive or toxic intermediates. Inspired by the elegant working mechanism of aldolase enzymes, a novel heterogeneously catalyzed process—reductive aminolysis—was developed for the efficient production of short amines from carbohydrates at low temperature. High-value bio-based amines containing a bio-derived C2 carbon backbone were synthesized in one step with yields up to 87 C%, in the absence of a solvent and at a temperature below 405 K. A wide variety of available primary and secondary alkyl- and alkanolamines can be reacted with the carbohydrate to form the corresponding C2-diamine. The presented reductive aminolysis is therefore a promising strategy for sustainable synthesis of short, acyclic, bio-based amines.

Full text of DOI:10.1002/anie.201708216

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Accepted Article
Title: Low temperature reductive aminolysis of carbohydrates to
diamines and aminoalcohols through heterogeneous catalysis
Authors: Michiel Pelckmans, Walter Vermandel, Frederik Van Waes,
Kristof Moonen, and Bert F. Sels
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201708216
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10.1002/anie.201708216
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COMMUNICATION
Low temperature reductive aminolysis of carbohydrates to
diamines and aminoalcohols through heterogeneous catalysis
Michiel Pelckmans, Walter Vermandel, Frederik Van Waes, Kristof Moonen and Bert F. Sels*
Short amines such as ethanolamines (EOAs) and ethylene
diamines (EDAs) are important compounds in today’s bulk and
fine chemicals industry.[1] They are e.g. used as catalysts in the
polyurethane synthesis[2] or as building blocks for the production
of cationic surfactants.[3] Today’s manufacture of EOAs and EDAs
relies on fossil-based ethylene, which is produced by oil and gas
3a, 4]
cracking or by dehydrogenation of ethane.[2a,
Besides
corrosion and environmental issues, their production involves
severe safety management to handle toxic intermediates like
ethylene oxide.[3a, 4b, 4c] The design and development of a safer
and more sustainable production route for amines (e.g. from
renewable carbon, solvent-free, at low temperature) are just
coming into prominence.[5]
Scheme 1. Two possible bio-based routes to C2-amines from glucose.
The high temperature requirement for R-A is elegantly
circumvented by Nature’s evolved enzyme catalysis. The Class 1
Aldolases (C1A) for instance use a lysine (ε-LYS) residue for
rapidly catalyzing the reversible aldol reaction at body
temperature with excellent selectivity by means of a protonated
Schiff base intermediate (PSB-IM).[14] In accordance with C1A,
Retro-aldolases (RALs) with different catalytic motifs that carry
out the reverse reaction were designed computationally.[15] The
general mechanism of the enzymatic R-A reaction is presented in
Scheme 2 (left).[15c] After nucleophilic attack of the ε-LYS group on
the carbonyl function, the PSB-IM is formed through dehydration.
Next, a base-catalyzed R-A-type reaction breaks the C-C bond
and the cleavage product is released as an aldehyde. Subsequent
reaction steps are dedicated to regenerate the catalytic ε-LYS site.
R-A catalysis over PSB-IM is also the rationale behind the original
observation of Westheimer and Cohen. They observed already in
1938 the ability of MMA and (to a lesser extent) DMA to catalyze
R-A reactions with diacetone alcohol.[16] Trimethylamine (TMA),
which is unable to form a PSB-IM, showed no catalytic effect.
Such organocatalytic R-A reactions using primary amine
organocatalysts have been reported in asymmetric reactions.[17]
Inspired by the elegant mechanism of RALs, we propose
here a one-step catalytic route - further denoted reductive
aminolysis - for the safe and sustainable production of bio-based
diamines and aminoalcohols from monosaccharides at low
temperature. The route encompasses the facilitating effect of an
amine on R-A C-C scission, analogous to that of the C1A
mechanism, but in absence of the enzymatic environment.
Instead of regenerating the catalytic amine after the C-C scission,
the enamine (or imine) IM is catalytically hydrogenated to produce
the desired short amine (Scheme 2, right). The success of the
proposed mechanism is demonstrated by a series of reactions
with monosaccharides that are carried out under both 0.1 MPa N2
and 7.5 MPa H2 (Figure 1). The catalytic data show that glucose
as well as xylose are converted with DMA into N,N-
dimethylformamide (DMF) and N,N-dimethylamino-2-propanone
(DMA-2-propanone) in absence of H2. The product yield, given in
C%, represents the fraction of carbon originating from the sugar
substrate that is found in the product. Slightly less DMF (8 C%) is
formed from xylose, compared to glucose (10 C% DMF), while the
amount of DMA-2-propanone is similar (11 C%) for both
monosaccharides.
Biomass is a widely available alternative feedstock for the
production of chemicals, especially of interest when the atom
economy of the reaction is high.[6] In light hereof, we propose a
novel synthesis route to short amines (Scheme 1) by direct
conversion of carbohydrates in presence of industrially available
amines, such as monomethylamine (MMA) and dimethylamine
(DMA). As opposed to an alternative multi-step route through
ethylene from bio-ethanol, the proposed route is a one-pot
reaction involving two consecutive reaction steps, being i) a retro-
aldol (R-A) C-C bond scission of the sugar molecule and ii)
reductive amination of the short carbonyl intermediates. Since no
CO2 is produced during C-C cleavage, the bio-based C2-amines
are formed with a ‘greener’ carbon efficiency than that of the bio-
ethanol route.[7] R-A-like reactions are well-studied in
carbohydrate chemistry for the synthesis of glycolaldehyde,[7-8]
glyceraldehyde,[9] lactic acid[10] and novel chemicals like methyl
and vinyl glycolate,[11] but they are also involved in the formation
11f, 12]
13]
of ethylene glycol[9,
and propylene glycol.[9,
The C-C
scission of the R-A reaction usually requires a high reaction
temperature (> 430 K). Zhang and coworkers for instance recently
demonstrated 10% EOA formation from cellulose by a 2-step
process. The first R-A step forming glycolaldehyde requires 563
K.[7] At the high temperature, not only the reactive carbonyl
compounds, but also the amine - present for subsequent
amination - and their combinations can undergo a plethora of
competitive side reactions such as (aldol) condensation,
hydrogenation, cyclization, disproportionation, overalkylation, …
eventually leading to poor selectivity (Table S1, SI).
[*]
M. Pelckmans, W. Vermandel, Prof. Dr. Bert F. Sels
Dept. M2S, KU Leuven
Celestijnenlaan 200F, 3001 Leuven (Belgium)
E-mail: bert.sels@kuleuven.be
Dr. ir. F. Van Waes and Dr. ir. K. Moonen
Eastman Chemical Company
Technologiepark 21, 9000 Ghent (Belgium)
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201708216
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Scheme 2. Left: a general description of the retro-aldol reaction pathway in computationally designed RALs using i) a nucleophilic ε-LYS residue for the generation
of a PSB-IM and ii) acid-base chemistry adapted with permission from [15c]. Right: reductive aminolysis with DMA inspired by the enzymatic R-A reaction but i)
involving the synthesis of a zwitterionic IM instead of the PSB-IM and ii) involving intramolecular proton transfer to produce this zwitterionic iminium IM and finally
iii) using additional redox catalytic activity to trap the attacking amine by hydrogenation.
The product mixtures obtained in absence of H2 are colored dark
brown, as a consequence of Maillard[18] and caramelization[19] side
reactions. In presence of H2 however, up to 51 C% of the
predominant C2-diamine N,N,N’,N’-tetramethyl ethylenediamine
(TMEDA) is produced from glucose. The reaction proceeds
rapidly (Figure S1, SI) and the enediamine TMEDA precursor
(Scheme 2) is detected only initially during the course of the
reaction and at very low concentration (< 5 C%), indicating its
efficient hydrogenation into TMEDA. Besides TMEDA, 15 C% of
the C3-diamine N,N,N’,N’-tetramethyl-1,2-propylenediamine
(TMPDA) is formed. Side products are DMF (4 C%), N,N-
dimethylaminoethanol (DMAE, 4 C%), N,N-dimethylamino-2-
propanol (DMA-2-propOH, 2 C%) and DMA-2-propanone (< 1
C%), the latter being the likely precursor of TMPDA and DMA-2-
propOH (Figure S1). The product mixture is colored pale yellow
instead of dark brown, strongly indicating less side reactions have
occurred. Indeed, N-incorporation from DMA into the short amine
products occurs highly efficiently (Table S2, SI). For the reaction
of xylose with DMA under H2, the amount of xylose C-atoms in
C2-amines (TMEDA and DMAE) equals that in the C3-amines
(TMPDA, DMA-2-propOH and DMA-2-propanone). Around 29
C% of C2-products and 31 C% of C3-products are obtained. DMF
(2 C%) formation, though high under N2, is largely prevented in
presence of H2.
atoms in the end product. From the catalytic reaction of fructose
with DMA under H2 (Figure S6, SI), considerably less C2-amines,
viz. TMEDA and DMAE, are produced (31 C%) compared to that
from glucose (55 C%). But also less C3-amines, viz. TMPDA,
DMA-2-propOH and DMA-2-propanone, are obtained from
fructose (13 C% instead of 19 C% for glucose), suggesting that
fructose is not the main precursor for the observed C3-amines in
the reductive glucose aminolysis. When the reaction with glucose
is carried out in absence of DMA, sorbitol is the main reaction
product (90 C%). This observation strongly corroborates the
active role of the amine in low-temperature C-C bond breaking.
Also, since sorbitol is not converted under similar low temperature
conditions (Figure S6), hydrogenolysis is excluded as a cause of
C-C scission, while sorbitol dehydrogenation does not take place.
This is in contrast with the catalytic results from Ernst and
coworkers who converted sorbitol - albeit in low yield - to C2 and
C3-diamines.[21] But the reaction required high temperature (473
K) to convert the sugar alcohol, precluding a high selectivity
towards the desired C2- and C3-products. Instead, heterocyclic
(methylated) piperazines (PIPs) were the dominant reaction
products as the result of cyclization.
In accordance with the proposed reaction route (Scheme 2,
right), the dominant formation of two C2-products (TMEDA and
DMAE) from glucose under H2 in presence of DMA proceeds
through two consecutive retro-aldol-type C-C scission reactions,
viz. from C6 to 3 C2, prior to metal-catalyzed hydrogenation. Only
1 C% hexitols, 2 C% N,N-dimethylglucamine, 1 C% C4 sugar
alcohol and 1 C% N,N-dimethylamino-1,2,3-butanetriol are
formed. Xylose undergoes a single retro-aldol reaction, explaining
the equal number of C2- and C3-aminated products. Although the
origin of the different C3-products in the glucose reaction is
currently under investigation, their formation likely results from
competitive isomerization[20] and/or dehydration reactions.
According to the mechanism of Scheme 2 (right), production of
either C2- or C3-amines depends on the carbonyl position in the
sugar C-skeleton. Isomerization or dehydration prior to R-A, shifts
the carbonyl position, hereby altering the number of sugar C-
Figure 1. Product distribution for glucose and xylose aminolysis obtained after
1 h (full sugar conversion) at 398 K with Ru/C under i) atmospheric N2 pressure
(0.1 MPa) and ii) elevated H2 pressure (7.5 MPa).
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For instance, a reference reaction of sorbitol with DMA in water at
indeed only minor formation of EDA (2 C%) was obtained. The
473 K instead of the usual 398 K indeed shows only 2 C% TMEDA, alkyl chain length of the N-source also affects the C2-diamine
1 C% DMAE and < 1 C% DMA-2-propOH after 4 h and only 2 C%
PIPs are obtained. Finally, 2-deoxy-D-glucose (2-DG) was
successfully converted under the reductive aminolysis conditions.
In accord to the R-A mechanism, this β-OH carbonyl compound
forms TMEDA (17 C%) and the more volatile dimethylethylamine
(DMEA) as the major products (Scheme S1 and Figure S14, SI).
Since the product formation occurs in absence of an α-OH group,
the peculiar C-skeleton rearrangement that initiates C-C scission,
which was reported for metal oxide catalyzed glucose-to-ethylene
glycol and epimerization reactions[22] is excepted to explain the C-
C scission.
The role of the metal catalyst is evident from Scheme 2.
Reaction in absence of the catalyst led to a dark colored product
mixture, indicative of unselective sugar conversion. Alike the
reaction results under N2, only DMA-2-propanone (11 C%) and
DMF (9 C%) were detected after 1 h for the reaction of glucose
with DMA in absence of Ru/C at 7.5 MPa H2. Furthermore, notable
catalyst stability was observed during catalyst recycling
experiments (Figure S7, SI). Ru/C was reused at least three times
without considerable deactivation. The metal nature of the
supported catalyst is less essential, as others like cheaper Ni
catalysts also afford high product selectivity. For instance, a
commercial silica supported 56 wt.% Ni catalyst (Ni-6458P,
Engelhard) yields 47 C% TMEDA, and 4 C% DMAE, 2 C%
TMPDA, 5 C% DMA-2-propOH, 7 C% DMA-2-propanone and 5
C% DMF under standard reaction conditions.
The reaction is not limited to DMA. Other amines such as
primary and secondary alkyl- and alkanolamines were also
converted successfully. Reductive aminolysis runs efficiently (see
Table 1) with both primary (up to 53 C% product yield) as well as
secondary amines (up to 84 C% product yield). The use of
secondary amines attains a higher yield of N-substituted acyclic
ethylene diamine (C2-diamine) in all cases, as compared to the
primary amine reactants. Tertiary amine reaction products are
less reactive than the secondary amine products, from which side
reactions such as overalkylation or cyclization may thus be
expected. However, no substantial formation of overalkylation
products was detected here for the reductive aminolysis with the
primary amines. Moreover, cyclization side reactions of the
secondary amine reaction products to PIPs were hardly analyzed
here. This is most likely on account of the low reaction
temperature. Less than 1 C% of N,N’-dimethyl-PIP was for
instance formed in the reaction of glucose with MMA (Table 1,
entry 1) and only 2 C% of N,N’-bis(2-hydroxyethyl)-PIP was
produced from the reaction with ethanolamine (EOA, entry 4).
In order to get the high C-C scission product selectivity (like
product yield; increasing alkyl chain length simultaneously
increases the electron density at the N-atom (making it a better
nucleophile), but also increases steric hindrance (decreasing its
accessibility) towards the carbonyl substrate. Both factors can
explain the lower yield in presence of ethylamine, in comparison
to reactions with MMA and N-butylamine (compare entry 2 with
entries 1 and 3).
Table 1. Aminating agent scope for the reductive aminolysis of glucose into C2-
diamines.[a]
Entry Glucose Amine Water
Amine
Product
Yield
[C%]
[g]
[g]
[g]
1
2
3
2.5
2.5
2.5
12.5
18.0
20.0
34.0
15.0
20.0
12.5
7.5
43
31
34
53
51
33
5.0
4[b,c] 1.0
0.0
5
6
5.0
2.5
10.0
5.0
7[b,d] 1.0
8[b,c,e] 1.0
34.0
30.0
0.0
0.0
71
84
„
„
„
„
„
„
9[b,c,e] 1.0
10[f,g] 665
22.0
8.0
63
87
84
1665
665
11[f,g] 665[h]
12[f,i] 1500
1665
7600
665
„
„
„
„
81
1500
[a] Reaction conditions: 398 K, 7.5 MPa H2 pressurized at RT, 0.5 g Ru/C and
1 h reaction. [b] Reaction at 403 K and 8.5 MPa H2 with 0.3 g catalyst. Yield
determined via 13C-NMR. [c] 2 h reaction. [d] 4.5 h reaction. [e] 0.3 g Ni-6458P
instead of Ru/C. [f] Fed-batch reaction (see Experimental section, SI) [g] 27 g
Ni-KL6504 instead of Ru/C. [h] Industrial starch-derived glucose syrup instead
of glucose. [i] 20 L scale at 413 K with 32 g Ni-KL6504.
An exceptionally high product yield of N,N’-bis(2-hydroxyethyl)-
N,N’-dimethylethylenediamine (BHEDMEDA) is obtained for the
reductive glucose aminolysis with MEOA (entries 7-12). Similar to
DMA, the reaction with MEOA runs efficiently also with Ni
catalysts. To our delight, use of the commercial Ni-6458P instead
of the more expensive Ru/C results in even higher C2-diamine
yield. An excellent yield of 84 C% BHEDMEDA was ultimately
obtained, instead of 71 C% with Ru/C. The reaction in presence
of Ni is also faster (within 2 h, entry 8) compared to Ru (within 4.5
h, entry 7). In our effort to explain for the superior BHEDMEDA
yield upon using the hydroxyl methylamine, two effects are
considered; stabilization of the enamine IM and the absence of
water. Although the precise explanation is currently under
with secondary amines), avoidance of
a
competitive
intramolecular proton transfer in the zwitterionic iminium IM to
form the imine, which is ultimately hydrogenated to the amino
sugar alcohol, is essential (Scheme S2, SI). The reaction with
MMA (entry 1) for instance resulted in a 16 C% corresponding N-
methylglucamine side product. The selectivity therefore strongly
depends on the amine reagent, the more alkylated ones favoring
C-C scission, because of prevention of the competitive
intramolecular proton transfer. Accordingly, selective reductive
amination of sugars with NH3 to short amines is difficult, and
investigation,
a mechanism involving a hydroxyl-mediated
stabilization of the enamine IM is the working hypothesis.
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Table 2. Variations of temperature, pressure and molar DMA excess for the aqueous reductive aminolysis of glucose with Ru/C.[a]
Entry
Temperature
[K]
Pressure H2
[MPa]
nDMA: nglucose
[mol : mol]
YTMEDA
[C%]
YDMAE
[C%]
YTMPDA YDMA-2-propOH
YDMA-2-propanone
[C%]
YDMF
[C%]
[C%]
[C%]
1
373
398
423
398
398
398
398
398
7.5
7.5
7.5
5.0
10.0
7.5
7.5
7.5
12
12
12
12
12
5
34
51
31
35
44
4
3
4
3
2
4
2
3
4
7
15
17
9
1
2
3
1
2
5
3
2
2
< 1
< 1
4
4
4
5
4
2
3
4
3
2
3
4
5
13
10
16
13
< 1
2
6
7
9
22
50
3
8[b]
15
< 1
[a] Reaction conditions: 5 g glucose, 0.5 g Ru/C and 1 h reaction. [b] 4 g glucose.
aminolysis of glucose with DMA and Ru/C is thus carried out
preferably at 398 K, 7.5 MPa H2 and at molar excess DMA-to-
glucose of at least 12.
Notably, the successful reaction with MEOA (and EOA) is carried
out in absence of a solvent. As can be seen from Table 1, addition
of 25 wt.% H2O to the batch reaction system with MEOA
negatively affects the C2-diamine yield from 84 C% to 63 C%. It
is suggested that, particularly in the presence of larger water
content, competitive reactions occur form the glucose during the
heating phase, before the required temperature for efficient C-C
scission is reached. Therefore, the reaction was carried out in fed-
batch mode using an aqueous glucose feed (entry 10); a similarly
high BHEDMEDA yield of 87 C% was thus obtained.
The reductive aminolysis presented here is not able to
directly convert polymerized glucose like cellulose and starch into
short amines, likely due to inefficient hydrolysis in the alkaline
conditions. However, an industrial starch-derived sugar syrup
(see Table S4) was successfully converted into a similar
BHEDMEDA yield, as obtained from the reaction with purified
crystalline glucose (compare entries 10 and 11). Moreover, the
reaction was scalable up to 20 L (entry 12), while maintaining the
same high BHEDMEDA yield (81 C%).
In summary, a new heterogeneously catalyzed process for
the manufacture of bio-based short amines from carbohydrates at
low temperature is presented. High-value amines containing a
bio-derived C2 carbon backbone were synthesized in one step
with yields up to 87 C% in absence of a solvent at a temperature
below 405 K. The presence of the amine is a prerequisite to allow
the low temperature C-C breakage of the monosaccharide
backbone, while the metal catalyst converts the unsaturated imine
or enamine intermediates into the short amines by hydrogenation.
A wide variety of available primary and secondary alkyl- and
alkanolamines can be reacted with glucose to the corresponding
C2-diamine. The presented reductive aminolysis is therefore a
promising strategy to foresee a sustainable synthesis of short
acyclic bio-based amines, useful as chemical building blocks,
catalysts and CO2 absorbents.
Reaction conditions for the reductive aminolysis of glucose
with DMA in presence of Ru/C were varied systematically to
demonstrate the effect of temperature, pressure and molar
excess of DMA-to-glucose (Table 2). TMEDA yield reaches an
optimum of 51 C% at a reaction temperature of 398 K. Selectivity
towards the C2-amines, viz. TMEDA and DMAE, drops both for
higher (423 K) and lower (373 K) reaction temperature. High H2
pressure favours the C2-product formation, while more DMA-2-
propanone and less TMPDA and DMA-2-propOH are obtained at
lower pressure, confirming that DMA-2-propanone is the likely
precursor of TMPDA and DMA-2-propOH. For efficient formation
of C2-amines (> 50 C%), a minimum of 12 mol DMA per mol
glucose is required. At a molar DMA excess of 9, only 22 C% of
TMEDA was formed. Interestingly, the total amount of C3-
products remains constant at a DMA excess of 5 and even slightly
increases at molar DMA excess of 9. Further increasing DMA
excess from 12 to 15 has negligible influence on the TMEDA yield.
Only minor decrease in TMPDA yield from 16 to 13 C% is
observed. Given that the DMA excess more strongly affects
formation of TMEDA than that of the C3-products, it can be
rationalized that C3-product formation occurs mechanistically
parallel to the formation of C2-products. Aqueous reductive
Acknowledgements
The authors thank the Flemish government for financial support
in the Carboleum icon project (Catalisti). M. P. acknowledges K.
Duerinckx for help with NMR measurements and prof. J. Thybaut
and Dr. P. Roose for helpful discussions.
Keywords: Biomass • amines • retro-aldol • heterogeneous
catalysis
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Low temperature reductive
aminolysis of carbohydrates to
diamines and aminoalcohols through
heterogeneous catalysis
Reductive aminolysis of carbohydrates to short diamines and aminoalcohols in
presence of heterogeneous metal catalysis is effective at low temperature thanks to
the facilitative effect of the amine reagent on the carbon-carbon scission.
This article is protected by copyright. All rights reserved.

10.1002/anie.201708216
Angewandte Chemie International Edition
COMMUNICATION
This article is protected by copyright. All rights reserved.