Heterogeneous C-H alkenylations in continuous-flow: Oxidative palladium-catalysis in a biomass-derived reaction medium

Article abstract of DOI:10.1039/c7gc01103b

Herein we report the unprecedented Fujiwara-Moritani reaction catalysed by the commercially available heterogeneous palladium catalyst Pd/C. The reaction works efficiently in GVL, a biomass derived solvent, in the coupling between variously substituted ac

Full text of DOI:10.1039/c7gc01103b

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, L.
Ackermann, S. Santoro and F. Ferlin, Green Chem., 2017, DOI: 10.1039/C7GC01103B.
This is an Accepted Manuscript, which has been through the
Volume 18 Number
7 7 April 2016 Pages 1821–2242
Royal Society of Chemistry peer review process and has been
accepted for publication.
Green
Chemistry
Accepted Manuscripts are published online shortly after
Cutting-edge research for a greener sustainable future
www.rsc.org/greenchem
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
author guidelines.
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, outlined
in our author and reviewer resource centre, 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.
ISSN 1463-9262
CRITICAL REVIEW
G. Chatel et al.
Heterogeneous catalytic oxidation for lignin valorization into valuable
chemicals: what results? What limitations? What trends?
rsc.li/green-chem

Please do not adjust margins
Page 1 of 4
Green Chemistry
View Article Online
DOI: 10.1039/C7GC01103B
Journal Name
ARTICLE
Heterogeneous C–H Alkenylations in Continuous-Flow: Oxidative
Palladium-Catalysis in a Biomass-Derived Reaction Medium
Francesco Ferlin,a Stefano Santoro,a Lutz Ackermann*b and Luigi Vaccaro*a
Received 00th January 20xx,
Accepted 00th January 20xx
Herein we report the unprecedented Fujiwara-Moritani reaction catalysed by commercially available heterogeneous
palladium catalyst Pd/C. The reaction works efficiently in GVL, a biomass derived solvent, in the coupling between
variously substituted acetanilides and electron-poor alkenes, with complete selectivity towards the ortho-substitution.
Moreover, the catalyst can be easily recycled and reused for consecutive reaction runs. We also developed a continuous-
flow procedure, through an easily accessible tailor-made reactor, which allows the production of the C–H alkenylated
products in grams per hour scale.
DOI: 10.1039/x0xx00000x
www.rsc.org/
universally are produced from fossil resources. The use of bio-
based solvents, i.e. chemicals that can be easily obtained from
renewable biomasses with very low carbon footprint, as
Introduction
In recent years, major efforts have been directed towards the
development of methodologies that allow the direct
functionalisation of generally inert C–H bonds.1 The vast
majority of the protocols reported to date make use of soluble
transition metals complexes as catalysts, thus operating in
homogeneous reaction conditions. The main focus of the
research in this field has been the definition of catalytic
systems that would enable the C–H functionalisation to occur
under mild reaction conditions and with good selectivity.2 At
the same time, there has been an increasing interest in the
design of more sustainable protocols for C–H
functionalisations, following the general need of realising
chemical transformations with the least possible formation of
waste and energy consumption.3 In this respect, one approach
alternative reaction media is rapidly gaining importance in
organic chemistry.7 Among these,

-valerolactone (GVL), a
derivative of lignocellulosic biomass, has demonstrated
remarkable potential as a substitute for widely used dipolar
aprotic solvents, such as DMF, DMAc, or NMP.8 In a few cases,
the use of GVL in place of common solvents resulted in
additional desirable effects, such as reduced metal-leaching
from heterogeneous palladium catalysts and improved catalyst
recyclability.8e-f
Very recently, we reported on the use of heterogeneous
palladium catalysts, simple and commercially available Pd/C
and Pd/Al2O3, to promote C–H functionalisation reactions,
such as the Catellani reaction8c and the C–H arylation of 1,2,3-
triazoles.8d In both cases the reactions were conducted in GVL
as reaction medium, the catalyst could be recovered and
reused without loss of efficacy, and the products were isolated
with very limited palladium content.
The Fujiwara-Moritani (FM) reaction is the palladium-catalysed
direct coupling of arenes with alkenes.9 The main advantage
over the classical Mizoroki-Heck reaction is that the FM
reaction does not require a prefunctionalisation of the
aromatic coupling partner, since the aryl-palladium
intermediate is generated through a C–H activation step. The
FM reaction thus offers a straightforward entry to aryl alkenes,
with wide potential application in organic synthesis. Typically,
FM reactions are catalysed by a palladium(II) salt and are
accelerated by the presence of Brønsted acids. It is quite
common indeed to use the acid as the sole reaction medium,
with possible consequences in terms of functional groups
tolerance. Concerning the oxidant, the most used ones are
Cu(OAc)2 and 1,4-benzoquinone (BQ), with relatively few
examples using air or molecular oxygen.10
is the use of insoluble catalysts that operate in
a
heterogeneous fashion.4 This strategy ideally allows for an
easy recovery and reuse of the catalyst, with consequent
reduction in waste generation and costs. Moreover, the use of
heterogeneous catalysts can result in a reduced metal
contamination of the desired products, which is highly
desirable for the practitioner in applied areas. A second, less
explored approach consists in performing the desired reaction
in an environmentally benign medium.5 It is well known in fact
that the vast majority of the waste generated in chemical
processes derives from the use of solvents,6 that almost
a.Laboratory of Green Synthetic Organic Chemistry, Dipartimento di Chimica,
Biologia e Biotecnologie, di Perugia, Via Elce di Sotto 8, 06123 Perugia,
Italy. E-mail: luigi.vaccaro@unipg.it.
b.
- -
, Germany. E-mail:
Lutz.Ackermann@chemie.uni-goettingen.de.
† Electronic Supplementary Information (ESI) available: additional experimental
details, full characterization and NMR spectra of all compounds. See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 2 of 4
ARTICLE
Journal Name
Our long-standing research interest in the development of methyl acrylate, benzyl acrylate and acrylonitrileV.ieSwuAbrtsictlietOuntleinde
sustainable chemical processes11 and our recent findings acetanilides, functionalized with either DeOleI:c1t0r.o10n3-9w/Cit7hGdCr0a1w10in3Bg
concerning the use of heterogeneous catalysts in GVL for or -donating groups, were also competent substrates,
palladium-catalysed reactions8c-g prompted us to investigate generally affording the product of mono-alkenylation in the
the possibility to develop a sustainable Fujiwara-Moritani ortho-position relative to the acetamido-group, confirming the
reaction.
excellent ability of this functionality in directing C–H activation
processes. Importantly, the presence of halide substituents on
the aromatic substrate is well tolerated, which paves the way
to further orthogonal functionalisations through classical
cross-coupling processes. In all the cases, the expected
products were obtained in good to excellent yields, without
noticeable formation of any side products.
Results and discussion
We began our study by reacting acetanilide (1a) with butyl
acrylate (2a) using 2.5 mol% of Pd/C (10% wt) as catalyst in
GVL (Table 1). We found that the reaction occurs smoothly
with 16 equivalents of acetic acid and 2 equivalents of either
Cu(OAc)2 or BQ as oxidant at 150 °C, affording exclusively the
desired ortho-functionalised product (3a) in 85-90% in 24
hours (Table 1, entries 1 and 2). Changing the additive to p-
toluenesulfonic acid (TsOH) allowed to reduce the amount
from 16 to 1 equivalent. Also, while the two tested oxidants
gave similar results when used in combination with AcOH, the
reaction with TsOH is more efficient with BQ than with AcOH
(Table 1, entries 3 and 4). Indeed, TsOH in combination with
BQ also allowed to reduce the reaction temperature to 85 °C.
Finally, we also tested the reaction using a polymer-bound p-
toluenesulfonic acid (PS-TsOH), since this would allow for an
easier recover and reuse of the additive together with the
catalyst (Table 1, entry 5). We were delighted to find that using
just 1 equivalent of this supported acid, with 2 equivalents of
BQ at 85 °C led to obtain product 3a in a striking 95% yield.
Table 1. Optimization of reaction conditions for the Fujiwara-Moritani
reaction in GVL.a
Entry
Acid
Oxidant
T (°C)
150
150
150
85
Yield
90%
85%
65%
87%
95%
1
2
3
4
5
a
AcOH (16 eq)
AcOH (16 eq)
TsOH (1 eq)
TsOH (1 eq)
PS-TsOH (1 eq)
Cu(OAc)2 (2 eq)
BQ (2 eq)
Cu(OAc)2 (2 eq)
BQ (2 eq)
BQ (2 eq)
85
Scheme 1. Scope of the Pd/C-catalysed Fujiwara-Moritani reaction in GVL.
Reaction conditions: 1 (0.5 mmol), 2 (0.55 mmol), Pd/C (2.5 mol%), PS-TsOH
(0.5 mmol), BQ (1 mmol), GVL (1 mL), 85 °C, 24h. a Reaction conducted with 5
mol% of Pd/C and 1 mmol of 2 for 48h.
Reaction conditions: 1a (0.5 mmol), 2a (0.55 mmol), Pd/C (2.5 mol%),
GVL (1 mL), 24h.
These latter reaction conditions were subsequently used to
explore the scope of the Fujiwara-Moritani reaction, using a
variety of substituted acetanilides and alkenes (Scheme 1).
Gratifyingly, the mono-alkenylation occurred selectively in the
ortho-position of acetanilide (1a) in the reaction with various
electron-poor alkenes, such as butyl acrylate, ethyl acrylate,
Crucial to our design of a sustainable process is the possibility
to efficiently recover and reuse the catalytic system, in this
case comprising the palladium catalyst and the polymer-
supported acid. We found that the catalyst/acid mixture can
be easily and efficiently reused for at least five consecutive
runs of the reaction between 1a and 2a, without noticeable
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 4
Green Chemistry
Please do not adjust margins
Journal Name
ARTICLE
loss of activity until the fourth run, and a limited reduction of
product yield in the fifth run (Table 2). Moreover, the amount
of metal released into the reaction medium was measured
after each run by ICP-OES analysis, which revealed that metal-
leaching from the supported catalyst is consistently very
limited (ca. 4 ppm, see Table 2). At this stage we also
performed a hot-filtration test and a Hg-poisoning test, in
order to get insights into the nature of the catalytically active
View Article Online
DOI: 10.1039/C7GC01103B
species. The results of these tests suggest
a possible
Figure 1. Continuous-flow Fujiwara-Moritani reaction.
heterogeneous catalysis (see SI for details), although a “release
and catch” mechanism12 is probably more likely, given the
reaction conditions and the well-known mechanism of the FM
reaction. To the best of our knowledge, this is the first
example of a FM reaction promoted by a simple and
commercially available operationally heterogeneous catalyst
that can be easily and efficiently recycled.13
Table 2. Catalyst recycling for the reaction between 1a and 2a in batch.a
Run 1
Run 2
Run 3
Run 4
Run 5
.
Yield
95%
4.0
95%
3.7
94%
3.8
93%
4.1
87%
4.2
Figure 2. Palladium leaching into solution in the continuous-flow Fujiwara-
Moritani reaction between 1a and 2a.
Pd leaching (ppm)
a
Reaction conditions: 1a (0.5 mmol), 2a (0.55 mmol), Pd/C (2.5 mol%),
GVL (1 mL), 85 °C, 24h.
Conclusions
In conclusion, we have shown that the Fujiwara-Moritani C–H
alkenylation reaction of acetanilides can be efficiently
catalysed by simple and commercially available Pd/C in
biomass-derived GVL as reaction medium. The ortho-
functionalized products are obtained in good to excellent
yields, and the catalyst can be easily recovered and reused for
consecutive reaction runs. Moreover, the process could be
performed in continuous flow conditions using a tailor-made
packed reactor. Performing the reaction in flow has additional
advantages in terms of shorter reaction times and improved
recoverability and durability of the catalyst.
The stability of the heterogeneous catalyst, i.e. its ability to
reliably promote the reaction for consecutive reaction runs,
led us to explore the possibility of scaling-up the process in
continuous flow.14 This approach is particularly suited for
heterogeneous catalysis, with beneficial consequences such as
the possibility to reduce the amount of solvent and the
increased mechanical stability of the catalyst.15 Thus, after
preparing a tailor-made reactor (see SI for details) we pumped
into it a GVL solution of the reactants (1a and 2a, 430 mmol
scale), BQ and TsOH at a 0.5 mL∙min-1 flow rate. After 29 hours
109 grams of product 3a were obtained in 97% yield,
demonstrating the suitability of this approach for medium-
scale continuous productions (Figure 1). Measuring the
amount of palladium released into the GVL solution by ICP-OES
analysis revealed limited metal leaching from the
heterogeneous support (ca. 4 ppm, see Figure 2), comparable
to that observed in batch conditions. In addition, GVL proved
not only to be a safer and greener polar aprotic solvent but
also a more chemically efficient alternative to classic and toxic
polar aprotic solvents as DMF and NMP. In fact, palladium
leaching was significantly lower in GVL than in DMF and NMP
(ca. 4 ppm vs 80 and 31 ppm, respectively) suggesting that also
the durability of the catalyst is higher in GVL than in these
solvents.
Acknowledgements
L. A. thanks the European Research Council under the
European Community 7th Framework Program and the Fonds
der Chemischen Industrie. The Università degli Studi di Perugia
is thanked for financial support. S.S. gratefully acknowledges
the MIUR for “Programma Giovani Ricercatori, Rita Levi
Montalcini” the fellowship N. PGR123GHQY.
Notes and references
1
For selected recent reviews, see: (a) Z. Huang, H. N. Lim, F.
Mo, M. C. Young and G. Dong, Chem. Soc. Rev. 2015, 44
,
We also tested the flow procedure for the reaction with
different acrylates and substituted anilides (see Figure 1),
obtaining in all cases excellent results in terms of product
yields (87-99%) and selectivities.
7764; (b) J. Yang, Org. Biomol. Chem. 2015, 13, 1930; (c) B.
Ye and N. Cramer, Acc. Chem. Res. 2015, 48, 1308; (d) K.
Shin, H. Kim and S. Chang, Acc. Chem. Res. 2015, 48, 1040;
(e) O. Daugulis, J. Roane and L. D. Tran, Acc. Chem. Res.
2015, 48, 1053; (f) B. Liu, F. Hu and B.-F. Shi, ACS Catal. 2015,
5
, 1863; (g) Y. Segawa, T. Maekawa and K. Itami, Angew.
Chem. Int. Ed. 2015, 54, 66; (h) M. Zhang, Y. Zhang, X. Jie, H.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 4 of 4
ARTICLE
Zhao, G. Li and W. Su, Org. Chem. Front. 2014,
Journal Name
M. Matsuda and S. Teranishi, Tetrahedron Lett. 1968, , 633;
1
, 843; (i) L.
9
Ackermann, J. Org. Chem. 2014, 79, 8948; (j) T. Mesganaw
and J. A. Ellman, Org. Process Res. Dev. 2014, 18, 1097; (k) S.
Tani, T. N. Uehara, J. Yamaguchi and K. Itami, Chem. Sci.
2014, 5, 123; (l) S. A. Girard, T. Knauber and C.-J. Li, Angew.
Chem. Int. Ed. 2014, 53, 74; (m) G. Rouquet and N. Chatani,
Angew. Chem. Int. Ed. 2013, 52, 11726; (n) J. Wencel-Delord
(c) Y. Fujiwara, I. Moritani, R. Asano aDnOdI:S1.0T.1e0r3Va9ien/wCis7AhGrtiiC,cl0eJ.1O1An0lm3inBe.
Chem. Soc. 1969, 91, 7166. For selected reviews, see: (d) T.
Kitamura and Y. Fujiwara, in From C–H to C–C Bonds: Cross-
Dehydrogenative-Coupling (Ed.: C.-J. Li), The Royal Society of
Chemistry, 2014, pp 33–54; (e) L. Zhou and W. Lu, Chem. Eur.
J. 2014, 20, 634; (f) J. Le Bras and J. Muzart, Chem. Rev. 2011,
111, 1170; (g) E. M. Ferreira, H. Zhang and B. M. Stoltz, in
The Mizoroki-Heck Reaction (Ed.: M. Oestreich), John Wiley
& Sons, Ltd: Chichester, UK, 2009, pp 345–382; (h) C. Jia, T.
Kitamura and Y. Fujiwara, Acc. Chem. Res. 2001, 34, 633. For
selected recent examples, see: (i) R. Das and M. Kapur,
Chem. Asian J. 2015, 10, 1505; (j) X. Liu and K. K. Hii, J. Org.
Chem. 2011, 76, 8022; (k) D.-H. Wang, K. M. Engle, B.-F. Shi
and J.-Q. Yu, Science 2010, 327, 315; (l) K. M. Engle, D.-H.
Wang and J.-Q. Yu, Angew. Chem. Int. Ed. 2010, 49, 6169;
(m) K. M. Engle, D.-H. Wang and J.-Q. Yu, J. Am. Chem. Soc.
2010, 132, 14137; (n) H. Zhang, E. M. Ferreira and B. M.
Stoltz, Angew. Chem. Int. Ed. 2004, 43, 6144.
and F. Glorius, Nat. Chem. 2013,
Chem. Rev. 2011, 111, 1315.
5, 369; (o) L. Ackermann,
2
For selected examples of meta- or para-selective C–H
functionalisation methodologies see: (a) S. Li, L. Cai, H. Ji, L.
Yang and G. Li, Nat. Commun. 2016, 7, 10443; (b) S. Bag, T.
Patra, A. Modak, A. Deb, S. Maity, U. Dutta, A. Dey, R.
Kancherla, A. Maji, A. Hazra, M. Bera and D. Maiti, J. Am.
Chem. Soc. 2015, 137, 11888; (c) J. Li, S. Warratz, D. Zell, S.
De Sarkar, E. E. Ishikawa and L. Ackermann, J. Am. Chem. Soc.
2015, 137, 13894; (d) J. Luo, S. Preciado and I. Larrosa, J. Am.
Chem. Soc. 2014, 136, 4109; (e) R. Tang, G. Li and J.-Q. Yu,
Nature 2014, 507, 215; (f) Y. Kuninobu, H. Ida, M. Nishi and
M. Kanai, Nat. Chem. 2015, 7, 712; (g) G. Yang, P. Lindovska, 10 For selected examples, see: (a) A. Bechtoldt, C. Tirler, K.
D. Zhu, J. Kim, P. Wang, R.-Y. Tang, M. Movassaghi and J.-Q.
Yu, J. Am. Chem. Soc. 2014, 136, 10807; (h) N. Hofmann and
L. Ackermann, J. Am. Chem. Soc. 2013, 135, 5877; (i) R. J.
Phipps and M. J. Gaunt, Science 2009, 323, 1593.
Raghuvanshi, S. Warratz, C. Kornhaaß and L. Ackermann,
Angew. Chem. Int. Ed. 2016, 55, 264; (b) F. W. Patureau and
F. Glorius, J. Am. Chem. Soc. 2010, 132, 9982; (c) J.-R. Wang,
C.-T. Yang, L. Liu and Q.-X. Guo, Tetrahedron Lett. 2007, 48
,
3
4
(a) L. Ackermann, A. R. Kapdi, K. Potukuchi and S. I.
5449.
Kozhushkov, in Handbook of Green Chemistry. Vol. 7: Green 11 For recent examples, see: (a) V. Kozell, M. McLaughlin, G.
Synthesis (Ed.: C.-J. Li), Wiley-VHC: Verlag, 2012, pp 259–305;
Strappaveccia, S. Santoro, L. A. Bivona, C. Aprile, M.
(b) C.-J. Li and B. M. Trost, Proc. Natl. Acad. Sci. 2008, 105
,
Gruttadauria and L. Vaccaro, ACS Sustainable Chem. Eng.
13197.
2016, 4, 7209; (b) G. Strappaveccia, T. Angelini, L. Bianchi, S.
For recent reviews, see: (a) S. Santoro, S. I. Kozhushkov, L.
Santoro, O. Piermatti, D. Lanari and L. Vaccaro, Adv. Synth.
Catal. 2016, 358, 2134; (c) D. Lanari, M. Alonzi, F. Ferlin, S.
Santoro and L. Vaccaro, Org. Lett. 2016, 18, 2680; (d) D.
Rasina, A. Lombi, S. Santoro, F. Ferlin and L. Vaccaro, Green
Chem. 2016, 18, 6380; (e) E. Ballerini, M. Curini, D. Gelman,
D. Lanari, O. Piermatti, F. Pizzo, S. Santoro and L. Vaccaro,
Ackermann and L. Vaccaro, Green Chem. 2016, 18, 3471; (b)
A. J. Reay and I. J. S. Fairlamb, Chem. Commun. 2015, 51
,
16289; (c) R. Cano, A. F. Schmidt and G. P. McGlacken, Chem.
Sci. 2015, , 5338; (d) L. Djakovitch and F.-X. Felpin,
ChemCatChem 2014, , 2175.
C. Fischmeister and H. Doucet, Green Chem. 2011, 13, 741.
(a) C. Jimenez-Gonzalez, C. S. Ponder, Q. B. Broxterman and 12 M. Gruttadauria, F. Giacalone and R. Noto, Green Chem.,
J. B. Manley, Org. Process Res. Dev. 2011, 15, 912; (b) C. 2013, 15, 2608.
Jiménez-González, A. D. Curzons, D. J. C. Constable and V. L. 13 For an earlier example of FM reaction using
Cunningham, Int. J. Life Cicle Assess. 2004, , 114. polyoxometallate material as catalyst, see: (a) L. L. Chng, J.
6
6
5
6
ACS Sustainable Chem. Eng. 2015, 3, 1221.
a
Pd-
9
7
8
(a) A. G. Corrêa, M. W. Paixão and R. S. Schwab, Curr. Org.
Synth. 2015, 12, 675; (b) Y. Gu and F. Jérôme, Chem. Soc.
Zhang, M. Amoura and J. Y. Ying, Adv. Synth. Catal. 2011,
353, 2988. However, in this example the catalyst needed to
be reloaded with PV3Mo9 after recycling in order to be used
for a subsequent reaction. Another protocol based on a
Pd(II) mesoporous organosilica material has been also
reported: (b) H. Duan, M. Li, G. Zhang, J. R. Gallagher, Z.
Huang, Y. Sun, Z. Luo, H. Chen, J. T. Miller, R. Zou, A. Lei and
Rev. 2013, 42, 9550; (c) I. T. Horváth, Green Chem. 2008, 10
,
1024.
(a) P. Pongr c , L. oll r and L. T. Mika, Green Chem. 2016,
18, 842; (b) Z. Zhang, ChemSusChem, 2016, 9, 156; (c) D.
Rasina, A. Kahler-Quesada, S. Ziarelli, S. Warratz, H. Cao, S.
Santoro, L. Ackermann and L. Vaccaro, Green Chem. 2016,
Y. Zhao, ACS Catal. 2015, 5, 3752.
18, 5025; (d) X. Tian, F. Yang, D. Rasina, M. Bauer, S. Warratz, 14 As recent representative reviews, see: (a) J. A. M. Lummiss,
F. Ferlin, L. Vaccaro and L. Ackermann, Chem. Commun.
2016, 52, 9777; (e) G. Strappaveccia, E. Ismalaj, C. Petrucci,
D. Lanari, A. Marrocchi, M. Drees, A. Facchetti and L.
Vaccaro, Green Chem. 2015, 17, 365; (f) G. Strappaveccia, L.
Luciani, E. Bartollini, A. Marrocchi, F. Pizzo and L. Vaccaro,
Green Chem. 2015, 17, 1071; (g) E. Ismalaj, G. Strappaveccia,
E. Ballerini, F. Elisei, O. Piermatti, D. Gelman and L. Vaccaro,
P. D. Morse, R. L. Beingessner and T. F. Jamison, Chem. Rec.
2017, DOI: 10.1002/tcr.201600139; (b) Sustainable Flow
Chemistry: Methods and Applications (Ed.: L. Vaccaro),
Wiley-VCH: Weinheim, Germany, 2017; (c) B. J. Reizman, Y.-
M. Wang, S. L. Buchwald and K. F. Jensen, React. Chem. Eng.,
2016, 1, 658; (d) A. Adamo, R. L. Beingessner, M. Behnam, J.
Chen, T. F. Jamison, K. F. Jensen, J.-C. M. Monbaliu, A. S.
Myerson, E. M. Revalor, D. R. Snead, T. Stelzer, N.
Weeranoppanant, S. Y. Wong and P. Zhang, Science 2016,
352, 61; (e) H. P. L. Gemoets, Y. Su, M. Shang, V. Hessel, R.
Luque and T. Noël, T. Chem. Soc. Rev., 2016, 45, 83; (f) D.
Cambié, C. Bottecchia, N. J. W. Straathof, V. Hessel and T.
Noël, Chem. Rev. 2016, 116, 10276; (g) A. Nagaki and J.
Yoshida, Top. Organomet. Chem. 2016, 57, 137.
ACS Sustainable Chem. Eng. 2014,
S. W. Lo, M. Y. Lui, G. R. Akien and I. T. Horv th, ACS Catal.
2014, , 1470; (i) E. I. G r , J. M. R. Gallo, D. M. Alonso, S.
2, 2461; (h) L. Qi, Y. F. Mui,
4
G. Wettstein, W. Y. Lim and J. A. Dumesic, Angew. Chem. Int.
Ed. 2013, 52, 1270; (j) S. G. Wettstein, D. M. Alonso, Y. Chong
and J. A. Dumesic, Energy Environ. Sci. 2012,
Q. Duan and F. Hu, Green Chem. 2012, 14, 1581; (l) L. Qi and
I. T. Horv th, ACS Catal. 2012,
5, 8199; (k) Z.-
2
, 2247; (m) I. T. Horv th, H. 15 L. Vaccaro, D. Lanari, A. Marrocchi and G. Strappaveccia,
Mehdi, . os, L. Boda and L. T. Mika, Green Chem. 2008,
10, 238.
For seminal reports, see: (a) I. Moritani and Y. Fujiwara,
Tetrahedron Lett. 1967, 8, 1119; (b) Y. Fujiwara, I. Moritani,
Green Chem. 2014, 16, 3680.
9
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins