A Switchable Domino Process for the Construction of Novel CO2-Sourced Sulfur-Containing Building Blocks and Polymers

Article abstract of DOI:10.1002/anie.201905969

α-Alkylidene cyclic carbonates (αCCs) recently emerged as attractive CO₂-sourced synthons for the construction of complex organic molecules. Herein, we report the transformation of αCCs into novel families of sulfur-containing compounds by orga

Full text of DOI:10.1002/anie.201905969

A Journal of the Gesellschaft Deutscher Chemiker
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International Edition
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Accepted Article
Title: A switchable domino process for the construction of novel CO2-
sourced sulfur-containing building blocks and polymers
Authors: Farid Ouhib, Bruno Grignard, Elias Van Den Broeck, André
Luxen, Koen Robeyns, Veronique Van Speybroeck, Christine
Jerome, and Christophe Detrembleur
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201905969
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10.1002/anie.201905969
Angewandte Chemie International Edition
COMMUNICATION
A switchable domino process for the construction of novel CO2-
sourced sulfur-containing building blocks and polymers
Farid Ouhib,[a]! Bruno Grignard,[a]! Elias Van Den Broeck,[b] André Luxen,[c] Koen Robeyns,[d]
Veronique Van Speybroeck,[b] Christine Jerome,[a] Christophe Detrembleur[a]*
polyurethanes and polycarbonates, opening new perspectives for
Abstract:
a-alkylidene cyclic carbonates (aCCs) recently emerged
the design of advanced materials.8
as attractive CO2-sourced synthons for the construction of complex
organic molecules. Herein, we report the transformation of aCCs into
novel families of sulfur-containing compounds by organocatalyzed
chemoselective addition of thiols, following a domino process that is
switched on/off depending on the desired product. The process is
extremely fast, versatile in substrate scope, provides selectively linear
thiocarbonates or elusive tetrasubstituted ethylene carbonates with
high yields following a 100% atom economy reaction, and valorizes
CO2 as a renewable feedstock. It is also exploited to produce a large
diversity of unprecedented functional polymers. It constitutes a robust
platform for the design of new sulfur-containing organic synthons and
important families of polymers.
The ring-opening of aCCs by thiols is potentially attractive to
drastically enlarge the scope of these CO2-based synthons but is
surprisingly unexplored. It is expected to provide new relevant
sulfur-containing products for both synthetic organic (e.g.
thiocarbonates)
poly(monothiocarbonates)).
and
polymer
Thiocarbonates
chemistries
are
(e.g.
notably
important synthetic intermediates in organic chemistry9 and are
used as protecting groups for thiols.10 Poly(monothiocarbonate)s
are attractive polymers for optic applications due to their high
refractive index,11 but also for water purification due to the strong
binding ability of sulfur atom to metals.12 Only one article reports
the reaction of thiols with aCCs, but only by UV activated thiol-
ene addition to yield the trisubstituted ethylene carbonate 1
(Scheme 1, previous work).13
Carbon dioxide (CO2) is an attractive abundant, safe and
renewable carbon source for the synthesis of organic cyclic
carbonates. Today, these molecules find large and diverse
applications as intermediates for fine chemical synthesis,
electrolytes in Li-ion batteries, polar aprotic solvents, and
monomers for the preparation of world-relevant polymers such as
polycarbonates and polyurethanes.1 The [3+2] cycloaddition of
CO2 to epoxides is the most popular and straightforward approach
to five-membered cyclic carbonates2 and, with the recent
breakthroughs in their catalyzed transformations,3 new CO2-
based organic molecules with a high degree of complexity are
now accessible.4
Previous work
O
O
OH
CO2
cat.
R3-SH
O
O
O
R1
O
S
R1
R2
R3
R2
!CC
DMPA, UV, r.t.
R1
R2
1
R3-SH
O
DBU, r.t.
This work
O
on/off
O
O
O
S
R3
R3
R1
Beside, a-alkylidene cyclic carbonates (aCCs), are rapidly
emerging as another important class of industrially relevant CO2-
sourced cyclic carbonates.5 They are produced by catalytic
carboxylative coupling of propargylic alcohols with CO2.6
Compared to the conventional 5-membered cyclic carbonates,
the presence of an exocyclic vinylic group facilitates the
regioselective ring-opening of the cyclic carbonate by various
nucleophiles, leading to new potentials in modern organic
chemistry for the selective construction of novel molecules. The
potential of aCCs for the preparation of new building blocks is
enormous but examples are still limited to b-oxo-carbamates, b-
S
R1 R2
O
R2
2
3
☑
☑
mild conditions (r.t., metal-free)
up to 100% yield and selectivity
switching on/off domino process
large scope of substrates
Extension to functional polymers:
O
O
O
O
HS-R2-SH
cat., r.t.
O
O
S
S
R2
O
O
O
O
O
R1
n
O
O
R1
Bis!CC
P2
on/off
☑
new polymers
tunable functionality
O
O
oxo-carbonates,
b-hydroxy-1,3-oxazolidin-2-ones,
α-
cat.
OH
CO2
R2
hydroxyketone or 3-dialkylaminooxazolidin-2-one.7,8 Recently,
some of us demonstrated their utility for the synthesis of functional
R1
S
S
HO
n
O
O
R1
P1
O
Scheme 1. Organocatalyzed addition of thiols to CO2-sourced a-alkylidene
cyclic carbonates and extension to functional polymers.
[a]
Center for Education and Research on Macromolecules (CERM),
CESAM Research Unit, University of Liège, Sart-Tilman B6a, 4000
Liege,
Belgium
E-mail: christophe.detrembleur@ulg.ac.be
Center for Molecular Modeling, Ghent University, Technologiepark 46,
6052 Zwijnaarde, Belgium
GIGA – CRC in vivo Imaging, University of Liege, Sart-Tilman B6A,
4000 Liège, Belgium.
Institute of Condensed Matter and Nanosciences (IMCN), Université
Catholique de Louvain, 1348 Louvain-la-Neuve, Belgium
The authors contributed equally to this work
In this work, we investigated the organocatalyzed thiolation of
aCCs as an unprecedented source of a large palette of novel
sulfur-containing organic scaffolds and polymers. We discovered
that DBU catalyzed the quantitative ring-opening of aCCs by
various thiols, yielding either the b-oxothiocarbonate 2 or the
elusive tetrasubstituted ethylene carbonate 3 at a high yield
(Scheme 1). Product 2 was formed extremely rapidly at r.t.,
whereas 3 resulted from a novel DBU-catalyzed reaction following
[b]
[c]
[d]
!
Supporting information for this article is given via a link at the end of
the document
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10.1002/anie.201905969
Angewandte Chemie International Edition
COMMUNICATION
Table 1. Scope of the organocatalyzed addition of thiols to aCCs.
R3-SH
!CC
O
O
O
O
O
O
R3-SH
O
O
O
SH
O
O
O
S
O
O
O
O
O
R1
O
SH
R3
R3
T2
T1
R1 R2
R1
S
DBU (1mol%)
DMF, r.t.
O
R2
R2
SH
O
SH
2
3
O
!CC
10
T4
!CC1
!CC2
!CC3
T3
Entry
αCC
Thiol
T1
Time
ConvαCC
Conv2
[%]a
9.1
100
6.5
64
100
3
Yield 2
[%]a
90.9
0
93.5
36
0
97
77
53
Yield 3
[%]a
9.1
100
6.5
64
100
3
[%]a
> 99
> 99
> 99
> 99
> 99
> 99
> 99
1
2
3
4
5
6
7
1 min
2h
1 min
2h
24h
1 min
2h
αCC1
αCC2
T1
23
47
23
47
αCC3
T1
8
24h
> 99
9
1 min
2h
1 min
2h
24h
1 min
2h
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
10.7
100
7.3
66.6
100
5.3
27
56
2
58
95
1
3
95
89.3
0
92.7
33.4
0
94.7
73
44
98
42
5
99
97
5
10.7
100
7.3
66.6
100
5.3
27
56
2
58
95
1
3
95
αCC1
αCC2
T2
T2
10
11
12
13
14
15
16
17
18
19
20
21
22
αCC3
αCC1
αCC1
T2
T3
T4
24h
1 min
24h
24hb
1 min
24h
24hb
a conversions and yields determined by 1H NMR. ConvαCC = conversion of αCC; Conv2 = conversion of 2. b reaction at 80°C. Conditions: [αCC]/[thiol] = 1/1 , αCC =
4 mmol, VDMF = 1 mL, r.t.
of T1 to
a
CC1 was then followed by 1H- and 13C-NMR
an on/off switchable domino process. Finally, the reactions were
implemented for the synthesis of novel families of sulfur
containing polymers, including unprecedented polycyclics, with
functionalities that were modulated by switching on/off the domino
process.
spectroscopy to understand the origin of this product (ESI 2.1).
After only 1 min, the cyclic carbonate was fully converted into the
expected b-oxothiocarbonate 2 as the main product (91%), and
the tetrasubstituted cyclic product 3 as the minor one (9%) (Table
1, entry 1). With the reaction time, 2 progressively disappeared in
favor of 3, suggesting that 3 resulted from a rearrangement of 2.
Product 3 was quantitatively recovered after 2h, and its structure
was confirmed by 1H- and 13C-NMR spectroscopies, HR-MS, and
XRD of the re-crystalized product (Scheme 2C; ESI 4.1, Table S8).
Various CO2-sourced aCCs (Table 1) were tested to evaluate
the influence of the steric hindrance on the selectivity of the
reactions after both 1 min and 2 h of reaction. All aCCs were fully
converted after only 1 min of reaction, demonstrating the
impressively fast ring-opening of the cyclic carbonate (see ESI
2.1-2.6 for kinetics of reactions). The selectivity in 2 after 1 min
First, we tested the reaction of 4,4-dimethyl-5-methylene-1,3-
dioxolan-2-one ( CC1, Table 1) prepared by the catalyzed
a
carboxylative coupling of CO2 to 2-methyl-3-butyn-2-ol) with
benzylthiol T1 under stoechiometric conditions at r.t. in DMF
without any catalyst. No reaction was observed after 24h.
In order to favor the ring-opening, DBU was added, as it was
demonstrated to facilitate the ring-opening of aCCs with
alcohols.8 Surprisingly, the unexpected tetrasubstituted ethylene
carbonate 3 was quantitatively formed after only 2 h at low DBU
loading (1 mol%) (Table 1, entry 2). This observation is in sharp
contrast to the selective DBU catalyzed ring-opening of aCCs by
alcohols or secondary diamines that yielded b-oxo-carbonates or
b-oxo-urethanes, respectively.8 Substituting T1 for 2-
slightly increased with the steric hindrance, from 91% for
to 93.5% for CC2 and to 97% for the bulkier CC3 (entries 1, 3
and 6, Table 1). In parallel, the selectivity in 3 after 2h drastically
decreased with the steric hindrance from 100% for CC1, to 64%
for CC2 and 23% for CC3 (entries 2, 4 and 7, Table 1). Bulky
a
CC1,
a
a
Furanmethanethiol
T2
gave
also
the
corresponding
tetrasubstituted ethylene carbonate (Table 1, entry 10), and not
a
the expected b-oxothiocarbonate 2. The DBU-catalyzed addition
a
a
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10.1002/anie.201905969
Angewandte Chemie International Edition
COMMUNICATION
Nucleophilic attack of the carbonyl group by the thiolate
provides the metastable five-membered intermediate that ring-
opens into the thiocarbonate. Proton transfer from DBUH+ gives
the corresponding enol that tautomerizes into the thiocarbonate
2’. This addition mode is very fast as 2’ is formed at 91% yield in
1 min. The process is under equilibrium as suggested by
calculations with a backward free energy barrier of only 22.5
kJ.mol-1 (ESI 3, Fig. S15). Importantly, the thiolate is also able to
add to the carbon of the C=C bond (addition pathway (2)).
Computational investigations suggest that this addition mode
provides the corresponding carbonate anion adduct that follows
an irreversible intramolecular cyclization, aided by DBUH+, to
provide the tetrasubstituted ethylene carbonate 3’ and the release
of the catalyst. A concerted mechanism might also be involved
(see ESI 3) but at this stage, it is not possible to discriminate the
two mechanisms. This addition pathway (2) (stepwise or
concerted) is however slow (complete in 2h, Scheme 2B)
compared to (1) as supported by all kinetics of reactions (ESI 2.1-
2.6), and in line with higher calculated free energy barriers for
pathway (2) (ESI 3). In contrast to the formation of 2’ that is
reversible, the reaction pathway to 3’ is assumed to be irreversible.
Therefore 2’ is progressively fully converted into 3’ in the
presence of DBU, and this irreversible reaction is the main driving
force for the cyclization. The formation of 2’ is therefore under
kinetic control whereas the formation of 3’ is under
thermodynamic one. Importantly, when acetic acid was added
after 1 min of reaction, the domino process was switched off, as
the result of the deactivation of DBU that avoids the reversible
reaction to occur, and thus 3’ to be formed; only 2’ is collected. It
is important to note that when alcohols were used in the presence
of DBU instead of thiols under identical conditions, the domino
process was not observed because the formation of the b-oxo-
carbonate is irreversible as the result of the poorer leaving group
ability of alcoholates compared to thiolates. The same conclusion
prevails for the reaction with amines.
groups on aCCs therefore strongly slowed down the
rearrangement of 2 into 3. By extending the reaction time to 24h,
2 was fully converted into 3 for
the bulkiest CC3 (entries 5 and 8, Table 1). The same trend was
noted for 2-Furanmethanethiol T2 (entries 9-16). The scope of
substrate was further extended by screening the reaction of CC1
a
CC2, compared to only 47% for
a
a
with thiols T3 and T4 (entries 17-22, Table 1). The corresponding
products 2 were produced at a high yield (98-99%) after 1 min.
Product 3 was formed at 58% yield with T3 when the reaction time
was extended to 24h, whereas trace amount of 3 was detected
for T4. By carrying out the experiments at 80°C for 24h, product 3
was almost quantitatively formed in both cases. For all
experiments, the products 2 were collected at high yields provided
that the reactions were quenched after 1 min by the addition of
acetic acid (10-20 mol%) that switched off the domino process.
The course of this domino process can thus be described as
illustrated in Scheme 2A for the
a
CC1/T1 reaction, and is
supported by computational investigations (see ESI 3 for details).
A
O
O
O
DBUH+
Ph
(1)
O
Ph
DBUH+
DBUH+
Ph
S
O
!CC1
S
Fast
O
O
+
S
O
O
O
O
+
DBU
O
(1)
Fast
(2)
Ph
DMF, r.t.
SH
T1
(1)
Fast
- DBU DBU
On
On
Off
(2)
Slow
+ HAc
- DBUH+
DBUH+
100
100
80
60
40
20
0
O
O
Ph
S
B
O
Ph
80
60
40
20
0
S
O
O
OH
O
cyclization
- DBU
O
Ph
S
O
O
0
20 40 60 80 100 120
O
S
Ph
Time (min)
O
3’
2’
To further support this proposed mechanism, the
thiocarbonate 2’ was synthesized according to conditions
established in Table 1 (Entry 1). The purified compound was then
dissolved in DMF to which 1 mol% of DBU was added (see ESI
2.7). The transformation of 2’ into 3’ was then monitored at r.t. by
1H-NMR spectroscopy. Scheme 2C shows that the thiocarbonate
2’ was progressively and fully converted into 3’ (ESI 2.7). Also,
O
C
O
DBU (1 mol%)
DMF, r.t.
O
O
O
S
S
O
2’
3’
O
0 min
O
S
O
tiny amount of
a
CC1 was detected (<1mol%) when DBU was
added to 2’ (Figure S13), supporting the reversibility of the
addition mode (1) (Scheme 2A). No reaction was observed in the
absence of DBU. Importantly, when two thiocarbonates of
different structure were mixed in the presence of DBU, four
tetrasubstituted ethylene carbonates were collected, attesting
again for the reversibility of the addition mode (1) (ESI 2.8, Figure
S14).
4 h
O
O
O
24 h
S
Screening experiments with other bases of different pKa have
shown that superbases such as TBD, MTBD and DBN also
catalyzed the fast formation of the thiocarbonate 2’ (Table S9, ESI
4.2). The rate of formation of 3’ was however lower compared to
the reaction catalyzed by DBU. Weaker bases such as NEt3,
DABCO and DMAP presented poor catalytic activity for the
formation 2’ and did not catalyze the synthesis of 3’. Mechanistic
studies are ongoing in our laboratories in order to explain this
difference of behavior.
7.3
7.0
4.1
2.2
1.9
1.6
f1 (ppm)
Scheme 2. A) Switchable domino-process for the aCC1/T1 reaction with B) the
yields of 2’ and 3’ vs time; C) 1H-NMR study for the DBU catalyzed
rearrangement of 2’ into 3’.
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10.1002/anie.201905969
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COMMUNICATION
This switchable domino process was then evaluated for the
construction of novel regioregular sulfur-containing polymers, by
polyaddition of CO2-sourced bis(a-alkylidene cyclic carbonate)
HO
HO
OH
OH
Monomers
Dithiols:
CO2
CO2 cat.
cat.
(bis
a
CC1 and bis
a
CC2, see ESI 4.3 for their synthesis) with
Bis!CCs:
O
SH
dithiols (DT1 and DT2) (Scheme 3). The conversions, linkage
selectivity, and molecular characteristics of the polymers are
collected in Table 2. The DBU catalyzed polyadditions provided a
novel family of polymers, poly(thioether-co-cyclic carbonate) P1a-
d (Scheme 3). All polymerizations were remarkably highly
selective for the thioether-co-cyclic carbonate linkages (³ 99%) at
r.t. (Figure S41-48), and high conversions were noted after 24h at
a low organocatalyst content (1 mol%) (entries 1, 4, 6, 8; Table 2).
Moderate to high number average molar masses (Mn) were noted,
ranging from 15,700 to 75,300 g/mol. By raising the catalyst
content, Mn were also drastically increased from 15,900 to 54,000
O
O
O
HS
O
O
O
O
SH
O
HS
O
O
O
O
O
N
DT1
DT2
Bis!CC2
Bis!CC1
Catalyst: DBU (1 mol%)
Catalyst: FA (3 mol%), DBU (1 mol%)
N
Catalyst
DMF, r.t.
F3C
HO
CF3
OH
N
N
DBU
CF3
CF3
FA
DBU
Polymers
Poly(monothiocarbonate)
Poly(thioether-co-cyclic carbonate)
O
O
O
O
O
O
O
O
O
S
S
S
P2a
P1a
P1b
O
O
S
n
g/mol for bis
(5 min instead of 24h), the polymer obtained by polymerizing the
bis CC1/DT1 mixture was the poly(monothiocarbonate) P2a
a
CC1/DT1 (entry 2; Table 2). For short reaction times
S
n
2
O
O
O
2
O
O
O
O
O
O
S
O
n
O
P2b
P2c
a
O
O
S
O
(90% thiocarbonate linkages) (entry 1, Table S10). These
linkages were progressively fully converted into thioether-co-
cyclic carbonate moieties, providing P1a, after few hours (entries
2-3; ESI 4.4, Table S10, Figures S36-37).
S
n
O
O
n
O
O
O
O
O
O
O
S
S
P1c
P1d
2
O
O
O
S
S
O
2
O
n
Importantly, for the bis
a
CC2/DT2 mixture, the polymerization
O
O
O
O
O
O
was extremely fast with a conversion of 95% after only 1 min, and
the selective formation of P1d (thioether-co-cyclic carbonate
linkage of 95%) with a Mn of 11,800 g/mol (entry 1, Table S11).
The rapid formation of this linkage is assumed to be the result of
the high leaving group ability of the thiolate of DT2 (Scheme 2A)
that favors the cyclization. These DBU catalyzed polymerizations
thus demonstrate that the domino process is impressively fast and
efficient, also on macromolecules. Although rapidly quenching the
O
S
S
O
P2d
n
O
O
S
O
O
S
O
n
Scheme 3. Polyadditions of dithiols with bis(a-alkylidene cyclic carbonate)s.
The type and content of polymer linkages has a drastic
influence on the glass transition temperature (Tg) of the polymer.
As a general trend, Tg significantly increased with the content of
thioether-co-cyclic carbonate linkages. The most impressive
effect on Tg was noted for the polymers prepared with DT2, for
instance from 61°C to 126°C with 19 and 99% of thioether-co-
cyclic carbonate linkages, respectively (entries 5 and 4, Table 2).
bis CC1/DT1 polyaddition by acetic acid provided the expected
a
P2a, only low Mn was obtained (4,300 g/mol; entry 1, Table S10).
In order to increase the Mn, the polymerization period should be
extended. However the domino process then occurred, leading to
the transformation of the thiocarbonate linkages into thioether-co-
cyclic carbonate ones (entries 2-3, Table S10).
Interestingly, by using bis CC2, unusual hindered polycyclic
a
With the objective to prepare polymers rich in thiocarbonate
linkages and of reasonable Mn, we carried out the polymerizations
in the presence of DBU (1 mol%) added with the fluorinated
alcohol FA (1,3-bis(2-hydroxyhexafluoroisopropyl) benzene, 3
mol %; Scheme 3, ESI 4.6). Under these conditions, the series of
structures were incorporated within the polymer backbone with an
impressive impact on the thermal properties of the polymer. High
Tg polymers were formed when bis
a
CC2 was polymerized with
DT2 (entries 8-9, Table 2, Figure S49).
In summary, we have developed a novel robust switchable
domino process for the construction of important sulfur-containing
organic molecules by organocatalyzed chemoselective addition of
thiols to CO2-sourced a-alkylidene cyclic carbonates.
Thiocarbonates but also challenging tetrasubstituted ethylene
carbonates were selectively produced at high yield and at r.t
following a 100% atom economy reaction under stoechiometric
conditions. This process was also exploited to prepare
unprecedented regioregular sulfur-containing polymers. The “on-
demand” modulation of the structure and functionality of the final
product by switching on/off the domino process offers enormous
synthetic possibilities for both organic chemistry and
macromolecular engineering.
poly(monothiocarbonate)s P2a-c with
a
selectivity in
thiocarbonate linkages of 70-82% were prepared after 24h
(Entries 3, 5, 7; Table 2). Interestingly, by tuning the FA content,
we have access to polymers with intermediate linkages content
and functionality (Table S12, Figure S41). No polymerization was
observed in the absence of DBU, even with 3 mol% FA. Despite
further mechanistic investigations are required to understand the
action mode of FA, this novel strategy towards regioregular
poly(monothiocarbonate)s with a potentially large scope of
structures (aliphatic and aromatic) is an attractive alternative to
the conventional epoxide/COS ring-opening copolymerization
that gives access to aliphatic polymers with limited functions.14
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10.1002/anie.201905969
Angewandte Chemie International Edition
COMMUNICATION
Table 2. Scope of the step-growth polyaddition of CO2-sourced bis(a-alkylidene cyclic carbonate)s with dithiols (see Scheme 3 for chemical structures).
Entry
Thiol
Catalyst
Catalyst
Conv.
(%)
Mn
Mw
Đa
Polymer linkagesb
Tg
BisaCC
content
(g/mol)a
(g/mol)a
(°C)c
(mol%)
1
2
3
4
5
6
7
8
9
1
5
3/1
1
3/1
1
3/1
1
3/1
2.58
1.94
1.94
1.81
2.12
2.09
2.48
1.37
2.05
DBU
DBU
FA/DBU
DBU
FA/DBU
>99
>99
95
>99
97
15900
54000
9200
22000
21300
41000
105000
17900
39800
45300
P1a/P2a: 99/1
P1a/P2a: 99/1
P1a/P2a: 18/82
P1b/P2b: 99/1
P1b/P2b: 19/81
45
47
9
126
61
DT1
BisaCC1
DT2
DT1
DT2
BisaCC1
BisaCC2
BisaCC2
DBU
>99
15700
32800
P1c /P2c: 99/1
76
32
FA/DBU
DBU
FA/DBU
98
>99
95
15300
75300
20800
38000
103000
42700
P1c/P2c: 30/70
P1d/P2d: 99/1
P1d/P2d: 84/16
d
-
115
adetermined by SEC in THF or DMF using PMMA as calibration; bdetermined by 1H-NMR in CDCl3 or DMF-d7 at rt; cdetermined by dynamic scanning calorimetry
(DSC). dTg higher than the degradation temperature of the polymer; Conditions: [bisaCC]/[DT] = 1/1, [bisaCC] = 2 M in DMF, r.t., 24h
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Experimental Details, supplementary characterizations and computational
studies are provided in Supporting information
Acknowledgements
The authors thank the Fonds de la Recherche Scientifique
(FNRS) and the Fonds Wetenschappelijk Onderzoek
–
Vlaanderen (FWO) for funding the EOS project n°O019618F (ID
EOS: 30902231), and FNRS in the frame of the NECOPOL
project (convention U.N054.17). C.D. is Research Director by
F.R.S.-FNRS.
Keywords: carbon dioxide • synthetic methods •
organocatalysis • domino process • polymerization
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10.1002/anie.201905969
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
COMMUNICATION
O
O
O
The
organocatalyzed
Farid Ouhib, Bruno Grignard, Elias
Van Den Broeck, André Luxen,
Koen Robeyns, Veronique Van
Speybroeck, Christine Jérôme,
Christophe Detrembleur*
R3-SH
on/off
O
R1
O
O
O
O
S
chemoselective addition of thiols to
a-alkylidene cyclic carbonates is
fast
thiocarbonates
tetrasubstituted
carbonates with high yields by a
switchable domino process. This
robust synthetic method is also
exploited for the facile construction
R3
O
R3
R1
S
R1 R2
DBU, rt
R2
O
R2
and
yields
or
linear
elusive
O
O
O
O
HS-R2-SH
cat., rt
O
O
S
S
O
O
O
O
ethylene
R2
R1
n
O
O
Page No. – Page No.
R1
☑
☑
☑
☑
mild conditions (rt, metal-free)
on/off
A switchable domino process for
the construction of novel CO2-
up to 100% yield and selectivity
on/off domino process
O
O
S
R1
of
a
large
diversity
of
elusive tetra-substituted ethylene
carbonates and polymers
large scope
O
O
R2
sourced
sulfur-containing
O
S
unprecedented sulfur-containing
polymers.
building blocks and polymers
n
This article is protected by copyright. All rights reserved.