HMF and furfural: Promising platform molecules in rhodium-catalyzed carbonylation reactions for the synthesis of furfuryl esters and tertiary amides

Article abstract of DOI:10.1016/j.jcat.2019.11.008

A biomass involved rhodium-catalyzed carbonylative synthesis of furfuryl esters and tertiary amides has been developed. 5-Hydroxymethylfurfural (HMF) was used as both substrate and CO surrogate for the first time in a carbonylation reaction, and both alkyl and aryl iodides were tolerated well to afford the desired furfuryl esters in moderate to good yields. In addition, furfural was also utilized as a CO source for the synthesis of tertiary amides. A variety of tertiary amides were obtained in moderate to excellent yields with good functional groups compatibility. Notably, tertiary amines were used as the amine source through a C[sbnd]N bond cleavage pathway in the absence of additional oxidant.

Full text of DOI:10.1016/j.jcat.2019.11.008

Journal of Catalysis 381 (2020) 215–221
Contents lists available at ScienceDirect
Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat
HMF and furfural: Promising platform molecules in rhodium-catalyzed
carbonylation reactions for the synthesis of furfuryl esters and tertiary
amides
Xinxin Qi a,c, Rong Zhou a, Han-Jun Ai a, Xiao-Feng Wu a,b,
⇑
a Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, People’s Republic of China
b Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Straße 29a, Rostock 18059, Germany
c Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663
North Zhongshan Rd., Shanghai 200062, People’s Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
A biomass involved rhodium-catalyzed carbonylative synthesis of furfuryl esters and tertiary amides has
been developed. 5-Hydroxymethylfurfural (HMF) was used as both substrate and CO surrogate for the
first time in a carbonylation reaction, and both alkyl and aryl iodides were tolerated well to afford the
desired furfuryl esters in moderate to good yields. In addition, furfural was also utilized as a CO source
for the synthesis of tertiary amides. A variety of tertiary amides were obtained in moderate to excellent
yields with good functional groups compatibility. Notably, tertiary amines were used as the amine source
through a CAN bond cleavage pathway in the absence of additional oxidant.
Received 19 October 2019
Revised 31 October 2019
Accepted 4 November 2019
Keywords:
Carbonylation
Rhodium catalyst
Furfuryl esters
Tertiary amides
Tertiary amines
Biomass conversion
Ó 2019 Elsevier Inc. All rights reserved.
1. Introduction
and other industries. While considering the versatile utility of fur-
furyl esters, the synthetic methods are rather limited, largely rely-
Nowadays, under the background of sustainable development,
we urgently need to displace our use of fossil carbon with alterna-
tives as the fossil reserves are diminishing. As the only currently
available carbon source apart from fossil resources, biomass has
become an attractive logical alternative to petroleum [1]. 5-
Hydroxymethylfurfural (HMF) and furfural, the potentially most
important platform molecules derived from lignocellulosic bio-
mass [2,3], can be subjected to a variety of chemical modifications
for preparing various useful intermediates [4] via hydrogenation
[5], oxidation [6], amination [7], etherification [8], decarboxylation
[9], and etc (Scheme 1, eq a and b). Thus, it is of great significance
to convert this biomass derived intermediates into higher value-
added products.
ing on the nucleophilic substitution of furfuryl alcohol (FA) with
acyl halide, anhydride, or activated ester with narrow substrates
scope and low efficiency [11]. Thus, the development of general
and efficient protocol for the preparation of furfuryl esters is highly
in demand. In recent years, transition-metal-catalyzed carbonyla-
tion reactions provide a straightforward alternative for preparing
carbonyl-containing compounds. But as an important C1 source,
CO gas suffers from the disadvantages of being highly toxic, flam-
mable and requires high-pressure equipment. Therefore, several
CO surrogates including metal-carbonyl complexes, formamides,
aldehydes, formic acid, oxalyl chloride etc. have been successively
explored [12]. Nevertheless, in most cases, the by-product gener-
ated after the extraction of carbonyl group is useless, and this is
a critical issue in terms of atom economy. Furthermore almost
none of the CO surrogates can be applied to the alkyl-involved rad-
ical carbonylation reactions, since the acyl radical would decar-
bonylate at 130 °C, and a really high pressure of CO is usually
needed to reverse the reaction (Scheme 1, eq c) [13]. Thus, to
explore a radical carbonylation approach without high pressure
is urgent and necessary. Herein, we wish to report a carbonylation
method with HMF as both CO surrogate and nucleophile for the
Furfuryl esters, a class of very important flavoring agents, are
naturally found in several products such as coffee, cocoa, nuts,
and pork meat [10]. Many methods have been developed for the
synthesis of these compounds due to their wide application as fla-
vor modifiers and flavoring enhancers in food, beverage, cosmetics
⇑
Corresponding author.
E-mail address: xiao-feng.wu@catalysis.de (X.-F. Wu).
https://doi.org/10.1016/j.jcat.2019.11.008
0021-9517/Ó 2019 Elsevier Inc. All rights reserved.

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X. Qi et al. / Journal of Catalysis 381 (2020) 215–221
ami
Scheme 1. Transformations of HMF and furfural.
synthesis of furfuryl esters via a CO-transfer pathway (Scheme 1,
eq d) [14]. It’s worth mentioning that this is the first example of
radical carbonylation reaction using biomass derived intermedi-
ates as the CO surrogates instead of high CO gas pressure. Addition-
ally, tertiary amides can be synthesized from aryl iodides with
tertiary amines by using furfural as the CO source as well
(Scheme 1, e).
the additive in 2-methyltetrahydrofuran at 125 °C for 24 h. The
desired product furan-2-ylmethyl benzoate (2a) was obtained in
65% yield (Table 1, entry 1). However, when using Pd(OAc)2, Pd
(dppp)Cl2 or [Ir(cod)Cl]2 as the catalysts, no target product was
obtained. These results are due to the extremely low conversion
of substrates, which implies the tested catalysts are luck of ability
for HMF decarbonylation and the HMF could be recovered (Table 1,
entry 2). With this in mind, we focused on rhodium complexes as
catalysts instead of palladium or iridium complexes due to their
higher decarbonylation ability of aldehydes. As expected, the final
product (2a) was obtained in 62% yield with [Rh(cod)Cl]2 as the
catalyst (Table 1, entry 3). Other catalysts such as Rh(nbd)2BF4
and [Rh(CO)2Cl]2 provided the desired product in lower yields
(Table 1, entry 4). A variety of ligands were also evaluated. How-
2. Results and discussion
Initially, iodobenzene (1a) and HMF were chosen as the model
substrates, with Rh(cod)2BF4 as the catalyst and DPPP as the ligand,
in the presence of Na2CO3 as the base and 4 Å MS (SiO2 powder) as

X. Qi et al. / Journal of Catalysis 381 (2020) 215–221
217
Table 1
entry 5). The reactions delivered unsatisfactory yields of 2a with
alternative bidentate phosphine ligands such as DPPE, DPPB, Xant-
phos, DPPF, and BINAP (Table 1, entry 7). Specifically with DPPP,
the yield was significantly decreased when the ligand-to-metal
ratio was changed to 1:1 or 2:1, which implies that there might
be two different rhodium-phosphine complexes for decarbonyla-
tion and carbonylation respectively (Table 1, entries 8–9). The base
was also critical for the reaction as the target product was not
detected when organic base such as Et3N, DBU and DiPEA were
used (Table 1, entry 10). Intriguingly, compared to Na2CO3, carbon-
ates bearing other alkali metal cations displayed no or little reac-
tivity (Table 1, entry 11). Other sodium bases screened delivered
the furfuryl ester in lower yield (Table 1, entry 12). Furthermore,
4 Å MS turned out to be vital to increase the reaction efficiency
(Table 1, entry 13). Finally, when the reaction time extended to
30 h, the yield of product decreased (Table 1, entry 14).
With the optimized reaction conditions in hand, the substrates
scope of aryl iodides was investigated and shown in Table 2. Sub-
strates with functional groups such as methyl, ethyl, t-butyl, meth-
oxy, trifluoromethoxy, and 3,4-dimethyl group, gave the target
products in moderate to good yields (2b-2i). Halides groups includ-
ing fluoro, chloro, and 3-fluoro-4-methyl, furnished the corre-
sponding products in moderate yields (2k-2o). Examination of
electron-withdrawing substituents showed that slightly lower
yields were produced compared to electron-donating groups (2p,
2q). Heteroaryl groups such as 5-iodoindole, and 3-
iodothiophene could also successfully deliver the corresponding
products in 32% and 46% yields (2s, 2t). Moreover, biphenyl and
naphthalene substituents also gave the desired products in moder-
ate yields (2v, 2w).
Optimization of the reaction conditions.a
Entry Variation from the standard reaction conditions
Yield (%)
1
2
3
4
5
6
7
8
None
65 (64)
0
62
37, 21
0
0
Pd(OAc)2, Pd(dppp)Cl2, or [Ir(cod)Cl]2 as the catalyst
[Rh(cod)Cl]2 as the catalyst
Rh(nbd)2BF4 or [Rh(CO)2Cl]2 as the catalyst
Rh(PPh)3Cl as the catalyst
PPh3, PCy3, BuPAd2 instead of DPPP
DPPE, DPPB, Xanphos, DPPF, BINAP instead of DPPP 16, 0, 11, 46, 0
DPPP (6 mol%)
DPPP (12 mol%)
Et3N, DBU, DIPEA instead of Na2CO3
K2CO3, Li2CO3, Cs2CO3 instead of Na2CO3
NaHCO3, NaOH, Na3PO4 instead of Na2CO3
without 4 Å MS
38
58
0
0
56, 0, 21
55
58
9
10
11
12
13
14
extend the reaction time to 30 h
a
Reaction conditions: iodobenzene (1 mmol), HMF (1.2 mmol), Rh(cod)2BF4
(6 mol%), DPPP (9 mol%), Na2CO3 (1 mmol), 4 Å MS (150 mg), 2-methyltetrahydro-
furan (2.5 mL), 125 °C, 24 h. Yields were determined by GC with dodecane as an
internal standard. Yields of isolated products are given within parentheses.
DPPP = 1,3-bis(diphenylphosphino)propane;
ethane;
(diphenylphosphino)-9,9-dimethylxanthene; DPPF = 1,10-bis(diphenylphosphino)-
ferrocene; BuPAd2 = butyldi-1-adamantylphosphine; cod = 1,5-cyclooctadiene;
nbd = norbornadiene.
DPPE = 1,2-bis(diphenylphosphino)
Xanphos = 4,5-bis
DPPB = 1,4-bis(diphenylphosphino)butane;
ever, with monodentate phosphine ligands such as PPh3, PCy3 and
BuPAd2, HMF could hardly be converted, only furnishing biphenyl
as the main byproduct (Table 1, entry 6) [15]. This phenomena was
also observed when Rh(PPh3)3Cl was used as the catalyst (Table 1,
Subsequently, various alkyl iodides were examined as well
(Table 3). Gratifyingly, most of them were compatible with the
standard reaction conditions, and the corresponding products were
Table 2
Synthesis of furfuryl esters from aryl iodides.a
a
Reaction conditions: aryl iodides (1 mmol), HMF (1.2 mmol), Rh(cod)2BF4 (6 mol%), DPPP (9 mol%), Na2CO3 (1 mmol), 4 Å MS (150 mg), 2-
methyltetrahydrofuran (2.5 mL), 125 °C, 24 h, isolated yields. b135 °C. c115 °C.

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X. Qi et al. / Journal of Catalysis 381 (2020) 215–221
Table 3
Synthesis of furfuryl esters from alkyl iodides.a
a
Reaction conditions: alkyl iodides (1 mmol), HMF (1.2 mmol), Na2CO3 (1 mmol), Rh(cod)2BF4 (6 mol
%), DPPP (9 mol%), 4 Å MS (150 mg), 2-methyltetrahydrofuran (2.5 mL), 135 °C, 24 h, isolated yields.
Table 4
isolated in moderate yields. In case of methyl and ethyl iodides,
lower yields were obtained, probably due to their low boiling point
(4a, 4b). Unfortunately, secondary and tertiary alkyl iodides pro-
vided the ether products rather than the desired esters.
Optimization of the reaction conditions for amide production.a
During the optimization process for furfuryl ester production, in
the case of using triethylamine as the base, traces of N,N-
diethylbenzamide could be detected. Based on literature [16], we
believe the amine group was from the organic base. However, no
additional oxidant was added which is compulsory according to lit-
erature [16]. Hence we turned attention to this and attempted to
improve the reaction efficiency. Iodobenzene and triethylamine
were chosen as the initial substrates, with 2-furaldehyde as the
CO source. The desired amide product was obtained in 32% yield
with Rh(cod)2BF4 as the catalyst and DPPP as the ligand in 2-
methyltetrahydrofuran (2 mL) at 110 °C for 24 h (Table 4, entry
1). Both bidentate and monodentate ligands screened resulted in
lower yields compared to DPPP (Table 4, entries 2–3). We next
examined rhodium catalyst precursors, the use of Rh(PPh3)Cl pro-
vided a higher yield (Table 4, entries 4–5). Solvents screening
showed that THF was the best solvent (Table 4, entries 6–7). The
yield can be increased to 51% when the temperature changed to
Entry
Variation from the standard reaction conditions
Yield (%)
1
2
3
4
5
6
7
8
None
32
0
DPPE, DPPB, DPPF instead of DPPP
Xantphos, PPh3 instead of DPPP
RhCl3, [RhCl(CO)2]2, Rh(pcy)Cl2 as the catalyst
Rh(acac)[CO]2, Rh(PPh3)Cl as the catalyst
THF, 1,4-dioxane, CH3CN as the solvent
Toluene, DCM, DMF as the solvent
140 °C
2-furaldehyde (1.2 mmol)
Et3N (1.8 mmol)
12 h
H2O (1 mmol)
11, 0
31, 0, 0
30, 40
42, 36, 0
34, 0, 30
51
59
60
60
63
9
10
11
12
13
Iodobenzene (1.2 mmol), 2-furaldehyde (1 mmol)
68 (65)
a
Reaction conditions: iodobenzene (1 mmol), 2-furaldehyde (2 mmol), Rh(-
cod)2BF4 (2.5 mol%), dppp (4 mol%), Et3N (2 mmol), 2-methyltetrahydrofuran
(2 mL), 110 °C, 24 h. Yields were determined by GC with dodecane as an internal
standard. Yields of isolated products are given within parentheses.
Table 5
Synthesis of amides from aryl iodides.a
a
Reaction condition: aryl iodides (1.2 mmol), 2-furaldehyde (1 mmol), triethylamine (1.8 mmol),
H2O (1 mmol), Rh(PPh3)3Cl (2.5 mol%), dppp (4 mol%), THF (2 mL), 140 °C, 12 h, isolated yields.
b160 °C.

X. Qi et al. / Journal of Catalysis 381 (2020) 215–221
219
140 °C (Table 4, entry 8). It was noteworthy that with lower
amount of 2-furaldehyde and Et3N, the wished amide product
can be obtained in higher yield (Table 4, entries 9–10). There was
no improvement when the reaction time decreased to 12 h (Table 4,
entry 11). Moreover, H2O turned out to be an effective additive to
this reaction (Table 4, entry 12). Finally, the ratio between
iodobenzene and 2-furaldehyde was studied and the yield of the
amide product can be improved to 68% (Table 4, entry 13).
With the best reaction conditions in hand, the substrates testing
were carried out subsequently. Various aryl iodides were trans-
formed into the corresponding amides in low to good yields
(Table 5). In the case of amines, symmetrical amines can be acti-
vated to provide the desired amide products in moderate to good
yields (Table 6, 6fb-6ff). For unsymmetrical alkyl amine substrates,
the corresponding products were isolated with a moderate yield
and selectivity (Table 6, 6fg-6fi). Notably, only one major amide
product was obtained with aryl substituent (Table 6, 6fj, 6fk).
In order to get more insight into the reaction mechanism for
furfuryl esters synthesis, several control experiments were carried
out (Scheme 2). First, in the absence of catalyst, ligand or base, no
desired product could be observed. Additionally, there was no pro-
duct detected by GC when 2 equivalents of TEMPO (2,2,6,6-tetrame
thylpiperidinooxy) was used under the standard reaction condi-
tions. These preliminary studies suggest that a free radical path-
way might be involved. To reveal the detail mechanism, in-situ
electron paramagnetic resonance (EPR) experiments with DMPO
(5,5-dimethyl-1-pyrroline N-oxide) were performed (Scheme 2,
a-c). The EPR measurement shows very weak signals in the
Table 6
Synthesis of amides from tertiary amines.a
a
Reaction condition: 4-iodoanisole (1.2 mmol), 2-furaldehyde (1 mmol), amine (1.8 mmol), H2O
(1 mmol), Rh(PPh3)3Cl (2.5 mol%), DPPP (4 mol%), THF (2 mL), 12 h, 140 °C, isolated yields.
Scheme 2. Control experiments.

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X. Qi et al. / Journal of Catalysis 381 (2020) 215–221
1319;
absence of substrates (Scheme 2, a). When alkyl iodides and HMF
were added into the reaction, radical signals were detected and
the EPR spectrum is very complex due to the superimposition of
EPR signals arising from different spin adducts (Scheme 2, b).
Switching the alkyl iodide to iodobenzene resulted in a similar
EPR spectrum (Scheme 2, c), which implies that free iodine radical
might be generated in the reaction.
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In summary, HMF, a renewable resource, played a dual role as
both CO surrogate and reaction reagent in a rhodium-catalyzed
carbonylative reaction for the synthesis of furfuryl esters. This is
the first example of a carbonylation process using a biomass
derived intermediate as CO surrogate in the absence of gaseous
CO. Furthermore, a rhodium-catalyzed carbonylative C-N bond
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was utilized as the CO precursor, and a variety of tertiary amides
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General procedure for furfuryl esters synthesis: Rh(cod)2BF4
(6 mol%), DPPP (0.09 mmol), Na2CO3 (1 mmol) and 4A MS (SiO2,
powder, 150 mg) were transferred into an oven-dried tube
(15 mL), which was evacuated and backfilled with N2 (5x). 2-
Methyltetrahydrofuran (2.5 mL), alkyl or aryl iodide (1 mmol),
HMF (1.2 mmol) were added into the tube via syringe and sealed
with Teflon plug. The reaction mixture was stirred at 125 °C for
24 h. After the reaction was complete, the mixture was concen-
trated by rotary evaporation. The crude product was purified by
column chromatography (EA/PE = 1/20) on a silica gel to afford
the desired product.
General procedure for amides synthesis: Rh(PPh3)3Cl (2.5 mol
%) and DPPP (0.04 mmol) were transferred into an oven-dried tube
(15 mL), which was evacuated and backfilled with N2 (5x). THF
(2 mL), H2O (1 mmol), aryl iodides (1.2 mmol), furfural (1 mmol)
and amine (1.8 mmol) were added into the tube via syringe and
sealed with Teflon plug. The reaction mixture was stirred at
140 °C for 12 h. After the reaction was complete, the mixture was
concentrated by rotary evaporation. The crude product was puri-
fied by column chromatography (EA/PE = 1/20) on a silica gel to
afford the desired product.
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Declaration of Competing Interest
[10] G.A. Burdock, Fenaroli’s Handbook of Flavor Ingredients, fifth ed., CRC Press,
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We have no conflict of interest to declaration!
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Acknowledgment
The authors thank the financial supports from NSFC (21772177,
21602201).
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Supplementary data to this article can be found online at
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