A CO2-induced ROCO2Na/ROCO2H buffer solution promoted the carboxylative cyclization of propargyl alcohol to synthesize cyclic carbonates

Article abstract of DOI:10.1039/c9cy02311a

A CO₂-induced ROCO₂Na/ROCO₂H buffer solution is developed and employed in the carboxylative cyclization of propargyl alcohol to generate α-alkylene cyclic carbonates. The introduction of CO₂ into the propargyl a

Full text of DOI:10.1039/c9cy02311a

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DOI: 10.1039/C9CY02311A
ARTICLE
CO2-induced ROCO2Na/ROCO2H buffer solution promoted
carboxylative cyclization of propargyl alcohol to synthesize cyclic
carbonate
Received 00th January 20xx,
Accepted 00th January 20xx
Shaorui Yan,a Ruinian Zhou,a Feng Han,a Mengmeng Feng,a Chengxia Miao,a,b Shuai Zhang*,a and
Shiyun Ai*,a
DOI: 10.1039/x0xx00000x
A CO2-induced ROCO2Na/ROCO2H buffer solution is developed and employed in the carboxylative cyclization of propargyl
alcohol to generate α-alkylene cyclic carbonates. The Introduction of CO2 into propargyl alcohol/sodium tertiary pentoxide
system can provide ROCO2Na/ROCO2H buffer solution with both basic and acidic species. The basic and acidic species can
simultaneously promote the generation of carbonate anion intermediate and the interaction between alkyne moieties of
propargyl alcohol and H+ proton, facilitating the carboxylative cyclization. What’s more, the bulky (n-C4H9)4N+ cation of
tetrabutylammonium bromide as an additive plays a crucial role in enhancing the nucleophilicity of the carbonate anion
intermediate. Various α-alkylene cyclic carbonates are obtained in this catalytic system with relatively good yields at 80 °C.
alkyne moieties of propargyl alcohol. For example, after being
incorporated with Ag metal sites, porous polymers represent
excellent catalytic activity for the synthesis of cyclic
Introduction
CO2，the main kind of greenhouse gas, is a promising C1 source
because that it is cheap, nontoxic, abundant and renewable.1,2
The recycling of CO2 to value-added chemicals or fuels has
drawn worldwide attention, which is accorded with the
requirement of green chemistry and sustainability
development. For example, CO2 can be used for the
construction of C-C, C-N, C-O and C-H bonds to prepare a series
of valuable molecules.3-6 Therefore, investigations focused on
CO2 recycling and transformation are highly desired, and have
been widely ongoing. Cyclization of carbon dioxide with
propargyl alcohol to give α-alkylene cyclic carbonate is one of
synthetic hotspots for CO2 fixation. There are already many
catalysts capable of converting propargyl alcohols and carbon
dioxide to α-alkylene cyclic carbonates, especially with terminal
propargyl alcohols as substrates. The activation of alkyne
moieties and CO2 is crucial for this carboxylative cyclization. Cu
complex,7 Ag complex,8 1,8-diazabicyclo-[5.4.0]-7-undecenium
2-methylimidazolide ([DBUH][MIm]),9 N-heterocyclic olefins
(NHO),10 Fluorine microporous organic polymer-silver (F-MOPs-
Ag),11 porous silver coordination polymer (Ag-TCPE).12 have
been used in carboxylative cyclization of non-terminal propargyl
alcohol. Transition metal complexes (Scheme 1a), such as Cu
complex,7 Ag complex,8,11-12 are commonly employed for the
carboxylative cyclization of non-terminal propargyl alcohol,
since these transition metal complexes can efficiently active the
carbonates.8,11-12 However, transition metal complexes are
usually expensive and toxic. Proton (H+) can interact with the
election-rich alkyne moieties of propargyl alcohols, and
probably can be employed in the carboxylative cyclization. On
the other hand, alkaline environment is crucial to this
carboxylative cyclization, because it facilitates the generation of
the carbonate anion intermediate. Taking together, CO2-
induced buffer solution provides a promising solution to the
carboxylative cyclization, since it has both basic and acidic
species.
O
a)
O
OH
O
O
CO2
O
R1
O
R1
R2
R2
[M]+
Ar
+
R1
Ar
Ar
R2
b)
O
H2O
+
CO2
H+
H+
in situ
HO
O
carbonic
acid
O
O
ROH
RO
+
CO2
CO2
+
+
in situ
buffer
solution
RO
RO
O
O
Na+
Na+
O
c)
This work:
O
OH
O
O
NaOtP
O
R1
O
R1
R2
CO2
R2
H+
Ar
a.
R1
Ar
O
College of Chemistry and Material Science, Shandong Agricultural University,
Ar
R2
Taian, Shandong, 271018, China
Buffer
O
OtP
b. State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical
Engineering, Ningxia University, Yinchuan, Ningxia, 750021, China
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
solution
Scheme 1. The carboxylative cyclization of non-terminal propargyl alcohol.
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Table 1. Optimization of reaction conditions.
DOI: 10.1039/C9CY02311A
When CO2 is added into aqueous solution, acidic solution can be
obtained, in which the pH can decrease to about 3.0 (Scheme
1b). In situ carbonic acid (CO2/H2O and CO2/alcohol system), can
be easily recovered and removed by adjusting CO2 pressure and
temperature. Up to now, these carbonic acids, have been
widely investigated to replace traditional inorganic/organic
O
NaOtP (2.4 equiv.)
TBAB (2.4 equiv.)
OH
O
O
Ph
+ CO2
1,4-dioxane
(2.0 MPa)
Ph
2a
1a
strong acids, such as in the field of pretreatment of biomass
materials
NaOtP
(equiv.)
Entry
T/oC
P/MPa
t/h
Yield/%
13-14
and acid-catalyzed reactions.15-19 For example,
compared with CO2-free pre-treatments, high pressure
CO2/H2O system with in situ formation of carbonic acid assists
the autohydrolysis of wheat straw, leads to higher dissolution
of hemicellulose into xylo-oligosaccharides and xylose, and
afford much higher total sugars yield.20-21 He and coworkers
described the selective hydrodeoxygenation of lignin β-O-4
model compounds and aromatic ketones in acidic
PdCl2/CO2/MeOH system, to produce phenethoxybenzene and
ethylbenzenes/phenols, respectively.19 The introduction of CO2
(1 MPa) promotes the generation of in situ methylcarbonic acid
in CO2/MeOH system, which acts as an acidic catalyst and
remarkably improves the reaction efficiency.
Although significant advancements of the carboxylative
cyclization and in situ carbonic acid system have been achieved,
their subtle integration, especially the application of in situ
buffer solution in the carboxylative cyclization is attracting and
highly desired. As shown in Scheme 1b, CO2 can react with
alcohol and sodium alkoxide to generate alkyl carbonic acids
and carbonate salts with both basic and acidic species, which
can serve as potential buffer solution. And the CO2-induced
buffer solution can find promising applications in the synthesis
of cyclic carbonates. Herein, we describe the CO2-induced
buffer system can promote the carboxylative cyclization of non-
terminal propargyl alcohols to cyclic carbonates with good
yields (Scheme 1c). In this buffer solution, acidic proton can
interact with alkyne mioety of non-terminal propargyl alcohol
by electrophilic attack, facilitating the subsequent nucleophilic
attack of carbonate anion to generate α-alkylene cyclic
carbonate (Scheme 1c).
1
2
2.4
2.4
2.4
2.4
2.4
1.2
0.5
2.4a
2.4b
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
2.4
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
70
90
1.0
1.5
2.0
3.0
4.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
12
24
24
24
41
66
70
69
64
43
NR
23
NR
57
34
25
NR
17
50
26
NR
45
78
39
50
3
4
5
6
7
8
9
10c
11d
12e
13f
14g
15h
16i
17j
18
19
20
21
Results and Discussion
In order to obtain the optimized conditions for the synthesis of
carbonate, 1-(phenylethynyl)cyclohexan-1-ol (1a, 1 mmol) is
chosen as the model substrate. The carboxylative cyclization of
1a is investigated closely in the presence of sodium tertiary
pentoxide (NaOtP) and tetrabutylammonium bromide (TBAB) at
80 °C in 1,4-dioxane (Table 1). NaOtP and 1a can form
ROCO2H/ROCO2Na buffer solution under high CO2 pressure,
which probably promotes the carboxylative cyclization. CO2
pressure and the dosage of NaOtP can significantly affect the
generation and equilibrium of ROCO2H/ROCO2Na buffer
solution in this system. Therefore, their influences are the
priorities for investigation. As shown in Table 1, the yields of
carbonate 2a increase with the elevated CO2 pressure (entries
1-3). When it is higher than 2.0 MPa, the effect of CO2 pressure
is no longer significant, similar or lower yields (70%, 69%, 64%)
are obtained at 2.0, 3.0, 4.0 MPa CO2 pressure, respectively
Reaction conditions: 1-(phenylethynyl)cyclohexan-1-ol (1a) (1.0 mmol, 200.3 mg),
NaOtP (2.4 mmol, 264.2 mg), TBAB (2.4 mmol, 773.7 mg), 1,4-dioxane (3 mL), 2.0
MPa CO2, 80 oC; the products are isolated by column chromatography. a NaOtBu
(2.4 mmol, 230.6 mg) instead of NaOtP. b KOtBu (2.4 mmol, 269.3 mg) instead of
NaOtP. c 1.2 eq TBAB. d 0.5 eq TBAB. e 0.1 eq TBAB. f TMAB (2.4 mmol, 369.7 mg)
instead of TBAB. g TEAB (2.4 mmol, 504.4 mg) instead of TBAB. h THAB (2.4 mmol,
1177.7 mg) instead of TBAB. i TBAI (2.4 mmol, 886.5 mg) instead of TBAB. j TBACl
(2.4 mmol, 667.0 mg) instead of TBAB.
(entries 3-5). Slightly reducing the dosage of NaOtP results in
obvious decrease of yields (43%, 0%, entries 6-7). When the
dosage of NaOtP is 0.5 equiv., no carbonate 2a is obtained
(entry 7). Replacement of NaOtP by sodium tertiary butoxide
(NaOtBu) or potassium tertiary butoxide (KOtBu) also leads to
2 | J. Name., 2012, 00, 1-3
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poor yields (23%, 0%, entries 8-9). On the other hand, TBAB is On the other hand, electron-donating groups canViiemwpArrtoicvleeOntlhinee
DOI: 10.1039/C9CY02311A
used as additives in this system, based on the proposed idea electron density of alkyne moieties. Therefore, it is not
that the bulk mass of (n-C4H9)4N+ cation enhances the necessary to use high CO2 pressure for these propargyl alcohol
nucleophilicity of intermediate carbonate anion.22 As expected, substrates. High pressure even can result in the reduced yields
70% yield is obtained when 2.4 equiv. TBAB is used (entry 3). (2b, 2n). These results indicate the subtle property of our
The lower dosage of TBAB results in significantly decreased developed reaction system. Unexpectedly, propargyl alcohol
yields (entries 10-12, 70%-25%). What’s more, only 0% and 17% with thiophenyl moiety (2t) and terminal propargyl alcohol (2u)
yields are observed when the volume of bulky cation is reduced are not applicable in this reaction system, which probably is
by using tetramethylammonium bromide (TMAB) and ascribed to the strong H+-philicity of thiophene group (2t) and
tetraethylammonium bromide (TEAB) instead of TBAB (entries the poor H+-philicity of terminal alkyne moiety (2u). Taken
13-14), which is agreement with the proposition about bulky together, the method we have obtained has a relatively good
cations. However, when tetraheptylammonium bromide applicability for most of the non-terminal tertiary propargyl
(THAB) is employed instead of TBAB, only 50% yield of 2a is alcohol.
obtained (entry 15), indicating the subtlety of the volume of
bulky cation in this reaction system. On the other hand, 26% and
Table 2 Scope of the synthesis of cyclic carbonate.a
O
O
O
O
0% yields are obtained when tetrabutyl ammonium iodide
(TBAI) and tetrabutyl ammonium chloride (TBACl) are employed
(entries 16-17). Solvents with medium polarity, such as THF and
1,4-dioxane, even their mixed solvent can give 61%, 53% and
49% yields (Table S1). Furthermore, the yield decreases
significantly with the increasing polarity of solvent. 26% yield is
obtained when acetonitrile is employed (Table S1). No reaction
takes place in strong polar solvents, such as DMAc, NMP (Table
S1). These phenomena probably are ascribed to that higher
polar solvents can trap the generated H+, inhibiting the
interaction between H+ and alkyne moiety. Further
investigation about the influence of reaction time and
temperature is also performed. Prolonging the reaction time
can improve the yield (entries 3, 18-19), a high yield of 78% is
obtained in 24 h. Increasing or decreasing the temperature have
adverse influence on the yields (entries 20-21). Lower yields
(39%, 50%) are found at 70 oC or 90 oC. Finally, based on these
results above, the optimal condition is well developed.
Me
Et
O
O
O
O
O
O
O
O
O
b
b
2a
2d
, 53%
, 78%
O
2b
2c
, 64% (33%)
, 59% (53%)
O
O
O
O
O
F
Br
Me
O
O
O
c
O
O
O
c
b
b
2g
2h
, 74%
, 71%
2e
2f
, 47% (77%)
O
, 33% (66%)
O
O
O
Et
O
Br
F
O
O
O
O
O
O
O
O
c
c
, 64%, 55%,b 58%c
O
, 54% (49%)
O
c
2i
2l
, 66%
, 79%
2j
2k
O
O
Me
Et
O
O
O
O
O
O
O
O
c
c
c
c
2m
2o
2s
2p
, 71%
, 65%
O
, 42%
2n
, 28%, 46%
O
O
O
O
O
Br
O
O
O
O
O
O
Having established the optimized reaction condition, the
application scope of this reaction system is subsequently
explored (Table 2). As shown in Table 2, various functionalized
non-terminal propargyl alcohols were tested under optimal
S
OMe
c
c
c
2q
2r
, 79%
, 61%, 42%
O
2t
, NR
, 67%
O
O
o
condition at 80 C. Functional groups, such as alkyl, methoxyl,
halogen, aryl groups present excellent compatibility in this
reaction system, lots of α-alkylene cyclic carbonates with
various functional groups (2a-2s) are obtained with moderate
to good yields. To investigate the effect of buffer solution,
different CO2 pressures are used for several substrates.
Interestingly, based on the yields of 2b, 2c, 2e, 2f, 2j, 2k, 2n, it
can be concluded that high pressure, such as 3.0 MPa is not
favorable for propargyl alcohol substrates with electron-
donating groups (2b, 2c, 2j, 2n) at the para position of benzene
ring, lower or similar yields are obtained compared with the
yields under lower CO2 pressure (Table 2). However, at higher
CO2 pressure, propargyl alcohols with electron-withdrawing
groups (2e, 2f, 2k, 2q), such as -F, -Br give higher yields than
those at relatively lower CO2 pressure. These interesting
phenomena are probably ascribed to the reaction activity
between alkyne groups and H+ in the buffer system. The
electron-withdrawing groups reduce the electron density of
alkyne moieties, thereby more H+ concentration are required to
stratify the smooth interaction between alkyne groups and H+.
2u
, NR
a
Unless otherwise stated, the reactions were carried out with propargyl alcohol
(1.0 mmol), NaOtP (2.4 mmol, 264.2 mg), TBAB (2.4 mmol, 773.7 mg), under the
condition of 2.0 MPa CO2, 80 oC, 24 h in 3 mL 1,4-dioxane; the products are isolated
by column chromatography; b 3.0 MPa; c 1.0 MPa. NR = No Reaction.
To gain insight into the reaction mechanism, several control
reactions were performed. Initially, it is proposed that the bulk
(n-C4H9)4N+ cation improves the nucleophilicity of carbonate
anion intermediate. To prove this proposition, TBAB is replaced
by 15-crown-5 (Scheme 2a) because of its chelating ability with
Na+ cation to generate bulky cation. Expectedly, 67% yield of 2a
was obtained, proving that the bulk mass cation is the main
contribution of TBAB, while the Br- anion makes a lower
contribution.22 In other word, (n-C4H9)4N+ tert-pentoxide is
generated from TBAB and NaOtP, and promotes the
carboxylative cyclization reaction. Notably, the chelated Na+
cation can’t interact with alkyne moiety of 2a. Therefore, the H+
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cation is the only possibility for the interaction with alkyne In summary, CO2-induced ROCO2Na/ROCO2H buffVeierwsAorltiuclteioOnnlinies
DOI: 10.1039/C9CY02311A
moiety. To provide some evidences on the proposed CO2- generated from NaOtP and propargyl alcohol, which possesses
induced buffer solution, the existence of H+ is one of the crucial both acidic and basic properties. And this buffer solution
factors. It is envisioned that H+ cation interact with alkenyl promotes the carboxylative cyclization of propargyl alcohol to
moiety and facilitate the subsequent nucleophilic attack of generate cyclic carbonates. The basic and acidic sites in buffer
carbonate anion intermediate. On the other hand, based on the can promote the generation of carbonate salt intermediate and
results in Table 1-2, more H+ by high CO2 pressure has no its subsequent nucleophilic successively, facilitating the
obvious or unfavourable effects on the yields of propargyl carboxylative cyclization. Various α-alkylene cyclic carbonates
alcohols without electron-withdrawing groups. The addition of are obtained in this catalytic system with relatively good yields
tert-pentyl alcohol (1.0 equiv., tPOH) as extra proton source at 80 °C. These results achieved mark this protocol as a
results in slightly lower yield (64%) of 2a (Scheme 2b), which is promising strategy of CO2 utilization. Further investigations on
agreement with the results in Table 1-2. Inspiringly, DBU (1,8- CO2 fixation in CO2-induced buffer solution are ongoing.
diazabicyclo[5.4.0]undec-7-ene) as strong organic base can
capture the generated H+ in the reaction system. As expected,
NaOtP
TBAB
the introduction of DBU (1.0 equiv.) leads to the significantly
reduced yield of 2a (25%, Scheme 2c). Therefore, H+ cation is
crucial and subtle to the success of the carboxylative cyclization.
Accordingly, based on these results, a CO2-induced buffer
reaction system is proposed (Scheme 3). Initially, NaOtP react
with TBAB to produce (n-C4H9)4N+ tert-pentoxide (A). After the
addition of propargyl alcohol (1a), it will reach an equilibrium
quickly between alcohol and sodium alkoxide (B, Scheme 3).
After the introduction of CO2, alkyl carbonic acid and alkyl
carbonate salts (C) are generated in the form of buffer solution.
In this buffer solution, alkyl carbonate salt serves as a base,
promoting the generation of intermediate C. Subsequently,
alkyl carbonic acid provide H+ cation to interact with electron-
rich alkyne moiety of substrate 1a, facilitating the nucleophilic
attack of carbonate anion. What’s more, the bulky cation (n-
C4H9)4N+ plays a key role in enhancing the nucleophilicity of the
carbonate intermediate. Finally, the product 2a is obtained in
good yield.
O
H
O
NaBr
O
Ph
O
Ph
1a
(n-C4H9)4N+
OtP
H
2a
A
(n-C4H9)4N+
O
O
H
O
(n-C4H9)4N+
+
O
O
Ph
B
Ph
D
H
O
CO2
O
(n-C4H9)4N+
O
tP
O
O
O
Ph
H
C
O
O
tP
O
Scheme 3. Proposed mechanism based on CO2-induced buffer solution.
O
a)
OH
NaOtP (2.4 equiv.)
15-crown-5 (2.4 equiv.)
O
O
Experimental
2.0 MPa CO2
80 oC
Ph
Ph
The synthesis of cyclic carbonates was carried out in an
autoclave (50 mL). Schlenk tubes (10 ml) were employed in the
synthesis of propargyl alcohols. 4-Ethyl phenylacetylene and 4-
ethynyltoluene were purchased from Aladdin, other reagents
were obtained from Maclean. All reagents were used without
further purification. Carbon dioxide with a purity of 99.9% was
commercially available (Yingchun Gas Company). The products
were purified by column chromatography and characterized by
NMR spectra (Brucker, 600 MHz) with CDCl3 as solvents (1H
NMR: 7.26 ppm; 13C NMR 77.16 ppm).
1a
(1.0 mmol)
OH
2a
, 67%
O
b)
c)
NaOtP (2.4 equiv.)
TBAB (2.4 equiv.)
tPOH (1.0 equiv.)
O
O
Ph
2.0 MPa CO2
80 oC
Ph
Ph
1a
(1.0 mmol)
OH
2a
, 64%
O
NaOtP (2.4 equiv.)
TBAB (2.4 equiv.)
DBU (1.0 equiv.)
O
O
General procedure for the synthesis of α-alkylidene cyclic
carbonates: Taking 1a as a model substrate, the reaction was
carried out in a 50 mL stainless-steel autoclave reactor with an
inner glass liner and a magnetic stirrer. The inner glass liner was
initially charged with 1a (200.3 mg, 1.0 mmol), TBAB (773.7 mg,
2.4 mmol), NaOtP (264.2 mg, 2.4 mmol), 1,4-dioxane (3 ml),
respectively. And then, the autoclave was sealed and CO2 (2
MPa) was introduced. The reaction mixture was stirred for 24 h
Ph
2.0 MPa CO2
80 oC
1a
(1.0 mmol)
2a
, 25%
Scheme 2. Control experiments. The reaction condition is similar to the optimized
conditions with several adjustments. a) 15-crown-5 (2.4 equiv.) instead of TBAB; b) the
addition of tert-pentyl alcohol (1.0 equiv.); c) the addition of DBU (1.0 equiv.).
Conclusions
o
at 80 C. After the reaction is over, the reactor is cooled in ice
water bath for 30 minutes and CO2 is released slowly. The
organic layer obtained by the extraction with ethyl acetate (20
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5
a) X. Liu, X. Li, C. Qiao, H. Fu and L. N. He, Angew. Chem. Int.
mL×3) was rinsed with saturated sodium chloride solution, the
organic layer was dried with anhydrous Na2SO4 and
concentrated in vacuum. The crude product was purified by
silica gel chromatography (petroleum ether/ethyl acetate =
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1
10/1). 2a was obtained as a white solid. H NMR (600 MHz,
CDCl3) δ 7.54 (d, J = 7.7 Hz, 2H), 7.35 (t, J = 7.7 Hz, 2H), 7.29 -
7.19 (m, 1H), 5.47 (s, 1H), 2.13 - 2.03 (m, 2H), 1.70 (td, J = 12.9,
11.7, 7.8 Hz, 7H), 1.34 (ddd, J = 12.0, 8.2, 3.6 Hz, 1H). 13C NMR
(151 MHz, CDCl3): δ 151.47, 151.01, 132.59, 128.63, 128.48,
127.51, 101.80, 87.30, 36.72, 24.44, 21.75.
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Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
We are grateful to China Postdoctoral Science Foundation
(Grant No. 2019M652447), Natural Science Foundation of China
(Grant No. 21972079), Natural Science Foundation of Shandong
Province (Grant No. ZR2017BB025, J16LC15), Incubation
Program of Youth Innovation in Shandong Province and the
Youth Science and Technology Innovation Fund of Shandong
Agricultural University (Grant No. 24166) for financial support.
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