Superelectrophilic activation of 5-hydroxymethylfurfural and 2,5-diformylfuran: Organic synthesis based on biomass-derived products

Article abstract of DOI:10.3762/bjoc.12.202

The reaction of 5-hydroxymethylfurfural (5-HMF) with arenes in superacidic trifluoromethanesulfonic acid (triflic acid, TfOH) as the solvent at room temperature for 1-24 h gives rise to 5-arylmethylfurfurals (yields of 17-91%) and 2-arylmethyl-5-(diarylme

Full text of DOI:10.3762/bjoc.12.202

Superelectrophilic activation of 5-hydroxymethylfurfural
and 2,5-diformylfuran: organic synthesis based on
biomass-derived products
Dmitry S. Ryabukhin1,2, Dmitry N. Zakusilo1,3, Mikhail O. Kompanets4,
Anton A.Tarakanov1, Irina A. Boyarskaya2, Tatiana O. Artamonova5,
Mikhail A. Khohodorkovskiy5, Iosyp O. Opeida6 and Aleksander V. Vasilyev*1,2
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2016, 12, 2125–2135.
1Department of Chemistry, Saint Petersburg State Forest Technical
University, Institutsky per., 5, Saint Petersburg, 194021, Russia,
2Institute of Chemistry, Saint Petersburg State University, Saint
Petersburg State University, Universitetskaya nab., 7/9, Saint
Petersburg, 199034, Russia, 3The All-Russia Scientific Research
Institute of Fats, ul. Chernyakhovskogo, 10, Saint Petersburg,
191119, Russia, 4L.M. Litvinenko Institute of Physico-Organic and
Coal Chemistry of NASU, Kharkivs’ke Hgw, 50, Kiyv, 02160, Ukraine,
5Institute of Nanobiotechnologies, Peter the Great St. Petersburg
Polytechnic University, Polytechnicheskaya ul., 29, Saint Petersburg,
195251, Russia and 6Department of Physical Chemistry of
Combustible Minerals, L.M. Litvinenko Institute of Physical Organic
and Coal Chemistry of NASU, Naukova St., 3a, Lviv, 79053, Ukraine
doi:10.3762/bjoc.12.202
Received: 29 June 2016
Accepted: 12 September 2016
Published: 05 October 2016
This article is part of the Thematic Series "Green chemistry".
Guest Editor: L. Vaccaro
© 2016 Ryabukhin et al.; licensee Beilstein-Institut.
License and terms: see end of document.
Email:
Aleksander V. Vasilyev* - aleksvasil@mail.ru
* Corresponding author
Keywords:
2,5-diformylfuran; Friedel–Crafts reaction; 5-hydroxymethylfurfural;
superacids; zeolites
Abstract
The reaction of 5-hydroxymethylfurfural (5-HMF) with arenes in superacidic trifluoromethanesulfonic acid (triflic acid, TfOH) as
the solvent at room temperature for 1–24 h gives rise to 5-arylmethylfurfurals (yields of 17–91%) and 2-arylmethyl-5-(diaryl-
methyl)furans (yields of 10–37%). The formation of these two types of reaction products depends on the nucleophilicity of the
arene. The same reactions under the action of acidic zeolites H-USY in high pressure tubes at 130 °C for 1 h result in the formation
of only 5-arylmethylfurfurals (yields of 45–79%). 2,5-Diformylfuran (2,5-DFF) in the reaction with arenes under the action of
AlBr3 at room temperature for 1 h leads to 5-(diarylmethyl)furfurals (yields of 51–90%). The reactive protonated species of 5-HMF
and 2,5-DFF were characterized by NMR spectroscopy in TfOH and studied by DFT calculations. These reactions show possibili-
ties of organic synthesis based on biomass-derived 5-HMF and 2,5-DFF.
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Beilstein J. Org. Chem. 2016, 12, 2125–2135.
Introduction
Nowadays great attention is paid to the use of renewable The main goal of this work was a study of reactions of 5-HMF
resources for obtaining fine chemicals and fuels (see numerous and 2,5-DFF with arenes under electrophilic activation with
reviews [1-16]). The biorefinery of renewable lignin-carbo- Brønsted and Lewis superacids. Previously superelectrophilic
hydrate materials affords various low-molecular weight organic activation of aldehyde groups was achieved for heteroaromatic
molecules, such as alcohols, carboxylic acids, (hetero)aromatic aldehydes [34-37], substituted benzaldehydes and o-phthalic
ketones and aldehydes, phenols, etc. These biomass-derived dicarboxaldehyde [38]. Based on these findings, one would
platform chemicals are considered as an alternative and dis- expect the activation of an aldehyde group of 5-HMF and 2,5-
placement to petroleum chemistry [17,18]. Among all these DFF, and its participation in the hydroxyalkylation of arenes.
compounds, the preparation and reaction of 5-hydroxymethyl- However, furan carboxaldehydes in such reactions were studied
furfural (5-HMF) attracts special attention (see fundamental in this work for the first time.
review from 2013 [19] and recent papers [20-25]). The high
functionality and reactivity of 5-HMF, due to the presence of It should be noted, that reactions of arenes with hydroxymethyl
oxymethyl and aldehyde substituents, along with the furan and aldehyde groups of 5-HMF and 2,5-DFF may lead to
moiety, allows many transformations and therefore the produc- various arylmethyl- and diarylmethyl-substituted furans, which
tion of new useful organic substances [26-30].
are otherwise hardly available molecules [39-46] and used for
the synthesis of bioactive compounds [47]. Thus, the superelec-
Based on our recent study on the synthesis of 5-HMF and its trophilic activation of 5-HMF and 2,5-DFF could be of great
oxidation to 2,5-diformylfuran (2,5-DFF) [31] (Figure 1), this value for organic synthesis.
work is focused on developing methods of organic synthesis on
the basis of electrophilic activation of these biomass-derived Results and Discussion
products.
The protonation of the carbonyl oxygen and hydroxy group of
5-HMF (1a) in strong acids gives rise to cationic species A, the
Superelectrophilic activation is the generation of highly reac- dehydration of the latter may result in the formation of
tive di-, tri- (or even higher) cationic species by protonation and heteroaromatic benzyl-type dication B (Scheme 1). Protonation
protosolvation of organic molecules with low nucleophilic of the aldehyde groups in 2,5-DFF (2) leads to cation C and
Brønsted superacids, such as CF3SO3H (TfOH) or FSO3H [32]. dication D (Scheme 1). All species A, B, C, and D may play a
The same activation may be achieved with strong Lewis acids role as reactive intermediates derived from 1a and 2 in
(AlX3, X = Cl, Br) by their coordination with basic centers of superacids. To estimate the electrophilic properties of cations A,
organic compounds, or with acidic zeolites, possessing both B, C, and D we performed quantum chemical calculations by
Brønsted and Lewis acidity [33].
the DFT method (Table 1). HOMO and LUMO energies, global
Figure 1: Formation of 5-HMF from D-glucose or D-fructose followed by oxidation to 2,5-DFF.
Scheme 1: Protonation of 5-HMF (1a) and 2,5-DFF (2) leading to cationic species A, B, C, D.
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Beilstein J. Org. Chem. 2016, 12, 2125–2135.
electrophilicity index ω [48,49], charge distribution, and contri- the LUMO. This indicates that this carbon atom may be an elec-
bution of atomic orbitals into the LUMO were calculated. The trophilic reactive center from both charge and orbital point of
dications B and D having high ω values of 9.6 and 8 eV, respec- view. Apart from that, the increase of positive charge on
tively, should be very reactive electrophiles. The carbon atom heteroaromatic carbons C1, C4 and the decrease of negative
of the protonated aldehyde group in species A, B, C, and D charge on atoms C2, C3, and Ofuran upon protonation of furans
bears a large positive charge and shows a great contribution in 1a and 2 reveal a significant positive charge delocalization into
Table 1: Selected electronic characteristics (DFT calculations) of starting furans 1a, 2 and cationic species A, B, C, and D.
Species
EHOMO, eV ELUMO, eV ω,a eV
q(CH2),b e
q(C=O),b e
k(CH2)LUMO,с % k(C=O)LUMO,с %
−6.82
−8.93
−10.43
−7.43
−8.57
−2.20
−4.59
−6.65
−3.06
−4.60
2.2
5.3
9.6
−0.066
0.379
0.6
27.8
1a
A
B
2
26.3
(COH+)
−0.060
0.428 (COH+)
0.528 (COH+)
0.391
6.9
24.0
(COH+)
0.054
26.1
3.1
5.5
8.0
–
–
–
–
−
–
15.4
5.7
31.2
(COH+)
0.400
0.417 (COH+)
C
D
22.9
(COH+)
−9.78
−5.91
0.488 (COH+)
q(Ofuran),b e
Species
q(C1),b e
q(C2),b e
q(C3),b e q(C4),b e
0.152
0.158
0.313
−0.192
−0.097
−0.162
−0.302
−0.220
−0.010
0.352
0.371
0.209
−0.464
−0.406
−0.374
1a
A
B
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Beilstein J. Org. Chem. 2016, 12, 2125–2135.
Table 1: Selected electronic characteristics (DFT calculations) of starting furans 1a, 2 and cationic species A, B, C, and D. (continued)
0.210
0.161
0.228
−0.209
−0.106
−0.119
−0.209
−0.217
−0.119
0.210
0.330
0.228
−0.568
−0.404
−0.376
2
C
D
aGlobal electrophilicity index ω = (EHOMO + ELUMO)2/8(ELUMO − EHOMO). bNatural charges. cContribution of atomic orbitals into the molecular orbital.
the furan ring in species A, B, C, and D. However, from these The spectral data clearly prove that protonation of 1a in TfOH
calculations no unambiguous answer could be obtained that gives rise to dication A (Scheme 1). Thus, in the 13C NMR
reveals what cations in pairs A or B, and C or D may take part spectrum the signal at δ 67.5 ppm belongs to the protonated
in electrophilic reactions.
hydroxymethyl group CH2O+H2. This means that dehydration
of this group does not occur in TfOH and cation B is not
To investigate this issue in more detail we studied the proton- formed. For comparison, chemical shifts of carbocationic
ation of furans 1a and 2 in the superacid TfOH by NMR spec- centers in various benzyl cations (R2)ArC+ lie in a much more
troscopy. Upon dissolving 1a and 2 in TfOH in the NMR tube down-field range of ~182–270 ppm [50-57]. Comparison of 1H
the formation of deep-red solutions was observed. 1H and and 13C NMR spectra shows that signals of protons and carbons
13C NMR data of the generated cationic species are collected in in the furan ring of A are substantially down-field shifted in
Table 2 (see spectral figures in Supporting Information File 1). comparison with the corresponding signals of its neutral precur-
Table 2: 1H and 13C NMR data of furans 1a, 2 in CDCl3 and species A, D in TfOH at room temperature.
Species
Solvent
NMR data
13C
1H
CDCl3
2.84 (s, 1H, OH), 4.71 (s, 2H, CH2),
57.6 (CH2), 109.9 (C2), 122.8 (C3),
6.51 (d,(J = 3.5 Hz, 1H, H2), 7.21 (d, 152.4 (C4), 160.7 (C1), 177.7 (CHO)
J = 3.5 Hz, 1H, H3), 9.57 (s, 1H,
CHO)
1a
TfOH
5.85 (s, 2H, CH2), 7.44 (d, J = 4.2 Hz, 67.5 (CH2), 121.0 (C2), 148.5 (C3),
1H, H2), 8.79 (d, J = 4.2 Hz, 1H, H3), 152.8 (C4), 171.9 (C1), 175.9
9.04 (s, C=OH+)
(C=OH+)
A
2
CDCl3
TfOH
7.33 (s, 2H, H2), 9.86 (s, CHO)
119.1 (C2), 154.2 (C1), 179.2 (CHO)
8.48 (s, 2H), 9.84 (s, C=OH+)
136.8 (C2), 156.0 (C1), 186.6
(C=OH+)
D
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Beilstein J. Org. Chem. 2016, 12, 2125–2135.
sor 1a. This reveals a significant positive charge delocalization under the action of various acids (Table 3). In all cases
in the furan ring in A that is in good agreement with the DFT 5-(phenylmethyl)furfural (3a) as Friedel–Crafts reaction prod-
calculations (vide supra).
uct was obtained. Thus, only the hydroxymethyl or
halogenomethyl group in furans 1a–c were involved in the reac-
According to the NMR data (Table 2 and Supporting Informa- tions. The aldehyde group remained intact despite the DFT
tion File 1) protonation of 2 in TfOH leads to the O,O-diproto- calculations predicted a high electrophilicity for the carbon of
nated species D. Analogous to dication A, a down-field shift of the protonated aldehyde group (Table 1). The best results (the
signals of protons and carbons of the furan ring in 1H and highest yield of 3a) were achieved with TfOH at room tempera-
13C NMR spectra of D compared to the signals for 2 was ob- ture for 1 h (Table 3, entries 1, 7, and 9). Other acids were less
served, pointing out a charge delocalization in the furan moiety. efficient, leading to 3a in lower yields or harsher conditions
Also, the down-field shift of the 13C signal of the protonated (130 °C) were required for acidic zeolites H-USY, CBV-720
aldehyde group in species D indicates that this carbon should be and CBV-500 (Table 3, entries 3, 4, 8). Since the NMR data
a reactive electrophilic center. Contrary to that, the signal of the showed the generation of dication A from 1a (Table 2), this
carbon of the protonated aldehyde group in A is even slightly reaction, most probably, proceeds through an SN2 pathway,
up-field shifted compared to the same signal in 1a. This indi- where “pure” heteroaromatic cation B is not formed. At least
cates weak electrophilic properties of the protonated aldehyde the reaction may go through late transition state, in which the
group in A. Signals of protons bonded to aldehyde and C–O bond in the CH2O+H2 group is rather elongated, resulting
oxymethyl groups in species A and D were not registered in in a larger positive charge on this carbon than it has been pre-
1H NMR due to the fast proton exchange with the superacidic dicted by calculations (see Table 1). It should be noted, that the
medium at room temperature.
yields of reaction products in Tables 3–5 are isolated yields
after column chromatographic separation. The remaining mate-
Thus, the NMR data revealed that protonation of furans 1a and rials are some oligomeric compounds.
2 in superacid TfOH resulted in the formation of dications A
and D, respectively, although DFT calculations (Table 1) did Using these conditions (TfOH, rt, 1 h), we carried out reactions
not manifest that clearly.
of 5-HMF (1a) with various arenes in TfOH. Additionally we
investigated the reactions under the action of zeolite CBV-720,
Next, 5-HMF (1a), 5-(chloromethyl)furfural (1b) and since zeolites are considered as “green” catalysts in organic
5-(bromomethyl)furfural (1c), both of which are also promising synthesis [60-66] and the data are collected in Table 4. Simi-
biomass-derived products [58,59], were reacted with benzene larly to the reaction with benzene (Table 3), 1a with other
Table 3: Reactions of furans 1a–c with benzene under the action of various acids.
Entry
Reaction conditions
Yield of 3a,a %
Furan
Acid
T, °C
t, h
1
2
3
4
5
6
7
8
9
1a
1a
1a
1a
1a
1a
1b
1b
1c
TfOH (20 equiv)
TfOH (20 equiv)
zeolite CBV-500c
zeolite CBV-720c
H2SO4 (50 equiv)
AlCl3 (5 equiv)
rt
1
1
3
1
1
1
1
3
1
91
rt
–b
130
130
rt
47
45
19
rt
oligomers
TfOH (20 equiv)
zeolite CBV-500
TfOH (20 equiv)
rt
75
25
68
130
rt
aIsolated yields. bReaction was carried out without benzene, and starting 1a was quantitatively recovered. cThe ratio of 1a–c/zeolite Brønsted acidic
sites was around 2:1.
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Beilstein J. Org. Chem. 2016, 12, 2125–2135.
Table 4: Reactions of 5-HMF (1a) with arenes under the action of TfOH or acidic zeolite CBV-720.
Entry ArH
Reaction conditions
Reaction productsa
Total
yielda,
%
ArH
acid
T, °C
t, h
3
4
(equiv) (equiv)
1
toluene
1.2
TfOH (20) rt
1
56
isomers-4a (10%)
3b (23%), 3c (23%)
3b (44%), 3c (44%)
3b (24%), 3c (24%)
2
3
toluene
toluene
4
TfOH (20) rt
CBV-720b 130
3
1
isomers-4a (10%)
98
48
125
–
4
o-xylene
4
TfOH (20) rt
1
77
4b (23%)
4b (37%)
3d (32%), 3e (22%)
3d (37%), 3e (22%)
5
6
o-xylene
m-xylene
4
TfOH (20) rt
24
1
96
34
1.2
TfOH (20) rt
3f (28%)
4c (6%)
4c (20%)
4c (32%)
7
m-xylene
m-xylene
m-xylene
m-xylene
4
TfOH (20) rt
TfOH (20) rt
TfOH (20) rt
3
3f (75%)
3f (12%)
95
44
–
8
4
24
72
1
9
4
oligomers
10
2.5
CBV-720b, 130
CS2
3f (79%)
–
79
11
p-xylene
1.2
TfOH (20) rt
1
71
3g (53%)
4d (18%)
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Table 4: Reactions of 5-HMF (1a) with arenes under the action of TfOH or acidic zeolite CBV-720. (continued)
12
13
14
p-xylene
p-xylene
p-xylene
4
4
4
TfOH (20) rt
TfOH (20) rt
3
3g (91%)
3g (21%)
3g (78%)
4d (5%)
4d (17%)
–
96
38
78
24
1
CBV-720b, 130
CS2
pseudo-
cumene
15
4
TfOH (20) rt
1
72
4e (32%)
3h (28%), 3i (12%)
3h (53%), 3i (23%)
16
17
pseudo-
cumene
10
4
TfOH (20) rt
24
1
oligomers
–
pseudo-
cumene
CBV-720b, 130
CS2
–
76
1,2-dichloro-
benzene
18
19
4
4
TfOH (20) rt
1
1
–
–
53
11
3j (36%), 3k (17%)
3j (7%), 3k (4%)
1,2-dichloro-
benzene
CBV-720a, 130
CS2
20
21
anisole
anisole
4
3
TfOH (20) rt
1
1
–
–
51
52
3l (42%), 3m (9%)
3l (34%), 3m (18%)
CBV-720b, 130
CS2
22
23
veratrole
veratrole
4
4
TfOH (20) rt
2
1
–
–
62
21
3n (62%)
3n (21%)
CBV-720b, 130
CS2
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Table 4: Reactions of 5-HMF (1a) with arenes under the action of TfOH or acidic zeolite CBV-720. (continued)
24
mesitylene
5
TfOH (20) rt
2
–
17
3o (17%)
aIsolated yields. bThe ratio of 1a/zeolite Brønsted acidic sites was around 2:1.
arenes yielded 5-arylmethylfurfurals 3b–o in TfOH or with showing complex behavior of these furans under superacidic
zeolite CBV-720. However, the use of activated arenes, such as conditions.
toluene, xylenes and pseudocumene, afforded additional
Friedel–Crafts products, namely furans 4a–e (Table 4, entries 1, Concerning the reaction mechanism, according to NMR data
2, 4–8, 11–13, and 15). These compounds were formed by (see Table 2) the reactive species, derived from 1a in TfOH,
hydroxyalkylation due to the interaction of species A with is cation A. In zeolite cages the activation of the CH2OH
arenes (see related reactions [34-38]). The polymethylated group of 1a takes place due to the coordination of the basic
arenes possess a sufficient π-nucleophilicity for the reaction centers of this molecule with Brønsted and Lewis acidic sites of
with the protonated aldehyde group of the intermediates zeolite.
generated from 1a in TfOH. Whereas less nucleophilic arenes,
such as benzene (Table 3) and 1,2-dichlorobenzene (Table 4, 2,5-DFF (2) reacted with arenes under electrophilic activation
entries 18 and 19), did not give rise to the corresponding furans with formation of 5-diarylmethylfurfurals 5a–g (Table 5,
4. Also, the reactions with anisole and veratrole led only to Figure 2). Contrary to compound 1a, which was activated with
furans 3l, m and 3n, respectively, and no formation of com- the Brønsted superacid TfOH to achieve Friedel–Crafts prod-
pounds 4 was observed (Table 4, entries 20–23). Under the ucts 3 and 4 (Table 3 and Table 4), compound 2 gave better
superacidic conditions the substrates anisole and veratrole may results with strong Lewis acids AlX3 (X = Cl, Br) (Table 5,
be protonated at the oxygen atoms [33], thus leading to entries 4, 5, 9, 11, 13, and 15). The coordination of aluminum
a decreased π-nucleophilicity of these arenes. It should be noted halides with the aldehyde group results in the activation of one
that in the case of zeolites we explored CS2 as low coordinating of the aldehyde groups, catalyzing the reaction subsequently
solvent to avoid blocking zeolite acidic sites by π-donating with two arene molecules resulting in the 1,1-diarylated prod-
arenes.
uct. The second aldehyde group does not take part in the reac-
tion (compare with data from ref. [38]). This is due to both, an
Individually isolated compounds 3f and 3g being dissolved in insufficient electrophilic activation by these particular acids and
TfOH at room temperature for 24 h gave rise to mixtures con- the low nucleophilicity of benzene. Also the reaction of 2 with
taining furans 4c and 4d along with starting 3f and 3g, respec- benzene was promoted by zeolite CBV-500, which is more
tively. This may prove that compounds 4 are the secondary acidic than CBV-720 (see Supporting Information File 1), and
reaction products. It is interesting to note that compounds 4 the latter was not be able to give rise to 5a (Table 5, entries
were not observed in reactions with zeolite (Table 4, entries 3, 6–8).
10, 14 and 17), most likely, due to lower acidity of the zeolite
compared to TfOH and spatial restrictions in zeolite cages, Electron-donating xylenes in the reaction with 2 showed a more
diminishing the contact between protonated aldehyde groups complex behavior. The different isomeric xylenes led to com-
and the substrate (arene) molecules.
pounds 5b–e in the presence of AlBr3 (Table 5, entries 9, 11,
and 13). On the other hand, in the Brønsted superacid TfOH o-
We also varied reaction conditions (time, amount of arene) in and m-xylenes gave rise to complex oligomeric mixtures
TfOH to check yields of compounds 3 and 4. In general, in- (Table 5, entries 10 and 12) having masses up to 1400–1500 Da
creasing the reaction time up to 3–24 h led to an increase in the according to MALDI–MS (see Supporting Information File 1).
yield of furans 4 and a decreased yield of compounds 3 These oligomers may have formed due to the participation of
(compare pairs of entries in Table 4: 4 and 5, 7 and 8, 12 and both aldehyde groups of species D (see Scheme 1 and Table 2)
13). But during long reaction times (24–72 h) compounds 3 and in the reaction with these electron-rich arenes. Under the action
4 were completely cleaved in TfOH (Table 4, entries 9 and 16), of AlBr3 2,5-DFF did not react with 1,2-dichlorobenzene, due
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Beilstein J. Org. Chem. 2016, 12, 2125–2135.
Table 5: Reactions of 2,5-DFF 2 with arenes under the action of various acids.
Entry
ArH
Reaction conditions
Reaction products, 5
acid (equiv)
T, °C
t, h
substituents R in Ar
yielda (%)
1
benzene
benzene
benzene
benzene
benzene
benzene
benzene
benzene
o-xylene
o-xylene
m-xylene
TfOH (20)
rt
rt
2
H
5a (90%)
5a (74%)
5a (84%)
5a (92%)
5a (98%)
5a (13%)c
5a (46%)
–d
2
H2SO4 (50)
2
H
3
FSO3H (20), SO2
AlCl3 (5)
−45
rt
2
H
4
1
H
5
AlBr3 (5)
rt
1
H
6
CBV-500b
CBV-500b
CBV-720b
AlBr3 (5)
130
130
130
rt
1
H
7
10
10
1
H
8
H
9
3,4-Me2
oligomers
3,5-Me2
2,4-Me2
oligomers
2,5-Me2
2,5-Me2
3,4-Cl2
2,3-Cl2
–d
5b (72%)
10
11
TfOH (20)
AlBr3 (5)
rt
1
rt
1
5c (36%)
5d (15%)
12
13
14
15
m-xylene
TfOH (20)
AlBr3 (5)
rt
rt
rt
rt
1
1
1
1
p-xylene
5e (78%)
5e (87%)
5f (82%)
5g (16%)
p-xylene
TfOH (20)
TfOH (20)
1,2-dichlorobenzene
16
1,2-dichlorobenzene
AlBr3 (5)
rt
1
aIsolated yields. bThe ratio of 2/zeolite Brønsted acidic sites was around 2:1. cIncomplete conversion; 55% of starting 2 was recovered. dNo reaction
and quantitative recovery of starting 2.
Figure 2: X-ray crystal structure of compounds 5a (a), and 5c (b) (ORTEP diagrams, ellipsoid contour of probability levels is 50%, CCDC reference
numbers 5a: 1483523, 5c: 1483524).
2133

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took place in TfOH (Table 5, entries 15 and 16).
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Conclusion
We have developed a simple and effective synthesis of various
arylmethyl and diarylmethyl-substituted furans by reactions of
5-HMF and 2,5-DFF with arenes under electrophilic activation
by Brønsted/Lewis (super)acids or acidic zeolites H-USY.
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In these reactions 5-HMF in TfOH gives rise to 5-(aryl-
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arenes. Reactions of 5-HMF with arenes under the action of
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The electrophilic intermediates derived from the protonation of
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contribution to organic syntheses based on biomass-derived
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Supporting Information
doi:10.1002/anie.201510090
Supporting Information File 1
21.Galkin, K. I.; Krivodaeva, E. A.; Romashov, L. V.; Zalesskiy, S. S.;
Kachala, V. V.; Burykina, J. V.; Ananikov, V. P. Angew. Chem., Int. Ed.
2016, 55, 8338–8342. doi:10.1002/anie.201602883
22.Li, W.; Xu, Z.; Zhang, T.; Li, G.; Jameel, H.; Chang, H.; Ma, L.
BioResources 2016, 11, 5839–5853.
Experimental procedures, characterization of compounds,
1H, 13C, 19F NMR spectra, and data on DFT calculations.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-12-202-S1.pdf]
doi:10.15376/biores.11.3.5839-5853
23.Choudhary, V.; Mushrif, S. H.; Ho, C.; Anderko, A.; Nikolakis, V.;
Marinkovic, N. S.; Frenkel, A. I.; Sandler, S. I.; Vlachos, D. G.
J. Am. Chem. Soc. 2013, 135, 3997–4006. doi:10.1021/ja3122763
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Acknowledgements
This work was supported by the Russian Scientific Foundation
(grant no 14-13-00448). Spectral studies were performed at the
Center for Magnetic Resonance and Research Center for X-ray
Diffraction Studies of Saint Petersburg State University, Saint
Petersburg, Russia.
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