Searching for novel reusable biomass-derived solvents: Furfuryl alcohol/water azeotrope as a medium for waste-minimised copper-catalysed azide-alkyne cycloaddition

Article abstract of DOI:10.1039/c6gc01941b

Herein, we report the first application of the furfuryl alcohol/water azeotrope as a sustainable and easily recoverable reaction medium in organic chemistry. The applicability of this novel medium was tested in copper-catalysed azide-alkyne cycloaddition

Full text of DOI:10.1039/c6gc01941b

View Article Online
View Journal
Green
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: L. Vaccaro, D.
Rasina, F. Ferlin, S. Santoro and A. Lombi, Green Chem., 2016, DOI: 10.1039/C6GC01941B.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/greenchem

Page 1 of 6
Green Chemistry
View Article Online
DOI: 10.1039/C6GC01941B
Green Chemistry
RSCPublishing
ARTICLE
Searching for novel reusable biomass-derived
solvents: furfuryl alcohol/water azeotrope as medium
for the waste-minimised copper-catalysed azide-
alkyne cycloaddition†
Cite this: DOI: 10.1039/ b000000x
Received 00th January 2012,
Accepted 00th January 2012
Dace Rasina,a Aurora Lombi,a Stefano Santoro,a Francesco Ferlin,a and Luigi Vaccaro*a
DOI: 10.1039/b000000x
Herein, we report the first application of the furfuryl alcohol/water azeotrope as a sustainable and
easily recoverable reaction medium in organic chemistry. The applicability of this novel medium
was tested in the copperꢀcatalysed azideꢀalkyne cycloaddition (CuAAC), a reaction usually
conducted in mixtures of water and an organic solvent. Our reaction conditions allowed isolating
the expected triazoles in generally good yields and usually in shorter times compared to classical
reaction conditions, also proving a wide substrate scope. A large fraction of the furfuryl
alcohol/water azeotrope can be recovered by simple distillation at the end of the reaction, which
results in a dramatic decrease in waste production and Eꢀfactors, compared to typically employed
CuAAC procedures.
www.rsc.org/
Introduction
typically produced by hydrogenation of lignocellulosic
biomassꢀderived levulinic acid14,15 and, due to its physicalꢀ
The vast majority of the chemicals and fuel produced
nowadays comes from fossil nonꢀrenewable resources. On a
large scale, the replacement of these materials with alternatives
deriving from renewable resources is a high priority in order to
establish a more modern and competitive and sustainable
chemical production. Biomass represents the only renewable
source of carbon,1ꢀ4 and it has been estimated that 25ꢀ30% of
chemical commodities will be generated from biomass by
2030.2ꢀ4 In this perspective, large attention is currently devoted
to finding alternative platform chemicals deriving from
renewable biomass resources5 that could be used, directly or
after modifications, as fuels or for the production of valueꢀ
added chemicals and materials.6,7
chemical properties, represents an ideal replacement for dipolar
aprotic solvents (e.g. dimethylformamide, ꢀmethylꢀ2ꢀ
pyrrolidone), whose use is now strictly regulated because of
their toxicity.16
We have also been searching for other biomassꢀderived
chemicals that could find potential application as a reaction
medium in chemical processes, and we individuated furfuryl
N
alcohol (FA) as
a very interesting candidate. FA is
manufactured by hydrogenation of furfural, one of the products
deriving from degradation of hemicellulose (Scheme 1),17 and
has found its main application in the synthesis of resins and as
intermediate in organic syntheses.18
It has been calculated that most of the waste generation
associated to organic syntheses, particularly in pharmaceutical
industries, comes from the use of solvents.8 Moreover, life
cycle assessments have also confirmed that solvents account
for the majority of the environmental footprint in the
production of key areas such as the pharmaceutical industry.9 It
is therefore not surprising that chemical industries are
increasingly concerned about their choices in the use of
solvents.10 The replacement of commonly employed solvents,
which almost entirely derive from fossil resources, with
alternative reaction media that could be easily produced from
biomass would represent a major advancement in terms of
sustainability for the chemical industry.11 An interesting and
representative example of a biomassꢀderived chemical which
has recently come to attention as a possible substitute for
traditional solvents is γꢀvalerolactone (GVL).12,13 GVL is
H2O
H2
catalyst
O
H3O+
H2O
OH
H3O+
O
O
O
OH
OH
Biomass
(hemicellulose)
OH
OH
Pentoses (C5)
Furfuryl Alcohol
Furfural
Scheme 1. Reaction pathway for furfuryl alcohol production from biomass.
FA is a clear liquid that, as typical of alcohols, is miscible with
water and several organic solvents (e.g. acetone, ethylacetate,
benzene, chloroform).
A desirable feature for a sustainable reaction medium is the
possibility for it to be easily recovered at the end of the process
and reused. This would in fact dramatically reduce its
environmental impact. Pure FA has a relatively high boiling
point of 171 ºC, which would compromise its possible recovery
This journal is © The Royal Society of Chemistry 2013
Green Chem., 2014, 00, 1-3 | 1

Green Chemistry
Page 2 of 6
VJieowuArrtnicalelONnlainme e
ARTICLE
DOI: 10.1039/C6GC01941B
or, at least, make it very energetically demanding.10b However,
very interestingly, it forms an azeotrope with water (20 wt% of
FA) that boils at 98.5 ºC, which is a reasonable temperature for
distillation.
Table 1. CopperꢀCatalysed AzideꢀAlkyne Cycloadditiona
CuSO4—5H2O (2 mol%)
Naꢀascorbate (10 mol%)
R1
N
N
N
R2
R1 N3
+
(A) Imidazole (20 mol%),
FA/H2O (az.)
R2
The use of homogeneous mixtures of an organic solvent and
water as reaction medium is very common in organic
chemistry, mainly to ease the dissolution of both organic and
inorganic reagents, as well as inorganic additives and/or
catalyst. These organic solvent/water mixtures are used in
ratios that are generally suggested by practical tradition and
cannot be easily recovered and reused, therefore producing
waste. At this concern, we have developed several protocols
based on the use of safer media and solid catalytic systems19
and proposed that aqueous azeotropes can be a very effective
solution, combining the benefits of aqueous solvents with being
easily recoverable and reusable.20
or
(B) H2O/tꢀBuOH (2:1)
1
2
3
Solvent Time
system (h)
Conv.
(%)b
Entry
Product
N
Bn
N
N
A
B
6
100 (68)c
66
1
2
24
Ph
3a
N
Bn
N
N
A
B
3
100 (79)d
99
24
nBu
3b
MeO
Me
In this perspective, we reasoned that the FA/water azeotrope
could represent a sustainable and recoverable alternative to
commonly used mixtures of water and an organic solvent. Here
we should mention that, to the best of our knowledge, FA or
the FA/water azeotrope have never been used as reaction media
in organic chemistry applications.
In order to verify our hypothesis we decided to test the
FA/water azeotrope as medium in one of the most widely
applied reactions in organic synthesis which is typically
performed in aqueous/organic mixtures: the copperꢀcatalysed
azideꢀalkyne cycloaddition (CuAAC).21 As a typical click
reaction, CuAAC is a very robust reaction and normally
proceeds in mild conditions, ambient temperature, with low
catalyst loading, in different pH values and gives products in
high yields with minimal work up. Applications of CuAAC for
the preparation of materials of interest in different areas is
countless.22
N
N
24
24
100 (59)c
84
N
A
B
3
4
Ph
3c
3d
N
N
N
A
B
6
24
100 (87)c
100
Ph
Me
N
N
N
5
6
A
A
24
24
100 (81)d
98 (81)c
nBu
3e
N
C12H25
N
N
nBu
3f
Classical CuAAC is performed by in situ generation of Cu(I)
from Cu(II) salts (CuSO4 or Cu(OAc)2) using sodium ascorbate
or ascorbic acid as reductant in water media with organic coꢀ
7
A
6
98 (87)c
solvents such as alcohols (tꢀBuOH, EtOH, MeOH), DMSO,
N
acetonitrile, THF or CH2Cl2. Cu(I) salts can also be used
directly, but this typically requires inert atmosphere to prevent
oxidation. Addition of an organic base (2,6ꢀlutidine, Et3N,
imidazoles, DIPEA or pyridine) or different ligands can
stabilize Cu(I), reduce reaction times and improve reaction
yields.23 Recently, considerable attention has turned to green
chemistry approaches for CuAAC and immobilized Cuꢀ
catalysts,24 solventꢀfree conditions25 and reactions in flow26
have been reported.
N
Ph
O
N
A
B
3
3
100 (95)c
100
8
9
Ph
3h
N
N
EtO
O
N
A
A
6
3
100 (80)c
100 (91)c
Ph
3i
3j
MeO
N
N
N
N
10
11
CO2Me
Results and discussion
We started our investigation by testing the FA/water azeotrope as
reaction medium for the synthesis of 1,4ꢀdisubstitutedꢀ1,2,3ꢀ
triazoles from azides and alkynes (Table 1).
MeO
N
N
A
24
100 (91)c
OPh
3k
2 | Green Chem., 2014, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 3 of 6
Journal Name
Green Chemistry
View Article Online
ARTICLE
DOI: 10.1039/C6GC01941B
thiophenyl (entry 7), ketone (entry 8) and aromatic halides
(entries 12ꢀ14) are compatible with the reaction conditions, and
the related products are selectively formed without observable
sideꢀproducts formation. Ester functionalities are also tolerated
and no transesterification with FA was observed (entries 9 and
10). Interestingly, trimethylsilylacetylene gives TMSꢀ
containing triazole 3o as major product (entry 15), with a
limited (less than 10 %) formation of the monoꢀsubstituted
triazole 3p, as detected by GC analysis.28 However, product 3p
can be obtained by adding TBAF to the reaction mixture after 3
hours and stirring at 30 ºC for additional 21 hours (entry 16).
Moreover, our method allows the preparation in good yields of
bisꢀtriazoles (entry 17), a class of compounds that has found
applications in different fields.29
12
13
14
A
A
A
6
3
3
100 (93)c
100 (86)d
100 (84)c
N
Bn
N
N
Br
O
3m
MeO
N
N
N
Cl
O
3n
MeO
N
N
N
15
A
A
3
95 (68)e
TMS
Table 2. Preparation of 1,4ꢀdisubtitutedꢀ1,2,3ꢀtriazoles from alkylbromidesa
3o
3p
MeO
NaN3 (2 equiv.)
N
CuSO4—5H2O (2 mol%)
Naꢀascorbate (10 mol%)
16f
24
100 (67)e
N
N
N
R
N
N
R
Br
+
Ph
imidazole (20 mol%),
FA/H2O (az.) (0.2 M)
Ph
OH
4
2a
3
N
N
Time (h) Conv. (%)b
17
A
3
100 (82)c
N
N
Temperature
(ºC)
Entry
1
Product
N
N
Bn
Bn
3q
N
Bn
N
N
a Reaction conditions: 1 (1 mmol), 2 (1 mmol), CuSO4 5H2O (2 mol%), Naꢀ
ascorbate (10 mol%), (A) 5 mL FA/H2O (20 wt%), imidazole (20 mol%);
(B) 5 mL tꢀBuOH/H2O (1:2). b Conversion of 1 and 2 to 3 determined by GC
analysis using 4ꢀbromoanisole as internal standard; isolated yields in
parentheses. c Product is solid in the reaction medium and was isolated by
filtration. Product is a oil in the reaction medium and was isolated by
decantation of the azeotrope, addition of water to precipitate the product and
filtration. Product is a oil in the reaction medium and was isolated by
EtOAc/water workꢀup and subsequent column chromatography. Prepared
30
3
3
100 (92)c
100 (94)c
100 (87)c
89 (53)d
.
Ph
3a
N
Ph
N
N
d
2
3
4
30
30
60
O
O
Ph
e
3h
f
N
from trimethylsilylacetylene; TBAF (2 equiv.) was added after consumption
of starting materials (3h) and the mixture was stirred for additional 21h at 30
ºC.
EtO
N
N
18
48
Ph
3i
As catalyst we used what is probably the most commonly employed
system in CuAAC reactions: 2 mol% CuSO4 5H2O and 10 mol%
N
n-Hex
.
N
N
sodium ascorbate. In several cases, for the sake of comparison, we
also conducted the reaction in the representative water/tꢀBuOH (2:1)
mixture, which is commonly used in CuAAC reactions. When using
FA/water azeotrope we found optimal results by adding as
ligand a catalytic amount of imidazole (20 mol%).27
Reactions in FA/H2O azeotrope achieve full conversion in 3–
24 h, and usually the reaction time is shorter compared to the
same reaction conducted in tꢀBuOH/water (1:2) (Table 1,
Ph
3r
a Reaction conditions: 4 (1 mmol), 2a (1 mmol), CuSO4.5H2O (2 mol%), Naꢀ
ascorbate (10 mol%), imidazole (20 mol%), NaN3 (2 mmol), 5 mL FA/H2O
(20 wt%). b Conversion of 1 and 2 to 3 determined by GC analysis using 4ꢀ
bromoanisole as internal standard; isolated yields in parentheses. c Product is
solid in the reaction medium and was isolated by filtration. d Product is solid
in the reaction medium and was isolated by filtration and washed with water
and hexane to remove unreacted starting materials.
entries 1, 2 and 4). These results can be ascribed to the
apparently lower solubility of the products and substrates in
For the isolation of the products
3, we have defined two
FA/H2O azeotropes in comparison with tꢀBuOH/water (1:2).
general methods. First, if the product precipitated in the
reaction medium, simple filtration followed by washing of the
solid with water was sufficient to obtain pure products.
Otherwise, when the product was oil in the reaction medium
the solvent mixture was removed by decantation and water was
added to precipitate the product. In almost all the cases
products were pure and no additional purification was required,
with triazoles 3o and 3p being the only exceptions.
With adequate stirring, this determines a beneficial effect for
both reactions giving solid or oily products. Further
investigations are ongoing to deeper understand this
phenomenon.
Substrate scope is quite general, with both alkyl and aryl azides
and alkynes affording the corresponding products in yields
ranging from good to excellent. Various substituents such as
This journal is © The Royal Society of Chemistry 2012
Green Chem., 2014, 00, 1-3 | 3

Green Chemistry
Page 4 of 6
VJieowuArrtnicalelONnlainme e
ARTICLE
DOI: 10.1039/C6GC01941B
It is known that CuAAC reactions can also be conducted with chemicals employed and therefore the definition of a protocol
the in situ formation of the organic azide starting from a for their recovery and reuse is fundamental for the
corresponding alkyl halide and sodium azide.24a,30 To test minimisation of waste in synthetic processes.
whether this possibility is also applicable in the FA/water
azeotrope, we reacted alkyl bromides (4) with phenylacetylene Conclusions
2a and 2 equivalents of sodium azide in the presence of the
previously used catalytic system (Table 2). To our delight
benzyl bromide, 2ꢀbromoacetophenone and ethyl bromoacetate
In conclusion we reported what, to the best of our knowledge,
is the first application of biomassꢀderived furfuryl alcohol as a
reaction medium in organic chemistry. Using the FA/water
azeotrope instead of pure FA, the reaction mixture is easily
recoverable by simple distillation. The applicability of the
FA/water mixture as reaction medium was tested in the copperꢀ
reacted smoothly and the corresponding triazoles 3a, 3h and 3i
were isolated in 87ꢀ94% yields (Table 2, entries 1ꢀ3).
Unfortunately, the less reactive hexyl bromide gave low
conversion at 30 ºC. Higher temperature (60 ºC) and longer
reaction time (48 h) were required to achieve 89 % conversion
to 1ꢀhexylꢀ4ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazole 3r (Table 2, entry 4).
Isolated yield was moderate (53 %), since additional washing
of the solid product with hexane was necessary in order to
remove unreacted starting materials.
Finally, to test the recoverability of the reaction medium, we
performed the representative reaction between 4ꢀazidoanisole
1b and phenylacetylene 2a on a 30 mmol scale, in our standard
reaction conditions but at higher concentration (Scheme 2).
catalysed azideꢀalkyne cycloaddition,
a
reaction often
performed in mixtures of water and an organic solvent. Our
reaction conditions lead to the selective formation of the
expected triazoles in good to excellent yields, often in shorter
times compared to the reactions conducted in tꢀBuOH/water.
Moreover, a wide substrate scope was demonstrated, with
different functional groups being tolerated in our reaction
conditions. Finally, the use of the FA/water azeotrope lead to a
considerable reduction in waste generation compared to
classical CuAAC procedures, as proven by the dramatic
reduction in the Eꢀfactor values.
We believe that the FA/water azeotrope can represent a
sustainable and chemically efficient alternative reaction
medium, especially for reactions that work best in mixtures of
water and an organic solvent. Further investigations in this
perspective are currently ongoing in our laboratories.
MeO
CuSO4—5H2O (2 mol%)
Naꢀascorbate (10 mol%)
MeO
N
N
N
Ph
+
imidazole (20 mol%),
FA/H2O (az.)
N3
Ph
1M, 30 ºC, 3h
3c
1b
2a
30 mmol scale
yield: 91% by filtration
E-Factor = 4.3
Scheme 2. CuAAC Reaction on a 30 mmol scale.
Experimental
In these conditions the isolated yield of product 3c could be
considerably improved, from 59% to 91%, mainly as a
consequence of easier product isolation at a larger scale. At the
end of the process the FA/water azeotrope was distilled,
allowing the recovery of 21 g (81% of the initial amount, this
result can be certainly further optimized) of the mixture. NMR
analysis confirmed the purity of the recovered azeotrope, which
could be reused for subsequent reactions. We have reused the
same recovered azeotropes for three consecutive runs without
observing any change in the ratio of the mixture.
General procedure for the synthesis of 1,5-disubstituted 1,2,3-
triazoles
Imidazole (14 mg, 20 mol%), sodium ascorbate (20 mg, 10
mol%) and copper(II) sulfate pentahydrate (5 mg, 2 mol%)
were dissolved in 5 mL of furfuryl alcohol (20 wt%) water
mixture, in a screwꢀcapped vial equipped with a magnetic
stirrer. Alkyne (1 mmol) and azide (1 mmol) were added and
the resulting heterogeneous mixture was stirred vigorously at
30 °C, until GC analysis indicated complete consumption of the
reactants.
To assess the greenness of our procedure we calculated the Eꢀ
factor31 of our large scale reaction (Scheme 2), obtaining a
value of 4.3. As a comparison we also calculated the Eꢀfactors
for some typical CuAAC procedures. Usually these reactions
are performed in water and an organic coꢀsolvent, and the
recovery of the resulting mixture is practically not possible. In
our analysis we considered: i) the classical procedures reported
Acknowledgements
We gratefully acknowledge the Università degli Studi di
Perugia for financial support. S.S. gratefully acknowledges the
MIUR for financial support through the fellowship
PGR123GHQY, funded within “Programma Giovani
Ricercatori, Rita Levi Montalcini”. D.R. was supported by EC
7th Framework Program project REGPOTꢀCTꢀ2013ꢀ316149ꢀ
InnovaBalt.
by Sharpless and Fokin using t
ꢀBuOH/water,21c ii) a procedure
using CH2Cl2/H2O as reaction medium32 and, iii) a solventꢀfree
reaction.25a Even if in our calculation we neglected the fact that
typically these procedures require product purification by
column chromatography, still we calculated an average Eꢀ
factor of 106. Thus, our method leads to a significantly (96%)
smaller production of waste compared to classical CuAAC
procedures. This is not surprising, since this confirms
mathematically that solvents represent the largest mass of the
Notes
aLaboratory of Green Synthetic Organic Chemistry, CEMIN
Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia
Via Elce di Sotto, 8, 06123 Perugia, Italy.
–
Eꢀmail: luigi.vaccaro@unipg.it
4 | Green Chem., 2014, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 5 of 6
Journal Name
Green Chemistry
View Article Online
ARTICLE
DOI: 10.1039/C6GC01941B
9550ꢀ9570; (c) P. G. Jessop, Green Chem., 2011, 13, 1391ꢀ1398; (d) I.
T. Horváth, Green Chem., 2008, 10, 1024ꢀ1028; (e) C. Capello, U.
Fischer, K. Hungerbühler, Green Chem., 2007, 9, 927–934.
†
Electronic Supplementary Information (ESI) available: Experimental
details, characterization data, and copies of NMR spectra of all
compounds. See DOI: 10.1039/b000000x/
12 (a) D. Rasina, A. KahlerꢀQuesada, S. Ziarelli, S. Warratz, H. Cao, S.
Santoro, L. Ackermann and L. Vaccaro, Green Chem., 2016, in press,
DOI: 10.1039/C6GC01393G; (b) X. Tian, F. Yang, D. Rasina, M.
Bauer, S. Warratz, F. Ferlin, L. Vaccaro and L. Ackermann, Chem.
Commun., 2016, in press, DOI: 10.1039/C6CC03468C; (c) G.
Strappaveccia, E. Ismalaj, C. Petrucci, D. Lanari, A. Marrocchi, M.
Drees, A. Facchetti and L. Vaccaro, Green Chem., 2015, 17, 365ꢀ372;
(d) G. Strappaveccia, L. Luciani, E. Bartollini, A. Marrocchi, F. Pizzo
and L. Vaccaro, Green Chem., 2015, 17, 1071ꢀ1076; (e) E. Ismalaj, G.
Strappaveccia, E. Ballerini, F. Elisei, O. Piermatti, D. Gelman and L.
Vaccaro, ACS Sustainable Chem. Eng., 2014, 2, 2461ꢀ2464.
13 (a) P. Pongrácz, L. Kollár and L. T. Mika, Green Chem., 2016, 18, 842ꢀ
847; (b) Z. Zhang, ChemSusChem, 2016, 9, 156ꢀ171; (c) L. Qi, Y. F.
Mui, S. W. Lo, M. Y. Lui, G. R. Akien and I. T. Horváth, ACS Catal.,
2014, 4, 1470ꢀ1477; (d) E. I. Gürbüz, J. M: R. Gallo, D. M. Alonso, S.
G. Wettstein, W. Y. Lim and J. A. Dumesic, Angew. Chem. Int. Ed.,
2013, 52, 1270ꢀ1274; see also: (e) S. G. Wettstein, D. M. Alonso, Y.
Chong and J. A. Dumesic, Energy Environ. Sci., 2012, 5, 8199ꢀ 8203; (f)
Z.ꢀQ. Duan and F. Hu, Green Chem., 2012, 14, 1581ꢀ 1583; (g) L. Qi
and I. T. Horváth, ACS Catal., 2012, 2, 2247ꢀ2249; (h) I. T. Horváth, H.
Mehdi, V. Fábos, L. Boda and L. T. Mika, Green Chem., 2008, 10, 238ꢀ
242.
References
1
2
J. Clarke and F. Deswarte in Introduction to Chemicals from Biomass
(Eds.: J. Clarke, F. Deswarte), John Wiley & Sons, Ltd, 2008, pp. 1ꢀ28.
StarꢀColibri, funded under the Seventh framework Programme of the
European Union (2011): “Joint European Biorefinery Vision for 2030”,
http://www.starꢀcolibri.eu/files/files/visionꢀweb.pdf
3
4
U.S. Department of Energy (2005): “Biomass as Feedstock for a
Bioenergy and Bioproducts Industry:The Technical Feasibility of a
Billion-Ton
Annual
Supply”;
https://www1.eere.energy.
gov/bioenergy/pdfs/final_billionton_vision_report2.pdf
Organisation for Economic Coꢀoperation and Development (2009): “The
Bioeconomy
to
2030:
Designing
a
Policy
Agenda”,
http://www.oecd.org/futures/longtermtechnologicalsocietalchallenges/42
837897.pdf
(a) D. M. Alonso, J. Q. Bond and J. A. Dumesic, Green Chem., 2010,
12, 1493–1513; (b) G. W. Huber and A. Corma, Angew. Chem. Int. Ed.,
2007, 46, 7184–7201.
(a) P. Gallezot, Chem. Soc. Rev., 2012, 41, 1538ꢀ1558; (b) Pacific
Northwest National Laboratory (2007): “Top Value-Added Chemicals
from Biomass Volume II - Results of Screening for Potential Candidates
5
6
14 A. M. Raspolli Galletti, C. Antonetti, V. De Luise, M. Martinelli, Green
Chem., 2012, 14, 688ꢀ694.
from
Biorefinery
Lignin”,
15 S. W. Fitzpatrick, World Patent: WO 96/40609.
http://www1.eere.energy.gov/bioenergy/pdfs/pnnlꢀ16983.pdf; (c) U.S.
Department of Energy (2004): “Top Value Added Chemicals from
Biomass Volume I - Results of Screening for Potential Candidates from
16 R. K. Henderson, C. JiménezꢀGonzález, D. J. C. Constable, S. R. Alston,
G. G. A. Inglis, G. Fisher, J. Sherwood, S. P. Binksa and A. D. Curzons,
Green Chem., 2011, 13, 854ꢀ862.
Sugars
and
Synthesis
Gas”,
17 (a) D. Sun, S. Sato, W. Ueda, A. Primo, H. Garcia and A. Corma, Green
Chem., 2016, 18, 2579ꢀ2597; (b) M. J. Climent, A. Corma and S. Iborra,
Green Chem., 2014, 16, 516–547; (c) R. F. Perez and M. A. Fraga,
Green Chem., 2014, 16, 3942–3950.
18 (a) G. Li, N. Li, M. Zheng, S. Li, A. Wang, Y. Cong, X. Wang and T.
Zhang, Green Chem., 2016, 18, 3607ꢀ3613; (b) A. Gandini, in
Biopolymers – New Materials for Sustainable Films and Coatings, ed.
D. Plackett, John Wiley & Sons, Ltd, 2011, pp. 179–209; (c) J.ꢀP.
Lange, W. D. van de Graaf and R. J. Haan, ChemSusChem, 2009, 2,
437–441; (d) A. Gandini and M. N. Belgacem, in Monomers, Polymers
and Composites from Renewable Resources, Elsevier, Amsterdam,
2008, pp. 115–152; (e) A. Gandini and M. N. Belgacem, Prog. Polym.
Sci., 1997, 22, 1203–1379.
https://www1.eere.energy.gov/bioenergy/pdfs/35523.pdf
7
A. K. Chandel, G. Chandrasekhar, M. B. Silva and S S. da Silva,
Critical Reviews in Biotechnology, 2012; 32, 187–202; (b) V. Menon
and M. Rao, Progress in Energy and Combustion Science, 2012, 38,
522ꢀ550; (c) H. R. Ghatak, Renewable and Sustainable Energy Reviews,
2011, 15, 4042–4052; (d) S. Fernando, S. Adhikari, C. Chandrapal and
N. Murali, Energy & Fuels, 2006, 20, 1727ꢀ1737; (e) A. J. Ragauskas,
C. K. Williams, B. H. Davison, G. Britovsek, J. Cairney, C. A. Eckert,
W. J. Frederick Jr., J. P. Hallett, D. J. Leak, C. L. Liotta, J. R. Mielenz,
R. Murphy, R. Templer and T. Tschaplinski, Science, 2006, 311, 484ꢀ
489; (f) B. Kamm and M. Kamm, Appl. Microbiol. Biotechnol., 2004,
64, 137–145.
8
9
C. JimenezꢀGonzalez, C. S. Ponder, Q. B. Broxterman and J. B. Manley,
Org. Process Res. Dev., 2011, 15, 912–917.
C. JiménezꢀGonzález, A. D. Curzons, D. J. C. Constable and V. L.
Cunningham, Int. J. Life Cicle Assess., 2004, 9, 114–121.
19 (a) M. Alonzi, M. P. Bracciale, A. Broggi, D. Lanari, A. Marrocchi, M.
L. Santarelli and L. Vaccaro, J. Catal. 2014, 309, 260–267; (b) S.
Bonollo, D. Lanari, J. M. Longo, L. Vaccaro, Green Chem. 2012, 14,
164–169; (c) S. Bonollo, D. Lanari, T. Angelini, F. Pizzo, A. Marrocchi,
L. Vaccaro, J. Catal. 2012, 285, 216‒222; (d) O. Piermatti, F. Pizzo, L.
Vaccaro. J. Catal. 2011, 277 112–119; (e) A. Zvagulis, S. Bonollo, D.
Lanari, F. Pizzo, L. Vaccaro. Adv. Synth. Catal. 2010, 352, 2489–2496.
(f) L. Castrica, F. Fringuelli, L. Gregoli, F. Pizzo, L. Vaccaro. J. Org.
Chem. 2006, 71, 9536‒9539; (g) S. Bonollo, F. Fringuelli, F. Pizzo, L.
Vaccaro, Synlett 2008, 1574‒1578; (h) F. Fringuelli, F. Pizzo, L.
Vaccaro. Synlett 2000, 311‒314.
20 (a) M. Nocchetti, C. Petrucci, F. Costantino, O. Piermatti, L. Vaccaro,
Chem. Commun. 2015, 51, 15990ꢀ15993; (b) C. Petrucci, G.
Strappaveccia, F. Giacalone, M. Gruttadauria, F. Pizzo, L. Vaccaro, ACS
Sus. Chem. 2014, 2, 2813−2819; (c) C. Pavia, E. Ballerini, L. A. Bivona,
F. Giacalone, C. Aprile, L. Vaccaro, M. Gruttadauria, Adv. Synth. Catal.,
2013, 355, 2007–2018.
21 (a) F. Himo, T. Lovell, R. Hilgraf, V. V. Rostovtsev, L. Noodleman, K.
B. Sharpless and V. V. Fokin, J. Am. Chem. Soc., 2005, 127, 210–216;
(b) V. O. Rodionov, V. V. Fokin and M. G. Finn, Angew. Chem. Int.
Ed., 2005, 44, 2210–2215; (c) V. V. Rostovtsev, L. G. Green, V. V.
Fokin and K. B. Sharpless, Angew. Chem. Int. Ed., 2002, 41, 2596–
2599; (d) C. W. Tornøe, C. Christensen and M. Meldal, J. Org. Chem.,
2002, 67, 3057–3064.
10 (a) L. J. Diorazio, D. R. J. Hose and N. K. Adlington, Org. Process Res.
Dev., 2016, 20, 760ꢀ773; (b) D. Prat, A. Wells, J. Hayler, H. Sneddon,
C. R. McElroy, S. AbouꢀShehada and P. J. Dunn, Green Chem., 2016,
18, 288ꢀ296; (c) H. E. Gottlieb, G. GraczykꢀMillbrandt, G. G. A. Inglis,
A. Nudelman, D. Perez, Y. Qian, L. E. Shuster, H. F. Sneddon and R. J.
Upton, Green Chem., 2016, 18, 3867ꢀ3878; (d) C. M. Alder, J. D.
Hayler, R. K. Henderson, A. M. Redman, L. Shukla, L. E. Shuster and
H. F. Sneddon, Green Chem., 2016, 18, 3879ꢀ3890; (e) N. R. Babij, E.
O. McCusker, G. T. Whiteker, B. Canturk, N. Choy, L. C. Creemer, C.
V. De Amicis, N. M. Hewlett, P. L. Johnson, J. A. Knobelsdorf, F. Li, B.
A. Lorsbach, B. M. Nugent, S. J. Ryan, M. R. Smith and Q. Yang, Org.
Process Res. Dev., 2016, 20, 661ꢀ667; (f) C. P. Ashcroft, P. J. Dunn, J.
D. Hayler and A S. Wells, Org. Process. Res. Dev., 2015, 19, 740ꢀ747;
(g) D. Prat, J. Hayler and A. Wells, Green Chem., 2014, 16, 4546ꢀ4551;
(h) D. Prat, O. Pardigon, H.ꢀW. Flemming, S. Letestu, V. Ducandas, P.
Isnard, E. Guntrum, T. Senac, S. Ruisseau, P. Cruciani and P. Hosek,
Org. Process Res. Dev., 2013, 17, 1517ꢀ1525; (i) K. Alfonsi, J. Colberg,
P. J. Dunn, T. Fevig, S. Jennings, T. A. Johnson, H. P. Kleine, C.
Knight, M. A. Nagy, D. A. Perry and M. Stefaniak, Green Chem., 2008,
10, 31ꢀ36.
11 (a) A. G. Corrêa, M. W. Paixão and R. S. Schwab, Curr. Org. Synth.,
2015, 12, 675ꢀ695; (b) Y. Gu and F. Jérôme, Chem. Soc. Rev., 2013, 42,
22 For recent representative examples see: (a) X Zhang, S. Zhi, W. Wang,
S. Liu, J. P. Jasinskid, W. Zhang, Green Chem. 2016, 18, 2642–2646;
This journal is © The Royal Society of Chemistry 2012
Green Chem., 2014, 00, 1-3 | 5

Green Chemistry
Page 6 of 6
ARTICLE
VJieowuArrtnicalelONnlainme e
DOI: 10.1039/C6GC01941B
(b) S. Chassaing, V. Beneteau and P. Pale, Catal. Sci. Technol. 2016, 6,
923ꢀ957; (c) E. Haldon, M. C. Nicasio and P. J. Pérez, Org. Biomol.
Chem. 2015, 13, 9528ꢀ9550; (d) F. Alonso, Y. Moglie and G. Radivoy,
Acc. Chem. Res. 2015, 48, 2516ꢀ2528; (e) A. Qin, Y. Liu and B. Z.
Tang, Macromol. Chem. Phys. 2015, 216, 818ꢀ828; (f) H. Wu, H. Li, R.
TR. T. K. Kwok, E. Zhao, J. Z. Sun, A. Qin and B. Z. Tang, Sci. Rep.
2014, 4, 5107ꢀ5112; (g) M. Juríček, P. H. J. Kouwer and A. E. Rowen,
Chem. Commun. 2011, 47, 8740ꢀ8749; (h) Themed issue (4) Click
chemistry: function follows form, Chem. Soc. Rev. 2010, 39, 1221ꢀ1408
(i) C. R. Becer, R. Hoogenboom and U. S. Schubert, Angew. Chem. Int.
Ed. 2009, 48, 4900ꢀ4908. For alternative to Cu(I) catalyzed protocols
using organocatalysts see: (j) J. Thomas,S. Jana,J. John,S. Liekensb, W.
Dehaen, Chem. Commun., 2016, 52, 2885ꢀ2888; (k) J. Thomas, J. John,
N. Parekh, W. Dehaen, Angew. Chem. Int. Ed. 2014, 53, 10155ꢀ10159.
(l) D. Amantini, F. Fringuelli, O. Piermatti, F. Pizzo, E. Zunino and L.
Vaccaro. J. Org. Chem., 2005, 70, 6526ꢀ6529; (m) G. D'Ambrosio, F.
Fringuelli, F. Pizzo, L. Vaccaro. Green Chem., 2005, 7, 874ꢀ877.
23 V. O. Rodionov, S. I. Presolski, D. Díaz Díaz, V. V. Fokin and M. G.
Finn, J. Am. Chem. Soc., 2007, 129, 12705–12712.
24 (a) A. Pourjavadi, A. Motamedi, S. H. Hosseini and M. Nazari, RSC
Adv., 2016, 6, 19128–19135; (b) S. Chassaing, V. Bénéteau and P. Pale,
Catal. Sci. Technol., 2016, 6, 923–957; (c) K. Jacob and A. Stolle,
Synth. Commun., 2014, 44, 1251–1257; (d) C. S. Radatz, L. do Amaral
Soares, E. R. Vieira, D. Alves, D. Russowsky and P. H. Schneider, New
J. Chem., 2014, 38, 1410–1417; (e) A. Z. Ahmady, F. Heidarizadeh and
M. Keshavarz, Synth. Commun., 2013, 43, 2100–2109; (e) K. Jacob, A.
Stolle, B. Ondruschka, K. D. Jandt and T. F. Keller, Appl. Catal. Gen.,
2013, 451, 94–100; (f) Y. Wang, J. Liu and C. Xia, Adv. Synth. Catal.,
2011, 353, 1534–1542; (g) L. Bonami, W. Van Camp, D. Van
Rijckegem and F. E. Du Prez, Macromol. Rapid Commun., 2009, 30,
34–38; (h) B. H. Lipshutz and B. R. Taft, Angew. Chem. Int. Ed., 2006,
45, 8235–8238.
25 (a) L. Rinaldi, K. Martina, F. Baricco, L. Rotolo and G. Cravotto,
Molecules, 2015, 20, 2837–2849; (b) I. Jlalia, F. Meganem, J.
Herscovici and C. Girard, Molecules, 2009, 14, 528–539.
26 (a) A.ꢀC. Bédard and S. K. Collins, Org. Lett., 2014, 16, 5286–5289; (b)
S. B. Ötvös, I. M. Mándity, L. Kiss and F. Fülöp, Chem. – Asian J.,
2013, 8, 800–808.
27 Et3N, diisoproprylethylamine, and pyridine gave poorer results.
28 J. T. Fletcher, S. E. Walz and M. E. Keeney, Tetrahedron Lett., 2008,
49, 7030–7032.
29 Z.ꢀJ. Zheng, D. Wang, Z. Xu and L.ꢀW. Xu, Beilstein J. Org. Chem.,
2015, 11, 2557–2576.
30 For representative examples see: (a) Y. M. A. Yamada, S. M. Sarkar and
Y. Uozumi, J. Am. Chem. Soc., 2012, 134, 9285ꢀ9290; (b) M. Liu and O.
Reiser, Org. Lett., 2011, 13, 1102ꢀ1105; (c) P. Appukkuttan, W. Dehaen,
V. V. Fokin and E. Van der Eycken, Org. Lett., 2004, 6, 4223ꢀ4225.
31 R. A. Sheldon, Green Chem., 2007, 9, 1273–1283.
32 B.ꢀY. Lee, S. R. Park, H. B. Jeon and K. S. Kim, Tetrahedron Lett.
2006, 47, 5105–5109.
,
6 | Green Chem., 2014, 00, 1-3
This journal is © The Royal Society of Chemistry 2012