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Highly efficient and time economical purification

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Cite this: DOI: 10.1039/c7gc03324a

of olefin metathesis products from metal residues
using an isocyanide scavenger†
Grzegorz Szczepaniak, * Anna Ruszczyńska, Krzysztof Kosiński,
Ewa Bulska and Karol Grela *

Received 3rd November 2017,
Accepted 14th February 2018
DOI: 10.1039/c7gc03324a
rsc.li/greenchem
A sustainable protocol of olefin metathesis in non-degassed, undistilled ethyl acetate under air with com-
mercially available self-scavenging ruthenium catalysts is described. Furthermore, a time economical,
cost-effective and scalable method of removal of ruthenium residues is presented. Treatment of post-
reaction mixtures with an isocyanide scavenger and then with acid followed by a simple filtration is shown
to yield OM products with ruthenium contamination below 5 ppm even in highly challenging cases.
Finally, a telescope RCM/Suzuki–Miyaura sequence with a rapid and efficient purification protocol for
simultaneous removal of Ru and Pd residues from solution is described.

Introduction 2-methyltetrahydrofuran,12 polyethylene glycol,13 dimethyl car-

Olefin metathesis (OM) catalyzed with Mo, W or Ru complexes
is an efficient and selective method of creating new C(sp2)–
C(sp2) bonds.1 Thanks to the compatibility of OM with a wide
variety of functional groups, it is often used in the synthesis of
complex organic molecules2 and in polymer chemistry.3
Appropriate choice of the catalyst, reaction conditions and the
purification protocol, allow OM to fulfill the requirements of
green chemistry.4
Over 60 different OM catalysts are commercially available.5
The most popular group is the 2nd generation ruthenium com-
plexes bearing a N-heterocyclic carbene (NHC) as one of the
ligands, which exhibit high activity and stability and are widely
available.6 2nd generation catalysts are more active and stable
compared to Ru complexes with two phosphine ligands.7
Higher activity is caused by stronger σ-donating properties of
NHC ligands, while higher stability is a consequence of greater
shielding of the metallic center. Even higher stability is
observed in 2nd generation Hoveyda-type catalysts, where the
PCy3 group is replaced with a chelating –Oi-Pr group (Fig. 1).8
OM is most often performed in dichloromethane or
toluene. Both of these solvents are harmful, therefore their use
in the industry is avoided.9 They can be replaced with more
environmentally benign solvents like water,10 ionic liquids,11
bonate,14 p-cymene,15 methyl decenoate,16 glycerol,17 acetic
acid,18 ethyl acetate,19 or supercritical carbon dioxide.20
Alternatively, solvent-free OM can be performed.16,21
Due to the limited stability of ruthenium complexes in the
presence of oxygen and water, OM is generally conducted in
oxygen-free, dry solvents under an inert atmosphere.
Nevertheless, OM under air is possible.22
The rate of OM reactions can be controlled by choosing an
appropriate catalyst. Known ruthenium complexes include
both fast-initiating catalysts which are capable of mediating
the reaction even at 0 °C,23 as well as latent catalysts which
require an external stimulus to initiate the reaction, such as
increased temperature,24 light25 or pH change.26
The purification of OM products from ruthenium residues
poses a challenge to the pharmaceutical industry due to strin-
gent legal limits on heavy metal content in biologically active
compounds, typically less than 10 ppm.27 Furthermore, the
presence of catalyst residues may promote undesirable isomer-

Biological and Chemical Research Centre, Faculty of Chemistry, University of

Warsaw, Pasteura 1, 02-093 Warsaw, Poland.
E-mail: szczepaniak.grzegorz@gmail.com, karol.grela@gmail.com
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ Fig. 1 Selected commercially available olefin metathesis catalysts
c7gc03324a based on ruthenium.

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ization or degradation of the product.28 For this reason, the
development of economical and practical methods of purifi-
cation is of critical importance.29
The problem of ruthenium contamination in OM products
can be solved in several ways: (1) by using a low catalyst
loading, (2) by applying conventional methods of purification
to the product, (3) by conducting a heterogeneous OM, (4) by
using a self-scavenging catalyst, (5) by using scavengers.
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equiv.), require a long scavenging time (more than 1 h) and do
not reduce ruthenium content below 10 ppm.
In 2007, Diver et al. reported a new method for the removal
of ruthenium byproducts using the polar isocyanide D1
(Fig. 2A).46 Isocyanides promote the insertion of the carbene
ligand into the aromatic rings of the NHC ligand, known as
the Buchner reaction (Fig. 2B).47 Coordination of polar isocya-
nides to the metallic center causes the formation of polar, cat-

OM with a small amount of catalyst is a very attractive alytically inactive ruthenium complexes, which are easy to sep-
approach. Frugal use of the catalyst reduces costs and when arate with flash chromatography. The ruthenium content of
less than 10 ppm is used, the problem of ruthenium con- the resulting products is 120–2200 ppm. Use of an isocyanide
tamination is virtually eliminated.30 Unfortunately, the immobilized on silica gel (D2) combined with flash chromato-
minute amount of catalyst is prone to being deactivated by graphy affords OM products that contain less than 10 ppm
trace amounts of air, moisture or impurities.31 Highly pure Ru.48
substrates and solvents are required and optimizing the Recently, we reported a new, small-molecule ruthenium sca-
reaction to very small catalyst loadings is often time con- venger containing tertiary nitrogen atoms.49 Isocyanide QA is
suming, which can nullify any cost advantage of using less an odorless, easy to handle, crystalline solid that is insensitive
catalyst. Literature examples of OM of this type are limited to moisture and air and soluble in many organic solvents and
to simple compounds.32 The synthesis of complex mole- water. A small excess of QA with respect to the catalyst
cules typically requires catalyst loadings in excess of (4.4 equiv.) and a short binding time (30 min) are sufficient.
1000 ppm.33 Removal of ruthenium residues is accomplished by filtering
In laboratory-scale OM, the products are usually purified the post-reaction mixture through a short plug of silica gel, to
using flash chromatography. This technique often proves which QA binds strongly due to the presence of a piperazine
ineffective. Polar products synthesized with the use of large
amounts of catalyst require multiple steps of chromatography,
which causes a significant waste of the product,34 solvents,
sorbents and time, and still does not guarantee that the
product will contain less than 10 ppm Ru.35 The same applies
to crystallization and extraction, while distillation conducted
in the presence of ruthenium catalyst residues can cause a
migration of double bonds in the product.28b
Heterogeneous catalysis makes purification very simple and
enables catalyst reuse, which has economical implications.
However, Farina and coworkers recently criticized the concept
of heterogeneous catalysis using covalently immobilized tran-
sition metal complexes, underscoring that so far, no system of
this kind has found industrial applications.36 Reasons include
rapid deactivation, low turnover numbers, low turnover fre-
quency, leaching of the metal and overall complexity.
Several homogeneous OM catalysts with self-scavenging
properties are known.37 Such catalysts can be removed though
extraction,38 adsorption,39 nanofiltration,40 temperature
change41 or magnetic separation42 after the reaction is com-
pleted. Similarly to heterogeneous catalysts, these modifi-
cations often require multi-step syntheses and are therefore
expensive. Few self-scavenging catalysts are commercially avail-
able, which limits their scope of application.
Ruthenium scavengers are added after the reaction is com-
plete. They bind to the catalyst residues, creating new ruthe-
nium compounds that are easy to separate through extrac-
tion,43 adsorption44 or filtration.45 Their use does not require
any structural modifications to the catalyst, making them
usable together with a variety of commercially available com-
plexes. However, there is always the risk of contaminating the
product with the scavenger itself. Most scavengers described in Fig. 2 (A) Isocyanide scavengers described in the literature, (B) reactiv-
the literature have to be used in a large excess (more than 10 ity of isocyanides toward GII, (C) purification of OM products using QA.

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Green Chemistry
ring in its structure. This method yields OM products with
ruthenium content typically below 10 ppm (Fig. 2C).
Unfortunately, the use of silica gel becomes less effective and
economical as the polarity of the purified compounds
increases.
Herein, we present a new chromatography-free, cost-
effective, simple to use and time-economical method of purifi-
cation of OM products from ruthenium residues. It is based
on the use of a self-scavenging catalyst, the isocyanide QA and
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hydrochloric or citric acid. The obtained OM products exhibit
low ruthenium content (below 10 ppm).
Results and discussion
Several different ruthenium removal strategies were compared
(Scheme 1). The compound 1a was chosen as the test sub-
strate. It easily undergoes ring-closing metathesis (RCM),
giving the hard-to-purify product 1b. This difficulty is caused
by the presence of a polar moiety that tends to bind to ruthe-
nium. A commercially available 2nd generation Hoveyda-type
complex bearing a quaternary ammonium group in the NHC
ligand with a PF6− counterion (Ru1, 1.0 mol%) was selected as
the catalyst. The ionic tag causes a significant increase in
affinity to silica gel as well as a reduction of solubility in non-
polar solvents. It facilitates the removal of the catalyst and
allows noncovalent immobilization on solid supports.50
Ethyl acetate is considered to be an environmentally sus-
tainable, “green” solvent.9 The Skowerski group from Apeiron
Scheme 1 Removal of ruthenium from a reaction mixture by various purification methods.
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Synthesis recently investigated the influence of green solvents
on olefin metathesis with popular Ru-based catalysts.19b The
research showed that using ethyl acetate as the reaction
medium does not negatively affect the yield or selectivity of
OM and gives results comparable to conventional solvents,
such as toluene and dichloromethane. Furthermore, Ru1
exhibited better solubility in ethyl acetate than in toluene. In
light of these facts, we chose ethyl acetate as the solvent.
The reaction was conducted at 70 °C in air, using 8 mmol
of the substrate 1a (Scheme 1). After 2 h, the reaction mixture
from the flask FI was filtered through a frit into the flask FII to
remove any solid precipitates. Subsequently, two aliquots of
10 mL each were taken from the flask FII. One of them was
simply filtered through a syringe filter into the flask I, while
the other was filtered through a syringe filter and then
through silica gel into the flask II. After evaporating the
solvent, the ruthenium content in 1b in both flasks was deter-
mined with inductively coupled plasma mass spectrometry
(ICP-MS). The ruthenium level of the resulting product in flask
I was 864 ppm, while the additional silica gel filtration caused
the level in flask II to be reduced 30-fold, down to 28 ppm.
Next, the isocyanide scavenger QA (4.4 equiv. with respect
to Ru1) was added to the remaining contents of flask FII,
which were then stirred for 1 h at room temperature. The
entire mixture was then filtered into the flask FIII. Two ali-
quots (2 × 10 mL) were taken from the flask FIII and the two
filtration and ruthenium content determination procedures
were repeated. The product 1b obtained from the mixture fil-
tered only through a syringe filter (flask III) contained
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387 ppm Ru, while additional filtration through silica gel Table 1 Comparison of different ruthenium removal strategies
(flask IV) yielded a product with a very low ruthenium content
(less than 5 ppm).
Despite the product 1b from flask III exhibiting a 2-fold
reduction in ruthenium content compared to the use of Ru1
alone (flask I), GC analysis indicated that it was contaminated
with excess QA. This prompted us to search for an effective,
chromatography-free way of removing both the ruthenium resi-
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dues and the excess scavenger.

The isocyanide QA acts as a base due to the presence of ter-
tiary nitrogen atoms in its structure. The addition of 2.2
equivalents of hydrochloric acid or citric acid (CA) causes an
Method of purification, Rub [ppm]
immediate and quantitative precipitation of protonated QA
(HQA) from ethyl acetate. A solution of hydrochloric acid in Catalyst Conv.a [%] A B C D E F G
diethyl ether (10 equiv. with respect to Ru1) was added to the HII 99 4499 4134 3076 223 154 150 198
remaining contents of the flask FIII. The resulting mixture was Ru1 99 1265 40 270 0.9 9.8 9.0 8.8
stirred for 15 min at room temperature. Subsequently, two ali- Ru2 94 321 9.3 22 1.0 3.8 0.7 1.2
Ru3 78 57 3.8 10 0.3 1.3 0.4 0.4
quots (2 × 10 mL) were removed from the flask. One of them Ru4 44 230 19 96 1.2 212 71 6.2
was filtered through a frit (flask V) and after evaporation
a
yielded 1b with 2.7 ppm of Ru that was free from the isocya- Conversions were determined by GC analysis and are based on the
ratio of product/(product + starting material). b Ru content was deter-
nide QA. The other one was filtered through Celite (flask VI), mined by ICP-MS. All reactions used 1 mmol of substrate. Method A:
which reduced the Ru contamination level to 1.1 ppm. filtration through frit. Method B: filtration through silica gel. Method
In the next phase of our research, seven different methods C: (i) QA (4.4 mol%), 70–30 °C, 1 h, (ii) filtration through frit. Method
D: (i) QA (4.4 mol%), 70–30 °C, 1 h, (ii) filtration through silica gel.
(A–G) of removing ruthenium residues from the compound 1b Method E: (i) QA (4.4 mol%), 70–30 °C, 1 h, (ii) HCl (10 mol%, rt,
were evaluated with four commercially available self-scaven- 15 min), (iii) filtration through frit. Method F: (i) QA (4.4 mol%),
ging metathesis catalysts Ru1–4 and the unmodified Hoveyda 70–30 °C, 1 h, (ii) HCl (10 mol%, rt, 15 min), (iii) filtration through
Celite. Method G: (i) QA (4.4 mol%), 70–30 °C, 1 h, (ii) CA (10 mol%,
catalyst HII (Fig. 3). All reactions used 1 mmol of the substrate rt, 15 min), (iii) filtration through frit.
and ethyl acetate as the solvent and were conducted at 70 °C
under ambient atmosphere using 1.0 mol% of the catalyst.
The results are summarized in Table 1.
A simple filtration of the post-reaction mixture through a tration of the post-reaction mixture through a frit (method C)
frit (method A) proved ineffective for all evaluated catalysts afforded 1b with ruthenium content not exceeding 10 ppm
(>10 ppm Ru). The ruthenium contamination of the product only in the case of the complex Ru3. Use of the scavenger fol-
1b ranged from 57 ppm to 4499 ppm (Table 1, column A). lowed by filtration through silica gel (method D) yielded excel-
Filtration through silica gel (method B) gave good results with lent results for all ionically tagged catalysts, affording a
catalysts Ru2 and Ru3. Addition of the scavenger QA once the product with less than 2 ppm Ru. Use of QA followed by the
reaction was complete and stirring for 1 h followed by fil- addition of hydrochloric acid (method E and F) or citric acid
(method G) allowed the reduction of Ru content of 1b below
10 ppm without the use of silica gel, provided that catalysts
Ru1–3 were used.
As the polarity of the catalyst increased, the ruthenium
content of 1b fell for all seven methods of purification. The
best results were obtained for the complex Ru3. However, it
did not achieve full conversion of the substrate (78%), which
was presumably caused by the weak solubility of Ru3 in ethyl
acetate.
Hayashi recently reported an impressive one-pot synthesis
of (−)-oseltamivir accomplished in 60 min.51 That study
showed that when optimizing a reaction, time should be taken
into account in addition to yield and selectivity. Purification of
the final product is one of the most time-consuming steps in
the synthesis of organic compounds and strongly affects the
final yield. Our main goal was the development of an effective
and fast method of purifying compounds from ruthenium resi-
dues that would cause minimal losses of the product. Further
Fig. 3 Hoveyda type OM catalysts used in this study. tests were conducted with the complexes Ru1 and Ru2 (Fig. 3),

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which effected excellent conversion of the substrate and Table 2 Scope of the chromatography-free purification protocol E
afforded a product that had very low ruthenium content (less
than 5 ppm) when purified with the rapid chromatography-
free method E (Fig. 4).
To establish the scope and applicability of the new purifi-
cation method E, test RCM reactions with a selection of com-
pounds were performed (Table 2). Use of the ionically tagged
catalyst Ru2 with a Cl− counterion usually resulted in ruthe-
nium levels lower than 5 ppm. Only in two cases (9b and 13b)
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the contamination slightly exceeded 10 ppm. The use of the

less polar catalyst Ru1 caused an increase of the ruthenium
content. However, in the case of the most demanding sub-
strates, Ru1 provided higher conversions compared to Ru2.
This difference is due to the higher lipophilicity of the PF6−
anion, causing Ru1 to be more soluble in ethyl acetate.
The chosen protocol of removing the isocyanide from the
reaction mixture requires the use of a small amount of hydro-
chloric acid (2.2 equiv. with respect to QA). It can therefore be
used when purifying acid-sensitive compounds (9b) as well as
products that contain an amine group in their structure (19b).
Next, the possibility of applying the purification protocol E
on a large scale was explored (Fig. 5A). The RCM of diene 1a
with Ru1 (0.25 mol%) or Ru2 (1.0 mol%) was conducted using
1.4 g of the substrate. After purification, the ruthenium con-
tamination of the isolated product 1b did not exceed 10 ppm
in both cases.
To demonstrate that the methodology is effective when
large amounts of the catalyst are used, the reaction was per-
formed under ambient atmosphere using the estrogen deriva-
tive 22a and 4.0 equiv. of cis-1,4-diacetoxy-2-butene 21, using
2.5 mol% Ru2 (Fig. 5B). To our delight, the desired product
22b had very low ruthenium content (1.6 ppm).
Finally, we wanted to demonstrate that two different metals
could be removed simultaneously using QA. Isocyanides are
widely used as ligands in the synthesis of transition metal

Conversions were determined by GC analysis and are based on the ratio

of product/(product + starting material). Ru content was determined by
ICP-MS. All reactions used 1 mmol of substrate.
Fig. 4 Removal of ruthenium impurities using the chromatography-
free method E.

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Fig. 5 (A) Application of the purification protocol E on a gram scale,

Ru1 (0.25 mol%), Ru2 (1.0 mol%), aequivalents with respect to the cata-
lyst, (B) removal a large amount of ruthenium residues from the CM
product, bequivalents with respect to the 22a.

complexes due to their unique electronic properties.52 Since

palladium-catalyzed cross-couplings are very useful tools in
organic synthesis,53 we selected palladium as the second
metal. Similarly to ruthenium, palladium is very difficult to
remove from the desired product.54 The strategies of purifying
OM products from ruthenium can also be applied to remove
palladium residues.55 Recently, Diver et al. demonstrated that
isocyanide scavengers D1 and D2 allow the removal of palla-
dium species at different oxidation states from cross-couplings
reactions.56
In this work, we found that the use of QA followed by the
addition of citric acid facilitates efficient purification, remov-
ing both ruthenium and palladium residues from the product.
An RCM/Suzuki–Miyaura sequence was performed without the
direct isolation of intermediate 1b (Fig. 6). The RCM of 1a was
conducted in EtOAc under an ambient atmosphere in the pres-
ence of NHII (0.5 mol%). Upon completion of the RCM, the
reaction mixture was transferred to a preheated glass tube
charged with ethanol, phenylboronic acid and cesium carbon-
ate. (Ph3P)2PdCl2 (5.0 mol%) was added, and the resulting Fig. 6 Removal of Ru and Pd by-products from telescope RCM/
mixture was stirred at 80 °C for 10 min in air. The reaction Suzuki–Miyaura sequence, 1a (1.0 mmol), aequivalents with respect to
mixture was treated with QA and stirred for a further 1 h at the 1a.

room temperature, at which point ethanol and CA were added.

After 15 min, solvents were evaporated and the crude product
1c was placed on a short plug of aluminium oxide. The plug 1.17 ppm and 0.79 ppm, respectively. In the control experi-
was then washed with EtOAc. After removing the solvent, the ment, in which no QA was added, metal content was signifi-
ruthenium and palladium content in the product was cantly higher (49 ppm of Ru and 467 ppm of Pd). Finally, the

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Green Chemistry
metal content in the product afforded by our QA purification
protocol could be decreased to less than 0.5 ppm for both
metals with a simple crystallization. To the best of our knowl-
edge, it is the first example of a telescope57 RCM/Suzuki–
Miyaura sequence and simultaneous removal of ruthenium
and palladium by-products.
Conclusions
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A new simple and inexpensive method of removing ruthenium
residues from OM products was developed. It is based on the
use of a commercially available catalyst bearing a polar qua-
ternary ammonium moiety, the isocyanide scavenger QA and
an inorganic or organic acid. The method is scalable, does not
require time-consuming chromatography and is applicable to
demanding polar compounds. It is compatible with OM con-
ducted under ambient atmosphere in ethyl acetate and yields
products with low ruthenium contamination, typically below
5 ppm. Furthermore, the use of QA followed by the addition of
citric acid allows the simultaneous removal of ruthenium and
palladium species after a telescope RCM/Suzuki–Miyaura
sequence. This work provides a new tool to address the
problem of ruthenium contamination in pharmaceutical
syntheses utilizing olefin metathesis. The simplicity and scal-
ability of the described purification protocol make it an attrac-
tive option in laboratory and industrial settings.
Conflicts of interest
G. S. receives royalty payments from the commercial sales of
some of the catalysts and QA in this manuscript.
Acknowledgements
G. S. wishes to thank the Foundation for Polish Science
(“Ventures” Program and “START-2016” fellowship) for finan-
cial support. The project “Ventures/2013-11/8” is funded by the
“Ventures” program of the Foundation for Polish Science, co-
financed from the European Union Regional Development
Fund. The study was carried out at the Biological and
Chemical Research Centre, University of Warsaw, established
within a project co-financed by the European Union from the
European Regional Development Fund under the Operational
Programme “Innovative Economy”, 2007–2013.
Notes and references
1 (a) R. R. Schrock, Chem. Rev., 2009, 109, 3211–3226;
(b) A. H. Hoveyda and A. R. Zhugralin, Nature, 2007, 450,
243–251; (c) R. R. Schrock and A. H. Hoveyda, Angew.
Chem., Int. Ed., 2003, 42, 4592–4633.
2 (a) D. Hughes, P. Wheeler and D. Ene, Org. Process Res.
Dev., 2017, 21, 1938–1962; (b) C. S. Higman,
J. A. M. Lummiss and D. E. Fogg, Angew. Chem., Int. Ed.,
This journal is © The Royal Society of Chemistry 2018
View Article Online
Paper
2016, 55, 3552–3565; (c) A. Fürstner, Chem. Commun., 2011,
47, 6505–6511; (d) K. C. Nicolaou, P. G. Bulger and
D. Sarlah, Angew. Chem., Int. Ed., 2005, 44, 4490–4527.
3 A.-C. Knall and C. Slugovc, Olefin Metathesis: Theory and
Practice, ed. K. Grela, John Wiley & Sons, Inc., 2014, pp.
269–284.
4 (a) R. A. Sheldon, Green Chem., 2017, 19, 18–43;
(b) M. Eissen and D. Lenoir, ACS Sustainable Chem. Eng.,
2017, 5, 10459–10473; (c) P. T. Anastas and J. C. Warner, in
Green Chemistry: Theory and Practice, Oxford University
Press, New York, 1998.
5 Ł. Woźniak, G. Zieliński and K. Grela, Olefin Metathesis:
Theory and Practice, ed. K. Grela, John Wiley & Sons, Inc.,
2014, pp. 573–585.
6 (a) G. C. Vougioukalakis and R. H. Grubbs, Chem. Rev.,
2010, 110, 1746–1787; (b) C. Samojłowicz, M. Bieniek and
K. Grela, Chem. Rev., 2009, 109, 3708–3742.
7 (a) M. Scholl, S. Ding, C. W. Lee and R. H. Grubbs, Org.
Lett., 1999, 1, 953–956; (b) J. Huang, E. D. Stevens,
S. P. Nolan and J. L. Petersen, J. Am. Chem. Soc., 1999, 121,
2674–2678; (c) M. Scholl, T. M. Trnka, J. P. Morgan and
R. H. Grubbs, Tetrahedron Lett., 1999, 40, 2247–2250.
8 S. B. Garber, J. S. Kingsbury, B. L. Gray and A. H. Hoveyda,
J. Am. Chem. Soc., 2000, 122, 8168–8179.
9 (a) 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, 3879–3890;
(b) D. Prat, A. Wells, J. Hayler, H. Sneddon, C. R. McElroy,
S. Abou-Shehada and P. J. Dunn, Green Chem., 2016, 18,
288–296; (c) D. Prat, J. Hayler and A. Wells, Green Chem.,
2014, 16, 4546–4551.
10 (a) E. C. Gleeson, Z. J. Wang, W. R. Jackson and
A. J. Robinson, J. Org. Chem., 2015, 80, 7205–7211;
(b) Z. J. Wang, W. R. Jackson and A. J. Robinson, Green
Chem., 2015, 17, 3407–3414; (c) J. Tomasek and J. Schatz,
Green Chem., 2013, 15, 2317–2338; (d) K. Grela, Ł. Gułajski
and K. Skowerski, Alkene Metathesis in Water, in Metal-
Catalyzed Reactions in Water, ed. P. Dixneuf and
V. Cadierno, Wiley-VCH, 2013, ch. 8, pp. 291–333;
(e) K. Skowerski, G. Szczepaniak, C. Wierzbicka,
Ł. Gułajski, M. Bieniek and K. Grela, Catal. Sci. Technol.,
2012, 2, 2424–2427; (f ) D. Burtscher and K. Grela, Angew.
Chem., Int. Ed., 2009, 48, 442–454; (g) J. P. Jordan and
R. H. Grubbs, Angew. Chem., Int. Ed., 2007, 119, 5244–5247;
(h) Ł. Gułajski, P. Śledź, A. Lupa and K. Grela, Green Chem.,
2008, 10, 271–274; (i) Ł. Gułajski, A. Michrowska,
J. Narożnik, Z. Kaczmarska, L. Rupnicki and K. Grela,
ChemSusChem, 2008, 1, 103–109.
11 (a) P. Śledź, M. Mauduit and K. Grela, Chem. Soc. Rev.,
2008, 37, 2433–2442; (b) N. Audic, H. Clavier, M. Mauduit
and J.-C. Guillemin, J. Am. Chem. Soc., 2003, 125, 9248–
9249.
12 M. Smoleń, M. Kędziorek and K. Grela, Catal. Commun.,
2014, 44, 80–84.
13 X. Bantreil, M. Sidi-Ykhlef, L. Aringhieri, E. Colacino,
J. Martinez and F. Lamaty, J. Catal., 2012, 294, 113–118.
Green Chem.

Paper
14 (a) M. Drop, X. Bantreil, K. Grychowska, G. U. Mahoro,
E. Colacino, M. Pawłowski, J. Martinez, G. Subra, P. Zajdel
and F. Lamaty, Green Chem., 2017, 19, 1647–1652;
(b) H. Bilel, N. Hamdi, F. Zagrouba, C. Fischmeister and
C. Bruneau, Green Chem., 2011, 13, 1448–1452; (c) X. Miao,
C. Fischmeister, C. Bruneau and P. H. Dixneuf,
ChemSusChem, 2008, 1, 813–816.
15 A. V. Granato, A. G. Santos and E. N. dos Santos,
ChemSusChem, 2017, 10, 1832–1837.
Published on 22 February 2018. Downloaded by University of New England on 22/02/2018 15:17:36.
16 M. Kniese and M. A. R. Meier, Green Chem., 2010, 12, 169–
173.
17 N. Bakhrou, F. Lamaty, J. Martinez and E. Colacino,
Tetrahedron Lett., 2010, 51, 3935–3937.
18 C. S. Adjiman, A. J. Clarke, G. Cooper and P. C. Taylor,
Chem. Commun., 2008, 2806–2808.
19 (a) G. A. Abel, S. Viamajala, S. Varanasi and K. Yamamoto,
ACS Sustainable Chem. Eng., 2016, 4, 5703–5710;
(b) K. Skowerski, J. Białecki, A. Tracz and T. K. Olszewski,
Green Chem., 2014, 16, 1125–1130.
20 (a) A. Olmos, G. Asensio and P. J. Pérez, ACS Catal., 2016, 6,
4265–4280; (b) A. Fürstner, L. Ackermann, K. Beck, H. Hori,
D. Koch, K. Langemann, M. Liebl, C. Six and W. Leitner,
J. Am. Chem. Soc., 2001, 123, 9000–9006.
21 (a) A. S. Trita, L. C. Over, J. Pollini, S. Baader,
S. Riegsinger, M. a. R. Meier and L. J. Gooßen, Green
Chem., 2017, 19, 3051–3060; (b) J.-L. Do, C. Mottillo,
D. Tan, V. Štrukil and T. Friščić, J. Am. Chem. Soc., 2015,
137, 2476–2479; (c) J. Hitce, M. Crutizat, C. Bourdon,
A. Vivès, X. Marat and M. Dalko-Csiba, Green Chem.,
2015, 17, 3756–3761.
22 (a) L. Piola, F. Nahra and S. P. Nolan, Beilstein J. Org.
Chem., 2015, 11, 2038–2056; (b) S. Guidone, O. Songis,
F. Nahra and C. S. J. Cazin, ACS Catal., 2015, 5, 2697–2701.
23 (a) A. Hryniewicka, S. Suchodolski, A. Wojtkielewicz,
J. W. Morzycki and S. Witkowski, Beilstein J. Org. Chem.,
2015, 11, 2795–2804; (b) D. J. Nelson, P. Queval, M. Rouen,
M. Magrez, L. Toupet, F. Caijo, E. Borré, I. Laurent,
C. Crévisy, O. Baslé, M. Mauduit and J. M. Percy, ACS
Catal., 2013, 3, 259–264; (c) P. Kos, R. Savka and H. Plenio,
Adv. Synth. Catal., 2013, 355, 439–447; (d) M. Bieniek,
R. Bujok, M. Cabaj, N. Lugan, G. Lavigne, D. Arlt and
K. Grela, J. Am. Chem. Soc., 2006, 128, 13652–13653;
(e) A. Michrowska, R. Bujok, S. Harutyunyan, V. Sashuk,
G. Dolgonos and K. Grela, J. Am. Chem. Soc., 2004, 126,
9318–9325.
24 (a) A. Szadkowska and K. Grela, Curr. Org. Chem., 2008, 12,
1631–1647; (b) T. Ung, A. Hejl, R. H. Grubbs and
Y. Schrodi, Organometallics, 2004, 23, 5399–5401.
25 (a) V. Sashuk and O. Danylyuk, Chem. – Eur. J., 2016, 22,
6528–6531; (b) R. L. Sutar, E. Levin, D. Butilkov,
I. Goldberg, O. Reany and N. G. Lemcoff, Angew. Chem., Int.
Ed., 2016, 55, 764–767.
26 (a) A. Kozłowska, M. Dranka, J. Zachara, E. Pump,
C. Slugovc, K. Skowerski and K. Grela, Chem. – Eur. J., 2014,
20, 14120–14125; (b) H. J. Schanz, Curr. Org. Chem., 2013,
17, 2575–2591.
Green Chem.
View Article Online
Green Chemistry
27 European Medicines Agency, Specification limits for resi-
dues of metal catalysts CHMP/SWP/4446/2000, 2008.
28 (a) J. Engel, W. Smit, M. Foscato, G. Occhipinti,
K. W. Törnroos and V. R. Jensen, J. Am. Chem. Soc., 2017,
139, 16609–16619; (b) B. Schmidt, Eur. J. Org. Chem., 2004,
1865–1880; (c) S. H. Hong, D. P. Sanders, C. W. Lee and
R. H. Grubbs, J. Am. Chem. Soc., 2005, 127, 17160–17161.
29 (a) P. Wheeler, J. H. Phillips and R. L. Pederson, Org.
Process Res. Dev., 2016, 20, 1182–1190; (b) D. W. Knight, in
Handbook of Metathesis, ed. R. H. Grubbs, A. G. Wenzel,
D. J. O’Leary and E. Khosravi, Wiley-VCH Verlag GmbH &
Co. KGaA, 2015, pp. 379–388; (c) K. Skowerski and
Ł. Gułajski, Olefin Metathesis: Theory and Practice, ed.
K. Grela, John Wiley & Sons, Inc., 2014, pp. 559–571;
(d) G. C. Vougioukalakis, Chem. – Eur. J., 2012, 18, 8868–
8880; (e) H. Clavier, K. Grela, A. Kirschning, M. Mauduit
and S. P. Nolan, Angew. Chem., Int. Ed., 2007, 46, 6786–
6801.
30 (a) R. Gawin, A. Kozakiewicz, P. A. Guńka, P. Dąbrowski
and K. Skowerski, Angew. Chem., Int. Ed., 2017, 56, 981–
986; (b) V. M. Marx, A. H. Sullivan, M. Melaimi,
S. C. Virgil, B. K. Keitz, D. S. Weinberger, G. Bertrand
and R. H. Grubbs, Angew. Chem., Int. Ed., 2015, 54, 1919–
1923.
31 (a) B. J. Ireland, B. T. Dobigny and D. E. Fogg, ACS Catal.,
2015, 5, 4690–4698; (b) C. Lübbe, A. Dumrath,
H. Neumann, M. Schäffer, R. Zimmermann, M. Beller and
R. Kadyrov, ChemCatChem, 2014, 6, 684–688; (c) T. Nicola,
M. Brenner, K. Donsbach and P. Kreye, Org. Process Res.
Dev., 2005, 9, 513–515.
32 (a) J. Czaban, B. M. Schertzer and K. Grela, Adv. Synth.
Catal., 2013, 355, 1997–2006; (b) R. Kadyrov, Chem. – Eur.
J., 2013, 19, 1002–1012; (c) P. Kos, R. Savka and H. Plenio,
Adv. Synth. Catal., 2013, 355, 439–447; (d) K. M. Kuhn,
T. M. Champagne, S. H. Hong, W.-H. Wei, A. Nickel,
C. W. Lee, S. C. Virgil, R. H. Grubbs and R. L. Pederson,
Org. Lett., 2010, 12, 984–987.
33 (a) H. Li, J. P. Scott, C. Chen, M. Journet, K. Belyk,
J. Balsells, B. Kosjek, C. A. Baxter, G. W. Stewart, C. Wise,
M. Alam, Z. J. Song and L. Tan, Org. Lett., 2015, 17, 1533–
1536; (b) B. J. van Lierop, J. A. M. Lummiss and D. E. Fogg,
Olefin Metathesis: Theory and Practice, ed. K. Grela, John
Wiley & Sons, Inc., 2014, pp. 85–152; (c) X. Wei, C. Shu,
N. Haddad, X. Zeng, N. D. Patel, Z. Tan, J. Liu, H. Lee,
S. Shen, S. Campbell, R. J. Varsolona, C. A. Busacca,
A. Hossain, N. K. Yee and C. H. Senanayake, Org. Lett.,
2013, 15, 1016–1019; (d) J. Kong, C. Chen, J. Balsells-
Padros, Y. Cao, R. F. Dunn, S. J. Dolman, J. Janey, H. Li and
M. J. Zacuto, J. Org. Chem., 2012, 77, 3820–3828.
34 S. M. Goldup, C. J. Pilkington, A. J. P. White, A. Burton and
A. G. M. Barrett, J. Org. Chem., 2006, 71, 6185–6191.
35 J. H. Cho and B. M. Kim, Org. Lett., 2003, 5, 531–533.
36 S. Hübner, J. G. de Vries and V. Farina, Adv. Synth. Catal.,
2016, 358, 3–25.
37 G. Szczepaniak, K. Kosiński and K. Grela, Green Chem.,
2014, 16, 4474–4492.
This journal is © The Royal Society of Chemistry 2018

Green Chemistry
38 (a) M. Al-Hashimi, R. Tuba, H. S. Bazzi and R. H. Grubbs,
ChemCatChem, 2016, 8, 228–233; (b) J. Zhao, D. Wang,
B. Autenrieth and M. R. Buchmeiser, Macromol. Rapid
Commun., 2015, 36, 190–194; (c) C. P. Ferraz, B. Autenrieth,
W. Frey and M. R. Buchmeiser, ChemCatChem, 2014, 6,
191–198; (d) B. Autenrieth, F. Willig, D. Pursley,
S. Naumann and M. R. Buchmeiser, ChemCatChem, 2013,
5, 3033–3040; (e) M. Al-Hashimi, C. Hongfa, B. George,
Published on 22 February 2018. Downloaded by University of New England on 22/02/2018 15:17:36.
H. S. Bazzi and D. E. Bergbreiter, J. Polym. Sci., Part A:
Polym. Chem., 2012, 50, 3954–3959; (f ) S. H. Hong and
R. H. Grubbs, Org. Lett., 2007, 9, 1955–1957.
39 (a) M. Klučiar, K. Grela and M. Mauduit, Dalton Trans.,
2013, 42, 7354–7358; (b) W. Kośnik and K. Grela, Dalton
Trans., 2013, 42, 7463–7467; (c) K. Skowerski, P. Kasprzycki,
M. Bieniek and T. K. Olszewski, Tetrahedron, 2013, 69,
7408–7415; (d) K. Skowerski, C. Wierzbicka,
G. Szczepaniak, Ł. Gułajski, M. Bieniek and K. Grela, Green
Chem., 2012, 14, 3264–3268; (e) J. A. Schachner, J. Cabrera,
R. Padilla, C. Fischer, P. A. van der Schaaf, R. Pretot,
F. Rominger and M. Limbach, ACS Catal., 2011, 1, 872–876;
(f) A. Michrowska, Ł. Gułajski, Z. Kaczmarska,
K. Mennecke, A. Kirschning and K. Grela, Green Chem.,
2006, 8, 685–688; (g) A. Michrowska, Ł. Gułajski and
K. Grela, Chem. Commun., 2006, 841–843; (h) J. C. Conrad,
H. H. Parnas, J. L. Snelgrove and D. E. Fogg, J. Am. Chem.
Soc., 2005, 127, 11882–11883.
40 (a) P. Marchetti, M. F. Jimenez Solomon, G. Szekely and
A. G. Livingston, Chem. Rev., 2014, 114, 10735–10806;
(b) M. Rabiller-Baudry, G. Nasser, T. Renouard,
D. Delaunay and M. Camus, Sep. Purif. Technol., 2013, 116,
46–60; (c) G. Nasser, T. Renouard, S. Shahane,
C. Fischmeister, C. Bruneau and M. Rabiller-Baudry,
ChemPlusChem, 2013, 78, 728–736; (d) A. Kajetanowicz,
J. Czaban, G. R. Krishnan, M. Malińska, K. Woźniak,
H. Siddique, L. G. Peeva, A. G. Livingston and K. Grela,
ChemSusChem, 2013, 6, 182–192; (e) P. van der Gryp,
A. Barnard, J.-P. Cronje, D. de Vlieger, S. Marx and
H. C. M. Vosloo, J. Membr. Sci., 2010, 353, 70–77;
(f) D. Schoeps, K. Buhr, M. Dijkstra, K. Ebert and
H. Plenio, Chem. – Eur. J., 2009, 15, 2960–2965;
(g) A. Keraani, T. Renouard, C. Fischmeister, C. Bruneau
and M. Rabiller-Baudry, ChemSusChem, 2008, 1, 927–933.
41 (a) J. Suriboot, C. E. Hobbs, W. Guzman, H. S. Bazzi and
D. E. Bergbreiter, Macromolecules, 2015, 48, 5511–5516;
(b) Y. Yang, N. Priyadarshani, T. Khamatnurova, J. Suriboot
and D. E. Bergbreiter, J. Am. Chem. Soc., 2012, 134, 14714–
14717; (c) C. Hobbs, Y.-C. Yang, J. Ling, S. Nicola, H.-L. Su,
H. S. Bazzi and D. E. Bergbreiter, Org. Lett., 2011, 13, 3904–
3907; (d) C. Hongfa, H.-L. Su, H. S. Bazzi and
D. E. Bergbreiter, Org. Lett., 2009, 11, 665–667.
42 (a) S.-W. Chen, Z.-C. Zhang, N.-N. Zhai, C.-M. Zhong and
S. Lee, Tetrahedron, 2015, 71, 648–653; (b) S.-W. Chen,
Z.-C. Zhang, M. Ma, C.-M. Zhong and S. Lee, Org. Lett.,
2014, 16, 4969–4971; (c) M. J. Byrnes, A. M. Hilton,
C. P. Woodward, W. R. Jackson and A. J. Robinson, Green
Chem., 2012, 14, 81–84; (d) Z. Yinghuai, L. Kuijin,
This journal is © The Royal Society of Chemistry 2018
View Article Online
Paper
N. Huimin, L. Chuanzhao, L. P. Stubbs, C. F. Siong,
T. Muihua and S. C. Peng, Adv. Synth. Catal., 2009, 351,
2650–2656; (e) C. Che, W. Li, S. Lin, J. Chen, J. Zheng,
J. Wu, Q. Zheng, G. Zhang, Z. Yang and B. Jiang, Chem.
Commun., 2009, 5990–5992.
43 (a) D. W. Knight, I. R. Morgan and A. J. Proctor,
Tetrahedron Lett., 2010, 51, 638–640; (b) V. Farina, C. Shu,
X. Zeng, X. Wei, Z. Han, N. K. Yee and C. H. Senanayake,
Org. Process Res. Dev., 2009, 13, 250–254; (c) N. K. Yee,
V. Farina, I. N. Houpis, N. Haddad, R. P. Frutos, F. Gallou,
X. Wang, X. Wei, R. D. Simpson, X. Feng, V. Fuchs, Y. Xu,
J. Tan, L. Zhang, J. Xu, L. L. Smith-Keenan, J. Vitous,
M. D. Ridges, E. M. Spinelli, M. Johnson, K. Donsbach,
T. Nicola, M. Brenner, E. Winter, P. Kreye and W. Samstag,
J. Org. Chem., 2006, 71, 7133–7145; (d) R. L. Pederson,
I. M. Fellows, T. A. Ung, H. Ishihara and S. P. Hajela, Adv.
Synth. Catal., 2002, 344, 728–735; (e) H. D. Maynard and
R. H. Grubbs, Tetrahedron Lett., 1999, 40, 4137–4140.
44 (a) W. Liu, P. J. Nichols and N. Smith, Tetrahedron Lett.,
2009, 50, 6103–6105; (b) M. Westhus, E. Gonthier,
D. Brohm and R. Breinbauer, Tetrahedron Lett., 2004, 45,
3141–3142; (c) Y. M. Ahn, K. Yang and G. I. Georg, Org.
Lett., 2001, 3, 1411–1413; (d) L. A. Paquette, J. D. Schloss,
I. Efremov, F. Fabris, F. Gallou, J. Méndez-Andino and
J. Yang, Org. Lett., 2000, 2, 1259–1261.
45 (a) T. J. Cuthbert, E. Evoy, J. P. J. Bow, R. Guterman,
J. M. Stubbs, E. R. Gillies, P. J. Ragogna and
J. M. Blacquiere, Catal. Sci. Technol., 2017, 7, 2685–2688;
(b) B. A. Ondrusek and H. Chung, ACS Omega, 2017, 2,
3951–3957; (c) E. Borré, M. Rouen, I. Laurent, M. Magrez,
F. Caijo, C. Crévisy, W. Solodenko, L. Toupet,
R. Frankfurter, C. Vogt, A. Kirschning and M. Mauduit,
Chem. – Eur. J., 2012, 18, 16369–16382; (d) R. H. Lambeth,
S. J. Pederson, M. Baranoski and A. M. Rawlett, J. Polym.
Sci., Part A: Polym. Chem., 2010, 48, 5752–5757; (e) I. Pulko,
M. Sandholzer, M. Kolar, C. Slugovc and P. Krajnc,
Tetrahedron Lett., 2010, 51, 5827–5829; (f ) W. Liu,
P. J. Nichols and N. Smith, Tetrahedron Lett., 2009, 50,
6103–6105; (g) K. McEleney, D. P. Allen, A. E. Holliday and
C. M. Crudden, Org. Lett., 2006, 8, 2663–2666.
46 B. R. Galan, K. P. Kalbarczyk, S. Szczepankiewicz,
J. B. Keister and S. T. Diver, Org. Lett., 2007, 9, 1203–1206.
47 (a) J. R. Griffiths, E. J. Hofman, J. B. Keister and S. T. Diver,
Organometallics, 2017, 36, 3043–3052; (b) B. R. Galan,
M. Gembicky, P. M. Dominiak, J. B. Keister and S. T. Diver,
J. Am. Chem. Soc., 2005, 127, 15702–15703.
48 J. M. French, C. A. Caras and S. T. Diver, Org. Lett., 2013,
15, 5416–5419.
49 G. Szczepaniak, K. Urbaniak, C. Wierzbicka, K. Kosiński,
K. Skowerski and K. Grela, ChemSusChem, 2015, 8, 4139–
4148.
50 (a) A. Jana and K. Grela, Chem. Commun., 2018, 54, 122–
139; (b) A. Chołuj, A. Zieliński, K. Grela and
M. J. Chmielewski, ACS Catal., 2016, 6, 6343–6349;
(c) K. Skowerski, J. Białecki, S. J. Czarnocki, K. Żukowska
and K. Grela, Beilstein J. Org. Chem., 2016, 12, 5–15;
Green Chem.

Paper
(d) K. Skowerski, J. Pastva, S. J. Czarnocki and J. Janoscova,
Org. Process Res. Dev., 2015, 19, 872–877; (e) H. Balcar,
N. Žilková, M. Kubů, M. Mazur, Z. Bastl and J. Čejka,
Beilstein J. Org. Chem., 2015, 11, 2087–2096; (f) J. Pastva,
K. Skowerski, S. J. Czarnocki, N. Žilková, J. Čejka, Z. Bastl
and H. Balcar, ACS Catal., 2014, 4, 3227–3236;
(g) K. Skowerski, S. J. Czarnocki and P. Knapkiewicz,
ChemSusChem, 2014, 7, 536–542.
51 Y. Hayashi and S. Ogasawara, Org. Lett., 2016, 18, 3426–
Published on 22 February 2018. Downloaded by University of New England on 22/02/2018 15:17:36.
3429.
52 (a) B. Song and B. Xu, Chem. Soc. Rev., 2017, 46, 1103–1123;
(b) V. P. Boyarskiy, N. A. Bokach, K. V. Luzyanin and
V. Y. Kukushkin, Chem. Rev., 2015, 115, 2698–2779;
(c) S. Chakrabarty, S. Choudhary, A. Doshi, F.-Q. Liu,
R. Mohan, M. P. Ravindra, D. Shah, X. Yang and
F. F. Fleming, Adv. Synth. Catal., 2014, 356, 2135–2196;
(d) T. Vlaar, E. Ruijter, B. U. W. Maes and R. V. A. Orru,
Angew. Chem., Int. Ed., 2013, 52, 7084–7097.
53 (a) X. Chen, K. M. Engle, D.-H. Wang and J.-Q. Yu, Angew.
Chem., 2009, 48, 5094–5115; (b) K. C. Nicolaou, P. G. Bulger
and D. Sarlah, Angew. Chem., 2005, 44, 4442–4489;
(c) N. Miyaura and A. Suzuki, Chem. Rev., 1995, 95, 2457–
2483.
Green Chem.
View Article Online
Green Chemistry
54 (a) H. Ren, C. A. Strulson, G. Humphrey, R. Xiang, G. Li,
D. R. Gauthier and K. M. Maloney, Green Chem., 2017, 19,
4002–4006; (b) H. Miyamoto, C. Sakumoto, E. Takekoshi,
Y. Maeda, N. Hiramoto, T. Itoh and Y. Kato, Org. Process Res.
Dev., 2015, 19, 1054–1061; (c) E. J. Flahive, B. L. Ewanicki,
N. W. Sach, S. A. O’Neill-Slawecki, N. S. Stankovic, S. Yu,
S. M. Guinness and J. Dunn, Org. Process Res. Dev., 2008, 12,
637–645; (d) K. M. Bullock, M. B. Mitchell and J. F. Toczko,
Org. Process Res. Dev., 2008, 12, 896–899.
55 (a) H. Ren, C. A. Strulson, G. Humphrey, R. Xiang, G. Li,
D. R. Gauthier and K. M. Maloney, Green Chem., 2017, 19,
4002–4006; (b) R. Buscemi, F. Giacalone, S. Orecchio and
M. Gruttadauria, ChemPlusChem, 2014, 79, 421–426;
(c) W. P. Gallagher and A. Vo, Org. Process Res. Dev., 2015,
19, 1369–1373; (d) H. Miyamoto, C. Sakumoto,
E. Takekoshi, Y. Maeda, N. Hiramoto, T. Itoh and Y. Kato,
Org. Process Res. Dev., 2015, 19, 1054–1061; (e) L. Wang,
L. Green, Z. Li, J. McCabe Dunn, X. Bu, C. J. Welch, C. Li,
T. Wang, Q. Tu, E. Bekos, D. Richardson, J. Eckert and
J. Cui, Org. Process Res. Dev., 2011, 15, 1371–1376.
56 J. M. French, J. R. Griffiths and S. T. Diver, Adv. Synth.
Catal., 2015, 357, 361–365.
57 Y. Hayashi, Chem. Sci., 2016, 7, 866–880.
This journal is © The Royal Society of Chemistry 2018