Synthesis and polymerisation of α-alkylidene cyclic carbonates from carbon dioxide, epoxides and the primary propargylic alcohol 1,4-butynediol

Article abstract of DOI:10.1039/c9gc04320a

Using the bulk chemical 1,4-butynediol, readily available epoxides and carbon dioxide, a new series of unsubstituted exovinylene carbonates were synthesised. Chemoselective additions of diamines or diols to these cyclic carbonates allow the regiocontrolled synthesis of new functionalised polyurethanes and polycarbonates under mild conditions. This route to polyurethanes avoids the use of toxic isocyanates.

Full text of DOI:10.1039/c9gc04320a

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DOI: 10.1039/C9GC04320A
COMMUNICATION
Synthesis and polymerisation of -alkylidene cyclic carbonates
obtained from carbon dioxide, epoxides and the primary
propargylic alcohol 1,4-butynediol
Received 00th January 20xx,
Accepted 00th January 20xx
Saumya Dabral,a Ulrike Licht,b Peter Rudolf,b Gérard Bollmann,c A. Stephen. K. Hashmi
and
a,c
Thomas Schaub*a,b
DOI: 10.1039/x0xx00000x
Based on the bulk chemical 1,4-butynediol, readily available isocyanate-free route, offer an advantage of bypassing the
epoxides and carbon dioxide, a new series of unsubstituted handling of moisture sensitive reagents and toxic phosgene gas,
exovinylene carbonates were synthesised. Chemoselective thus making the overall process much safer than the classical
additions of diamines or diols to these cyclic carbonates allow the isocyanate/alcohol synthesis.25–31 However, the 5CCs ring
regiocontrolled synthesis of new functionalised polyurethanes and opening reactions suffer from drawbacks such as poor reaction
polycarbonates under mild conditions. This route to polyurethanes rate, lack of regiocontrol as well as generation of side products.
avoids the use of toxic isocyanates.
Exovinylene carbonates (EVCs), produced by the catalytic
carboxylative coupling of propargylic alcohols with CO2, on the
other hand, represent another emerging class of CO2-derived
cyclic carbonate building blocks.36 Compared to the 5CCs, due
to the establishment of a keto–enol equilibrium, the presence
of an exocyclic olefinic group in the EVCs offers higher reactivity
and regioselectivity for the ring-opening reactions. As a result
of this, these -alkylidene cyclic carbonates (CCs) have
allowed the synthesis of complex organic molecules such as -
oxo carbamates,37 -oxo-carbonates,38 -hydroxy-1,3-
oxazolidin-2-ones,38 -hydroxyketones,39,40 and 3-dialkyl
amino-oxazolidin-2-ones.41 Expanding this scope further,
Detrembleur and coworkers recently reported on the
Utilising carbon dioxide (CO2) as a feedstock for industrial
synthesis is not new, currently CO2 is used on a significant scale
(> 110 MT p.a.), mainly for the production of urea, carbonates,
methanol or salicylic acid.1,2 Among all products of the chemical
industry, due to their diverse fields of application, polymers
remain the most widely produced commodity chemicals.
Traditionally, most of the commercial polymers and plastics are
produced from non-renewable fossil resources. However,
depleting fossil reservoirs and increasing consumer demands as
well as environmental pollution and new legislative
requirements, have initiated a significant increase of the efforts
to find sustainable approaches for their synthesis.3–10 In line
with this, incorporating CO2 into new monomers, offers an
alternative way to achieve lower carbon footprints.
In the last years, significant advancements were made in
catalyst development for integrating the inert greenhouse gas
CO2 as a renewable C1 carbon feedstock, into valuable polymer-
building blocks and directly into polymers with high CO2 content
(polycarbonates, polyols, polyurethanes (PU), polyureas and
polyesters).11–15 Amongst these, five-membered cyclic
application of the CO -derived bis-EVCs as suitable building
2
blocks for the synthesis of new regioregular functional
isocyanate-free PUs and PCs.42 The scope was further expanded
to the organo-catalysed thiolation of CCs to sulphur containing
polymers.43 These discoveries inspired us to investigate realted
reaction pathways for our newly developed unique class of
previously inaccessible and now industrially relevant
unsubstituted αCCs, which are based on the cheap bulk
chemical 1,4-butynediol.44
Initially, we performed our preliminary studies with EVC 1
(prepared by the AgOAc-Davephos catalysed carboxylative
coupling of CO2 to 4-(benzyloxy)but-2-yn-1-ol)44 and EVC 2
(prepared by the AgOAc-Davephos catalysed carboxylative
coupling of CO2 to 4-hydroxybut-2-yn-1-yl p-tolylcarbamate).
These 1,4-butynediol-based CCs were chosen because they
provided a variation in functionalisation of the alkylidene side
chain. Scheme 1 shows the regioselective nucleophilic ring-
opening of the unsubstituted CCs 1 and 2 that were performed
for 24 h at room temperature either with ethanol (EtOH, 1 eq.)
carbonates (5CCs) represent an important class of CO -based
2
building blocks that are formed by reacting the corresponding
oxirane with CO2.16–24 5CCs, upon polyaddition with either
diamines or diols, provided the two important classes of
polymers, the poly(β-hydroxyurethane)s (PHUs)25–30 and
poly(carbonate)s (PCs).31–35 Especially the PHUs obtained by this
a. Catalysis Research Laboratory (CaRLa), Im Neuenheimer Feld 584, Heidelberg
69120, Germany.
b. BASF SE, Carl-Bosch-Str. 38, Ludwigshafen 67056, Germany.
c. Institute of Organic Chemistry, Heidelberg University, Im Neuenheimer Feld 270,
Heidelberg 69120, Germany.
*E-mail: thomas.schaub@basf.com.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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COMMUNICATION
Journal Name
O
primary or a secondary -OH group, in excellent yields of 95% and
97%, respectively. Encouraged by the stability of these new
DBU (2 mol%)
EtOH (1 eq.)
View Article Online
DOI: 10.1039/C9GC04320A
O
O
O
O
O
RT, 24 h
1a: 95%
O
O
Table 1. Nucleophilic ring-opening of epoxides with bulk chemical 1,4-butynediol
O
O
R
HO
OH
R
O
N
pyrrolidine (1 eq.)
RT, 24 h
Cat. (TBAB or BF3. OEt2
)
O
O
1
+
OH
O
O
Nucleophilic substitution
OH
1b: 89%
3
4
O
NH2
+
DBU (2 mol%)
C2H5
Epoxides (3)
Propargyl alcohol (4)
EtOH (1 eq.)
O
O
H
O
RT, 24 h
O
O
N
O
2a: 64%
O
further decomposes
O
OH
O
O
O
O
OH
O
O
4a: 62%
3a
NH2
+
pyrrolidine (1 eq.)
RT, 24 h
O
O
N
2
OH
O
2a: 70%
OH
further decomposes
4b: 45%
3b
3c
Scheme 1. EtOH and pyrrolidine initiated nucleophilic ring-opening of EVCs 1 and 2.
OH
O
O
OH
in the presence of 2 mol% 1,8-diazabicyclo [5.4.0]undec-7-ene
(DBU) or with pyrrolidine (1 eq.). Pleasingly, the reaction of both
nucleophiles with EVC 1 were quantitative and resulted in the
desired carbonate 1a and carbamate product 1b in high yields
of 95% and 89% respectively (Scheme 1, Top). When 2 mol% of
the related 1,5-Diazabicyclo[4.3.0]non-5-ene (DBN) instead of
DBU were used in the ring-opening of 1, we observed the same
reactivity. Moreover, the presence of isopropanol (secondary
alcohol) did not influence the outcome of the ring opening
reaction of EVC 1 with EtOH, hence highlighting the higher rate
of reaction of primary alcohol over secondary (see Section 5.1
in the Supporting Information). EVC 2, when subjected to these
conditions however, afforded elimination product (para-
toulidine) instead of the expected addition product (Scheme 1,
bottom, Section 5.2 Supporting Information). These results
were especially interesting as they highlighted the stability of
the ether bonds (R-O-R) of the alkylidene side-chain in EVC 1
over the carbamate functionality (RNH(CO)-OR) in EVC 2,
towards nucleophilic ring-opening rearrangement reactions.
Based on these results, we considered exploring readily
available epoxides (3a-e) as suitable precursors for the
synthesis of primary propargylic alcohols (4 a-e) via epoxide
ring-opening reactions initiated by the bulk chemical 1,4-
butanediol, (Table 1). These unprecedented nucleophilic
additions of 1,4-butanediol to epoxides were initiated by either
catalytic amounts of tetrabutylammonium bromide (TBAB) or
boron trifluoride etherate (BF3·OEt2) (see Section 2.0 of the
Supporting Information). The primary propargylic alcohols (4 a-
e) were isolated in moderate yields (40-75%). These products 4
were subsequently subjected to our established AgOAc-
DavePhos cyclisation conditions (Scheme 2).44
4c: 40%
OH
O
O
O
O
O
O
O
O
3d
3e
OH
OH
4d: 75%
4e: 62%
OH
OH
OH
O
O
O
O
O
O
O
O
OH
OH
O
O
O
AgOAc (1 or 5 mol%)
Davephos (1 or 5 mol%)
R
R
O
O
OH
CO2 (20 bar), MeCN, RT, 18 h
OH
OH
4 a-e
5 a-e
Reaction Scope
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OH
5a: 95%
OH
5d: 90%
OH
O
O
O
O
O
OH
O
O
O
O
O
O
O
O
O
O
O
OH
O
OH
OH
5e: 95%
Bis-ExoVCs
5c: 97%O
5b: 95%
Mono-ExoVCs
Scheme 2. Scope of the carboxylation cyclisation of propargyl alcohols (4a-e)
mono-EVCs, the methodology was next tested in the formation
of bis-CCs using 5 mol% catalyst loadings.
At room temperature, using 1 mol% AgOAc-DavePhos catalyst
loading, the propargylic alcohol 4a was cyclised to the
corresponding CC 5a in a high yield of 95% after 18 h reaction
time under 20 bar of CO2 pressure. Moreover, the secondary
hydroxy group thus generated in 5a, did not promote any inter-
or intra-molecular ring-opening reaction under the described
cyclisation conditions. Pleasingly, the product stability was
further expanded to CO2-based cycloadditon reactions of
styrene oxide (4b) and cyclohexene oxide (4c) derived
propargylic alcohols that, under similar reaction conditions, also
afforded the corresponding CCs 5b and 5c, bearing either a
2 | J. Name., 2012, 00, 1-3
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Starting from bisphenol-A diglycidyl ether and 1,4-butanediol further dehydrated gave 9 in 87% yield (Scheme 3, reaction 3),
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diglycidyl ether propargylic alcohols 4d and 4e, the the reaction of 5a with pyrrolidine took DpOlaI:c1e0.a1t03a9/sClo9wGCe0r4r3a2t0eA,
afforded the desired -oxo-urethane product 10 in very good
BuOH (1 eq.)
O
O
(1)
DBU (2 mol%)
O
OH
O
+
yield of 89% after performing the reaction for 6 h at room
temperature (Scheme 3, reaction 4). Furthermore, under similar
reaction conditions, reacting 1.0 equivalent of 5a with 0.5
equivalent of N,N-dimethylethylamine led to the formation of a
bis--oxo-urethane product 11 in a yield of 85% (Scheme 3,
reaction 5). Having successfully formed the corresponding
urethane and carbonate bonds from 5a, the reactions were
then extended onto bis-EVCs 5d/5e, which on reaction with
either two equivalents of pyrrolidine or butane-1-ol resulted in
the corresponding di-ring opened products (see Section 5.4 and
5.5 of the Supporting Information).
O
O
O
O
MeCN, RT, 24
h
O
OH
OH
6: 65% (87% glove box)
7: 25%
O
H2
DBU (2 mol%)
MeCN, RT, 24
O (1 eq.)
+
CO2
OH
(2)
No conversion observed in the absence of base
O
O
h
OH
OH
8: 40%
O
O
O
O
O
H2
N
O
O
NH
(1 eq.)
6
O
O
(3)
(4)
N
O
O
6
O
O
5a
OH
MeCN, RT,
1
h
O
OH
9: 87%
DBU (2 mol%)
MeCN, RT, 24
O
h
N
(1 eq.)
O
N
H
O
O
10: 89%
MeCN, RT,
6
h
Self polymer
Mn = 948
Mw= 2497
Ð = 2.63
OH
OH
O
HN
O
O
NH
(0.5 eq.)
O
O
N
O
(5)
O
N
O
O
MeCN, RT,
6 h
O
O
OH
11: 85%
Based on the above regioselective ring-opening reactions, the
polyaddition of bis-CCs (5d = M1 and 5e = M2) were finally
attempted with equimolar amounts of either a diamine (N,N’-
dimethylethylenediamine, N1) or a diol (1,4-butanediol, N2)
corresponding symmetrical bis-EVCs 5d and 5e were also
isolated in high yields of 90% and 95%, respectively. These new
CO2-derived bis-exovinylene carbonates were then studied in
co-polymerisation reactions. Based on our observations with
EVCs 1 and 2, the regio-controlled ring-opening reactions were
first studied on the mono-EVC 5a, bearing an ether linkage on
the side chain of the exocyclic olefin (Scheme 3) Subjecting 5a
to 2 mol% DBU, even in the absence of an external alcohol as
nucleophile, resulted in its self-polymerisation (due to presence
of secondary -OH groups) to give a dark coloured sticky
macromolecule with a weight average molecular mass (Mw) of
2497 g mol-1 (see Section 5.3 in the Supporting Information).
However, the addition of a primary alcohol (butane-1-ol) to 5a
in the presence of DBU (2 mol%) led to a regio-selective ring-
opening to afford 65% of the -oxo-carbonate product 6 (a -
Scheme 3: Nucleophilic ring-opening reactions of EVC 5a
keto tautomer)42 along with the formation of the
decarboxylated product 7 in 25% yield after a 24 h reaction time
(Scheme 3, reaction 1). Since 7 could be formed due to the
presence of water (H2O) in the reaction mixture, the reaction
was repeated in the glove box, which increased the yield of 6 to
87%. It is important to mention here that in the absence of DBU
no conversion wasobserved for the above reaction. This
underlines the catalytic activity of DBU, that possibly activates
the alcohol by hydrogen bonding which in turn increases its
nucleophilicity towards the EVC. Furthermore, a separate
reaction of EVC 5a with stoichiometric amounts of H2O in the
presence of DBU (2 mol%) as catalyst gave the decarboxylation
product 7 in 40% yield (Scheme 3, reaction 2). This observation
is especially interesting as parallels could be drawn to the
reactivity of CCs with H2O to the blowing process (an
important competing reaction) occurring between isocyanate
and H2O during the production of rigid polyurethane foams,
hence opening similar opportunities for future application of
EVCs to be looked into.45
Next the stability of the side-chain in EVC 5a towards primary
(1-hexylamine) and secondary (pyrrolidine) amines as
nucleophiles was tested. While the reaction of 5a with 1-
hexylamine in just 1 h at room temperature led to the formation
of the oxazolidone (formed by intramolecular ring-cyclisation
of the corresponding -oxo-urethane intermediate), which on
Figure 1: Comparison of 1H (Top) and 13 C NMR (Bottom) for the reaction of 5d
with N,N’-dimethyl-1,4-butanediamine (N1) and 1,4-butanediol (N2)
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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nucleophile to afford a novel class of CO2-based isocyanate-free 155 ppm respectively. Further peaks in the NMR were assigned on
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the basis of the similarity of these regions wDitOhIt:h10e.1p0r3o9d/uCc9tGsCis0o4l3a2t0eAd
for the individual reaction of 5d with pyrrolidine and butan-1-ol.
Similar studies were also performed on bis-EVC 5e (see Section 5.5
of the Supporting Information). Size exclusion chromatography (SEC)
was also performed on newly formed polymers, that indicated the
weight average molar mass (Mw) of 5701 g mol-1 and 7656 g mol-1 for
poly(-oxo-urethane)s and poly(-oxo-carbonate)s (Figure 2). Figure
1 shows the crude 1H NMR and 13C NMR spectra for the co-
polymerisation of bis-EVC M1 with nucleophiles N1 and N2. The
1
comparison of the H NMR spectra showed the full consumption of
the starting EVC 5d (M1) at room temperature, after 24 h reaction
time, while the comparison of 13C NMR spectra for the polymers
(M1-N1 and M2-N2) with the starting monomer M1 indicated the poly(-oxo-urethane)s (M1-N1) and (M2-N1) respectively (Table 2
appearance of new resonance peaks for the -keto group at  = 207 entries 1 and 2). On the other hand the Mw values for the poly(-oxo-
ppm and the urethane and carbonate carbonyl peaks at  = 156 and
R
HO
OH
CO2-sourced Polymers
+
O
Poly( -oxo-urethane)s

CO2
O
O
O
O
O
N
N
Monomers
O
O
O
O
O
O
O
N
O
O
O
O
O
O
OH
OH
OH
O
n
M1-N1
O
O
O
O
O
O
O
N
O
O
OH
O
OH
M1
n
O
O
OH
O
O
O
M2-N1
OH
O
O
O
Poly( -oxo-carbonate)s

O
O
O
OH
O
O
M2
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OH
OH
OH
O
n
Nucleophiles
HO
M1-N2
H
N
N
OH
H
O
O
N1
O
O
O
N2
n
O
OH
O
M2-N2
Figure 2: Representative structures of the monomers used and the corresponding polymers formed.
Table 2: Molecular weight characterisation of the poly(-oxo-urethane)s and poly(-oxo-carbonate)sa
Entry
Polymer
M1-N1
M2-N1
M1-N2
M2-N2
Solvent
MeCN
MeCN
MeCN
MeCN
Cat. b
-
-
DBU
DBU
Time (h)
24
24
24
24
Mn (g mol-1)
Mw (g mol-1)
5701
Convc
99
99
99
99
Đ
1
2
3
4
5204
3852
2113
1905
1.09
1.98
1.01
1.03
7656
2144
1971
a
c
Determined by GPC in EtOH-stabilised CHCl3 eluent using polystyrene standards for calibration. b 3 mol% DBU. Monomer conversions determined by 1H NMR
spectroscopy
substituent of the exocyclic olefinic group effected the
successful formation of the corresponding β-oxo-urethane and
carbonate)s (M1-N2) and (M2-N2) were found to be 2144 g mol-1 and
1971 g mol-1 respectively (Table 2, entries 3 and 4). Further studies
pertaining to the effect of solvents and the nature of the base-
catalyst on the molecular weight of the polymers are currently
underway in our laboratory.
β-oxo-carbonate.
Preliminary
ring-opening
reactions
performed on mono-EVC 5a and bis-EVC 5d and 5e in the
presence of either mono-amines or mono-alcohols as
nucleophiles (pyrrolidine, 1-hexylamine and butanol) thus led to
the of the corresponding β-oxo-urethane, oxazolidone and β-
oxo-carbonate products in very good yields and under mild
reaction conditions. The robustness of this system was then
extended to the synthesis of regioregular poly(β-oxo-
urethane)s and poly(β-oxo-carbonates)s obtained via co-
polymerisation of bis-EVC 5d and 5e with a diamine or a diol
Conclusions
In conclusion, for the first time we demonstrated the synthesis
of new CO2-based unsubstituted mono- and di-α-alkylidene
cyclic carbonates using readily available epoxides and 1,4-
butynediol as starting materials. These EVCs are envisioned as
cheap building-blocks for the synthesis of new region-regular
isocyanate-free polyurethanes and polycarbonates along with
incorporating CO2 as a chemical feedstock in the polymer
backbone. The synthesis of EVCs (5a-e) were based on the
nucleophilic ring-opening studies performed on EVC 1 and 2,
which highlight that stability of the ethereal side chain
respectively. The presence of the
-OH groups in the polymer
is of special importance as they could potentially initiate
secondary hydrogen bonding interactions, similar to those
found in PU adhesives thereby opening new avenues for their
application in the industry. The current protocol for the
synthesis of epoxide-based propargylic alcohols and the catalyst
recycling after the formation of the EVCs have to be further
4 | J. Name., 2012, 00, 1-3
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optimised in order to facilitate the scale-up synthesis of the
regioregular polymers at a reasonable cost.
2015, 5, 4636–4643.
View Article Online
20
S. Gennen, M. Alves, R. Méreau, TD. OTaI:s1s0a.1in0g3,9/BC.9GGiClb0e4r3t2,0CA.
Detrembleur, C. Jerome and B. Grignard, ChemSusChem,
2015, 8, 1845–1849.
Conflicts of interest
Two patents from the authors disclosing the catalyst system and
the new monomers are published (see ref 44b and 44c).
21
22
23
24
25
26
M. Alves, B. Grignard, R. Mereau, C. Jerome, T. Tassaing and
C. Detrembleur, Catal. Sci. Technol., 2017, 7, 2651–2684.
H. Büttner, J. Steinbauer and T. Werner, ChemSusChem,
2015, 8, 2655–2669.
W. Desens and T. Werner, Adv. Synth. Catal., 2016, 358,
622–630.
Acknowledgements
CaRLa (Catalysis Research Laboratory) is co-financed by the
Heidelberg University and BASF SE.
H. Büttner, L. Longwitz, J. Steinbauer, C. Wulf and T. Werner,
Top. Curr. Chem., 2017, 375, 50.
L. Maisonneuve, O. Lamarzelle, E. Rix, E. Grau and H.
Cramail, Chem. Rev., 2015, 115, 12407–12439.
L. Poussard, J. Mariage, B. Grignard, C. Detrembleur, C.
Jérôme, C. Calberg, B. Heinrichs, J. De Winter, P. Gerbaux, J.-
M. Raquez, L. Bonnaud and P. Dubois, Macromolecules,
2016, 49, 2162–2171.
B. Grignard, J.-M. Thomassin, S. Gennen, L. Poussard, L.
Bonnaud, J.-M. Raquez, P. Dubois, M.-P. Tran, C. B. Park, C.
Jerome and C. Detrembleur, Green Chem., 2016, 18, 2206–
2215.
S. Samanta, S. Selvakumar, J. Bahr, D. S. Wickramaratne, M.
Sibi and B. J. Chisholm, ACS Sustain. Chem. Eng., 2016, 4,
6551–6561.
G. Liu, G. Wu, S. Huo, C. Jin and Z. Kong, Prog. Org. Coatings,
2017, 112, 169–175.
K. Błażek and J. Datta, Crit. Rev. Environ. Sci. Technol., 2019,
49, 173–211.
N. Yadav, F. Seidi, D. Crespy and ValerioD’Elia,
ChemSusChem, 2019, 12, 724 –754.
J.-C. Lee and M. H. Litt, Macromolecules, 2000, 33, 1618–
1627.
S. Tempelaar, L. Mespouille, O. Coulembier, P. Dubois and
A. P. Dove, Chem. Soc. Rev., 2013, 42, 1312–1336.
W. Guerin, A. K. Diallo, E. Kirilov, M. Helou, M. Slawinski, J.-
M. Brusson, J.-F. Carpentier and S. M. Guillaume,
Macromolecules, 2014, 47, 4230–4235.
S. Paul, Y. Zhu, C. Romain, R. Brooks, P. K. Saini and C. K.
Williams, Chem. Commun., 2015, 51, 6459–6479.
Recent publications for the synthesis of EVCs by reacting
propargyl alcohols with CO2: [a] J. Qiu, Y. Zhao, Z. Li, H.
Wang, M. Fan and J. Wang, ChemSusChem, 2017, 10, 1120–
1127; [b] H. Zhou, G.-X. Wang and X.-B. Lu, Asian J. Org.
Chem., 2017, 6, 1264–1269; [c] Y. Yuan, Y. Xie, C. Zeng, D.
Song, S. Chaemchuen, C. Chen and F. Verpoort, Green
Chem., 2017, 19, 2936–2940; [d] Y. Yuan, Y. Xie, C. Zeng, D.
Song, S. Chaemchuen, C. Chen and F. Verpoort, Catal. Sci.
Technol., 2017, 7, 2935–2939; [e] Z. Zhou, C. He, L. Yang, Y.
Wang, T. Liu and C. Duan, ACS Catal., 2017, 7, 2248–2256;
[f] Z.-H. Zhou, Q.-W. Song and L.-N. He, ACS Omega, 2017,
2, 337–345; [g] Y. Yuan, Y. Xie, D. Song, C. Zeng, S.
Chaemchuen, C. Chen and F. Verpoort, Appl. Organomet.
Chem., 2017, 31, e3867; [h] S.-L. Hou, J. Dong, X.-L. Jiang, Z.-
H. Jiao and B. Zhao, Angew. Chemie Int. Ed., 2019, 58, 577–
581; [i] H. Zhou, R. Zhang and X. -B. Lua, Adv. Synth. Catal.
2019, 361, 326–334.
Notes and references
1
T. Schaub, R. A. Paciello and M. Limbach, in Applied
Homogeneous Catalysis with Organometallic Compounds: A
Comprehensive Handbook in Four Volumes, eds. B. Cornils,
W. A. Herrmann, M. Beller and R. A. Paciello, WILEY-VCH
Weinheim, 2018, pp. 1601–1614.
27
28
2
S. Topham, A. Bazzanella, S. Schiebahn, S. Luhr, L. Zhao, A.
Otto and D. Stolten, Ullmann’s Encycl. Ind. Chem., 2014, 1–
43.
3
4
S. A. Miller, Polym. Chem., 2014, 5, 3117–3118.
D. Esposito and M. Antonietti, Chem. Soc. Rev., 2015, 44,
5821–5835.
29
30
31
32
33
34
5
6
T. Iwata, Angew. Chemie Int. Ed., 2015, 54, 3210–3215.
V. Froidevaux, C. Negrell, S. Caillol, J.-P. Pascault and B.
Boutevin, Chem. Rev., 2016, 116, 14181–14224.
C. Zhang, T. F. Garrison, S. A. Madbouly and M. R. Kessler,
Prog. Polym. Sci., 2017, 71, 91–143.
7
8
S. Lambert and M. Wagner, Chem. Soc. Rev., 2017, 46, 6855–
6871.
9
Z. Sun, B. Fridrich, A. de Santi, S. Elangovan and K. Barta,
Chem. Rev., 2018, 118, 614–678.
10
11
12
13
G. John, S. Nagarajan, P. K. Vemula, J. R. Silverman and C. K.
S. Pillai, Prog. Polym. Sci., 2019, 92, 158–209.
Q.-W. Song, Z.-H. Zhou and L.-N. He, Green Chem., 2017, 19,
3707–3728.
R. Muthuraj and T. Mekonnen, Polymer (Guildf)., 2018, 145,
348–373.
J. Artz, T. E. Müller, K. Thenert, J. Kleinekorte, R. Meys, A.
Sternberg, A. Bardow and W. Leitner, Chem. Rev., 2018, 118,
434–504.
35
36
14
15
16
17
18
19
B. Grignard, S. Gennen, C. Jérôme, A. W. Kleij and C.
Detrembleur, Chem. Soc. Rev., 2019, 48, 4466–4514.
S. Dabral and T. Schaub, Adv. Synth. Catal., 2019, 361, 223–
246.
M. North, R. Pasquale and C. Young, Green Chem., 2010, 12,
1514–1539.
C. Martín, G. Fiorani and A. W. Kleij, ACS Catal., 2015, 5,
1353–1370.
G. Fiorani, W. Guo and A. W. Kleij, Green Chem., 2015, 17,
1375–1389.
M. Alves, B. Grignard, S. Gennen, R. Mereau, C.
Detrembleur, C. Jerome and T. Tassaing, Catal. Sci. Technol.,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

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Please do not adjust margins
Page 6 of 7
COMMUNICATION
Journal Name
37
38
C.-R. Qi and H.-F. Jiang, Green Chem., 2007, 9, 1284–1286.
P. Toullec, A. Carbayo Martin, M. Gio-Batta, C. Bruneau and
View Article Online
DOI: 10.1039/C9GC04320A
P. H. Dixneuf, Tetrahedron Lett., 2000, 41, 5527–5531.
Y. Zhao, Z. Yang, B. Yu, H. Zhang, H. Xu, L. Hao, B. Han and Z.
Liu, Chem. Sci., 2015, 6, 2297–2301.
Q.-W. Song, Z.-H. Zhou, M.-Y. Wang, K. Zhang, P. Liu, J.-Y.
Xun and L.-N. He, ChemSusChem, 2016, 9, 2054–2058.
N. B. Chernysheva, A. A. Bogolyubov and V. V Semenov,
Chem. Heterocycl. Compd., 2003, 39, 1057–1064.
S. Gennen, B. Grignard, T. Tassaing, C. Jérôme and C.
Detrembleur, Angew. Chemie Int. Ed., 2017, 56, 10394–
10398.
39
40
41
42
43
44
F. Ouhib, B. Grignard, E. VanꢀDenꢀBroeck, A. Luxen, K.
Robeyns, V. VanꢀSpeybroeck, C. Jerome and C. Detrembleur,
Angew. Chemie Int. Ed., 2019, 58, 11768–11773.
[a] S. Dabral, B. Bayarmagnai, M. Hermsen, J. Schießl, V.
Mormul, A. S. K. Hashmi and T. Schaub, Org. Lett., 2019, 21,
1422–1425; [b] B. Bayarmagnai, T. Schaub, V. Mormul, P.
Rudolf, WO 2019034648, 2017; [c] T. Schaub, P. Rudolf, U.
Licht, V. Mormul, S. Dabral, WO 2019219469A1, 2019.
E. Delebecq, J. -P. Pascault, B. Boutevin and F. Ganachaud,
Chem. Rev., 2013, 113, 80−118.
45
6 | J. Name., 2012, 00, 1-3
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