Tetraarylphosphonium Salt-Catalyzed Carbon Dioxide Fixation at Atmospheric Pressure for the Synthesis of Cyclic Carbonates

Article abstract of DOI:10.1021/acscatal.6b02265

Phosphonium salts exhibit great utility in organic synthesis. However, tetraarylphosphonium salts (TAPS) have found limited use as catalysts. We demonstrate the TAPS-catalyzed carbon dioxide fixation at atmospheric pressure for the coupling reaction with

Full text of DOI:10.1021/acscatal.6b02265

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Letter
Tetraarylphosphonium Salt-Catalyzed Carbon Dioxide Fixation
at Atmospheric Pressure for the Synthesis of Cyclic Carbonates
Yasunori Toda, Yutaka Komiyama, Ayaka Kikuchi, and Hiroyuki Suga
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.6b02265 • Publication Date (Web): 13 Sep 2016
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ACS Catalysis
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Tetraarylphosphonium Salt-Catalyzed Carbon Dioxide Fixa-
tion at Atmospheric Pressure for the Synthesis of Cyclic Car-
bonates
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Yasunori Toda,* Yutaka Komiyama, Ayaka Kikuchi, and Hiroyuki Suga*
Department of Materials Chemistry, Faculty of Engineering, Shinshu University, Wakasato, Nagano 380ꢀ8553, Japan
ABSTRACT: Phosphonium salts exhibit many of utilities in organic synthesis. However, tetraarylphosphonium salts (TAPS) have
found limited use as catalysts. We demonstrate the TAPSꢀcatalyzed carbon dioxide fixation at atmospheric pressure for the couꢀ
pling reaction with epoxides. 5ꢀMembered cyclic carbonates were obtained, including enantioꢀenriched carbonates. Mechanistic
studies revealed the origin of the behavior of TAPS to be the in situ formation of an active species by TAPS addition to epoxides
via halohydrin intermediates.
KEYWORDS: chemical fixation, carbon dioxide, epoxides, cyclic carbonates, phosphonium salts
Phosphonium salts are phosphorus(V) compounds featuring
a tetrahedral phosphonium cation, and are widely used in orꢀ
ganic synthesis as precursors of Wittig reagents, phase transfer
CO2 holds great potential as an abundant, inexpensive, nonꢀ
flammable, nontoxic, and renewable C1 building block.5 The
chemical fixation of CO2 into valuable products has recently
received much attention. One of the most wellꢀknown methods
is the coupling of CO2 and epoxides for the synthesis of 5ꢀ
membered cyclic carbonates.6 Considerable effort has been
devoted to the development of efficient catalytic systems for
this transformation, especially Lewis acidic metalꢀbased sysꢀ
tems.7,8 The use of bifunctional catalysts consisting of an elecꢀ
trophilic metal ion and a nucleophilic halide ion significantly
accelerates the process under mild conditions.8f,g Meanwhile,
the area of organocatalysis for the CO2 coupling with epoxides
is relatively limited,9 despite the fact that bifunctional strateꢀ
gies are particularly utilized in organocatalytic reactions10 In
addition, it is still challenging to perform the reaction at ambiꢀ
ent CO2 pressure. Although quaternary ammonium and phosꢀ
phonium salts are commonly employed for the CO2 fixation,11
in contrast to metal catalysis, bifunctional catalysts based on
onium salts have been rarely reported.4 We posited that a hyꢀ
drogen bond donor, a hydroxyl group properly attached to a
TAPS, might promote the CO2 insertion into epoxides through
synergistic effects of an ionic Brønsted acid and a halide ion.
Here, we demonstrate the first use of TAPS 1 for the chemical
fixation of CO2 with epoxides 2 at atmospheric pressure, leadꢀ
ing to cyclic carbonates 3. Moreover, the present study emꢀ
phasizes the importance of functional and structural requireꢀ
ments of TAPS for the activation of epoxides.
catalysts,
ionic
liquids,
and
other
applications.1
Tetraarylphosphonium salts (TAPS) with the formula
[Ar1(Ar2)3P+]Xꢀ can be readily prepared by coupling reactions
of an aryl halide (Ar1ꢀX) and a triarylphosphine ((Ar2)3P),
which are stereoelectronically tunable.2 The exploration of
TAPS function especially for catalysis is hence attractive, but
their catalytic ability has remained unexploited.1n It is exꢀ
pected that TAPS 1 might serve as a bifunctional catalyst
composed of a Brønsted acidic site and a nucleophilic site by
introduction of a hydroxyl group on an aromatic ring (Figure
1). We reasoned that chemical fixation of carbon dioxide
(CO2) with epoxides 2 to produce cyclic carbonates 3 would
be a suitable target for validating this catalyst design because
Brønsted acidꢀactivation of an epoxide 2 by a TAPS 1 could
facilitate the epoxide ringꢀopening step by the counter anion
(Xꢀ) of a TAPS.3,4 This devised system raised the inherent
question of not only whether the activation of epoxides was
possible but also whether the carbonate product by incorporaꢀ
tion of CO2 could be obtained. In fact, to the best of our
knowledge, there are no examples of TAPSꢀcatalyzed CO2
fixation reactions, and the challenge inspired us to probe a
novel application of TAPS as interesting catalysts.
At the outset of our study, we prepared TAPS 1a from 2ꢀ
bromoꢀpꢀcresol in only oneꢀstep by using Pdꢀcatalyzed couꢀ
pling reaction with triphenyl phosphine, and attempted Xꢀray
crystallographic analysis (Figure 2). In the crystalline state, 1a
exists as a hydrate form, and hydrogen bonding between the
hydroxyl group of 1a and the water molecule was inferred
based on the distance of the two oxygen atoms: O(1)H－O(2)
= 2.581 Å. This implies that ionic Brønsted acid 1 could actiꢀ
vate an epoxide through hydrogen bond interaction, and motiꢀ
vated us to investigate the CO2 fixation.
Figure 1. Working hypothesis: The design of TAPS as a
bifunctional catalyst for the coupling of CO2 and epoxides.
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Table 1. Screening of catalysts and optimization of the
reaction conditionsa
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Figure 2. Preparation and ORTEP drawing (30% probability
ellipsoids) of TAPS 1a.
Entry
catalyst
solvent
yieldb
(%)
41
(mol%)
1a: G = Me, X = Br
4 (10)
(M)
1
2
oꢀxylene (0.1)
oꢀxylene (0.1)
oꢀxylene (0.1)
oꢀxylene (0.1)
oꢀxylene (0.1)
oꢀxylene (0.1)
oꢀxylene (0.1)
oꢀxylene (0.1)
oꢀxylene (0.1)
oꢀxylene (0.1)
PhCl (0.1)
The initial experiment was performed using styrene oxide
(2a), 10 mol% of TAPS 1a, and a balloon of CO2 in oꢀxylene
at 120 °C for 12 hours (Table 1, entry 1). The reaction affordꢀ
ed desired product 3a in low, but promising yield (41%). Difꢀ
ferent types of catalysts 4ꢀ8 including ammonium salt 7 were
then screened, because TAPS 1 could potentially catalyze the
ringꢀopening step in an intermolecular manner (Table 1, enꢀ
tries 2ꢀ6). Interestingly, none of the catalysts yielded the prodꢀ
uct, and starting material 2a was nearly completely recovered.
These results clearly showed that the orthoꢀhydroxyl group of
1a and phosphonium moiety were crucial in the reaction proꢀ
gress, implying the importance of bifunctional catalysis. This
was supported by an experiment employing catalytic amounts
(10 mol%) of phenol and tetraphenylphosphonium bromide
(8) to see conversion of 2a (Table 1, entry 7). As expected,
only a trace amount of 3a was obtained, and phenol itself did
not yield 3a (Table 1, entry 8). Other Brønsted acꢀ
id/nucleophilic Lewis base binary systems were also investiꢀ
gated, but were not effective compared with 1a (Table 1, enꢀ
tries 9 and 10). Switching the solvent to chlorobenzene and
increasing the concentration improved the yield up to 78%,
and finally, the use of 15 mol% of 1a afforded 3a in 90% isoꢀ
lated yield (Table 1, entries 11ꢀ13).12 Next, the electronic efꢀ
fect of the substituents on the phenol moiety was investigated
to learn if the Brønsted acidity of the hydroxyl group in 1
would affect the reaction progress (Table 1, entries 14 and 15).
To our surprise, introduction of a strong electronꢀwithdrawing
group (1b: G = CF3) resulted in low yield, whereas an elecꢀ
tronꢀdonating group (1c: G = OMe) did not change the activiꢀ
ty. It should be noted that the use of 1b afforded a bromohyꢀ
<2
3
5 (10)
<2
4
6 (10)
<2
5
7 (10)
<2
6
8: Ph4PBr (10)
<2
7
PhOH (10) + 8 (10)
PhOH (10)
<2
8
<2
9
PhOH (10) + DMAP (10)
TsOH (10) + Py [PPTS] (10)
1a (10)
<2
<2c,d
10
11
12
13
14
15
16
17
18
54
1a (10)
PhCl (0.3)
78
1a (15)
PhCl (0.3)
90 (90)
35
1b: G = CF3, X = Br (15)
1c: G = OMe, X = Br (15)
1d: G = Me, X = I (15)
1e: G = Me, X = OTf (15)
1f: G = Me, X = PF6 (15)
PhCl (0.3)
PhCl (0.3)
86
PhCl (0.3)
85
PhCl (0.3)
<2d
<2d
PhCl (0.3)
aUnless otherwise noted, all reactions were carried out on a 0.20 mmol scale using
styrene oxide (2a) under a balloon of CO2 at 120 °C for 12 h. See Supporting
Information for details. bDetermined by 1H NMR analysis using 1,1,2,2ꢀ
tetrachloroethane as an internal standard (Isolated yield is shown in parentheses).
cFull conversion of 2a. dPhenylacetaldehyde was observed as a major byꢀproduct.
Table 2. Substrate scope of TAPS-catalyzed CO2 fixation
at atmospheric pressurea
1
drin intermediate in 11% yield by H NMR. In addition, we
scrutinized the effects of counter anions of TAPS 1 (Table 1,
entries 16ꢀ18). TAPS 1d, having an iodide ion (Iꢀ), marginally
decreased the yield, even though the nucleophilicity of Iꢀ is
stronger than Brꢀ in aprotic solvent (Table 1, entry 16). On the
other hand, the attempts using TAPS 1e and 1f, involving lessꢀ
nucleophilic counter anions such as triflate (TfOꢀ) and hexꢀ
afluorophosphate (PF6ꢀ), led to no formation of cyclic carꢀ
bonate 2a (Table 1, entries 17 and 18). It is obviously shown
that a nucleophilic counter anion is necessary to obtain the
cyclic carbonates.
The initial scope of substrates 2 is summarized in Table 2.
Styrene oxide derivatives 2b and 2c afforded the products in
good yields, and terminal epoxides 2dꢀg, bearing halide, amiꢀ
no, and alkyl groups also underwent the CO2 fixation effecꢀ
tively. Moreover, glycidol derivatives 2hꢀn were examined,
and various substituents on the ether oxygen atom were tolerꢀ
ated to give the products in moderate to high yields.
aUnless otherwise noted, all reactions were carried out on a 0.30 mmol scale using
epoxides 2 under a balloon of CO2 in PhCl at 120 °C for 12 h. See supporting
Information for details.
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Taking into account the system established, enantioꢀpure
on alkyl halides.3b Indeed, cisꢀ2o was observed during the
course of the reaction, which is consistent with our mechanisꢀ
tic assumption. Based on the above studies, we concluded that
the formation of 9 from 2 could involve halohydrin intermediꢀ
ates initiated by bifunctional epoxide activation of 1.15 Notaꢀ
bly, the experimental results also imply that the rateꢀ
determining step of the whole transformation might be atꢀ
tributed to CO2 capture because of the evidence that epoxide
2o epimerized rapidly.
1
epoxides were submitted to the optimized reaction conditions
to give the optically active carbonates (Scheme 1). In spite of
the utility of 5ꢀmembered cyclic carbonates in asymmetric
synthesis,13 only a few examples have been described where
they were obtained in nearly enantioꢀpure form by hydrogen
bond donorꢀcatalyzed CO2 fixation reactions.3j,10e To our deꢀ
light, enantiomerically pure and commercially available epoxꢀ
ides (R)ꢀ2f and (S)ꢀ2k were converted to the corresponding
cyclic carbonates with high enantiomeric excesses, respectiveꢀ
ly (3f: 99% ee, 3k: 99% ee). These results suggested that regiꢀ
oselective ringꢀopening proceeds at the methylene C−O bond
of terminal epoxides (β attack) because ringꢀopening at the
methine C−O bond (α attack) would cause racemization of the
chiral center. Furthermore, the reaction was performed on
gramꢀscale by using 1 mol% of TAPS 1d, affording 3h in exꢀ
cellent yield (Scheme 2). Compared with other reported hyꢀ
drogen bond catalysis,3,4 the loading of TAPS is privileged
while somewhat high temperature is needed. For this scaleꢀup
process, the use of 1d, bearing Iꢀ as a counter anion, with a
higher concentration of solvent drastically accelerated the CO2
fixation (See Supporting Information).
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Scheme 1. Optically active carbonate synthesis
1d (1 mol%)
CO2 balloon (1 atm)
O
O
O
O
O
PhCl (10 M)
100 °C, 24 h
O
2h: 1.1 g
(10 mmol)
3h: 1.5 g (95%)
Scheme 2. Gram-scale synthesis
Scheme 3. Mechanistic studies
In pursuit of practical application, we tried to recycle TAPS
after the reaction. Unexpectedly, the epoxide adduct 9a was
recovered instead of 1d by silica gel column chromatography.
To identify whether 9a was a deadꢀend product of the catalytic
cycle or not, control experiments shown in Scheme 3 were
conducted. a) First, 9a was submitted to the CO2 fixation conꢀ
ditions, however, no carbonate 3h was obtained at all. b) By
contrast, the treatment of 15 mol% of 9a with epoxide 2k
cleanly afforded the corresponding carbonate 3k as the sole
product, and 9a was not changed at the end of the transforꢀ
mation (~95% recovery of 9a by 1H NMR).14 c) The stoichioꢀ
metric reaction using 1d in the absence of CO2 was also examꢀ
ined, leading to the formation of the adduct 9a (92%). These
results strongly suggested TAPS 1d was added to epoxide 2h
in situ to generate 9a that catalyzed the overall process. Next,
we investigated the reaction of transꢀdeuterated epoxide 2o to
gain mechanistic insight into the initial epoxide ringꢀopening
step (Scheme 3d).3a,8g,9b Curiously, transꢀ2o was transformed
to the mixture of transꢀ and cisꢀ3o (69%), and the adduct 9b
(7%). It should be emphasized that stereochemistry inforꢀ
mation at the βꢀcarbon of transꢀ2o was significantly lost under
the reaction conditions. Thus, we postulated that the ringꢀ
opening of epoxides would proceed with the help of halide
ions and be reversible, allowing for scrambling of the βꢀ
carbon stereocenter presumably due to a halide ion exchange
In summary, we have demonstrated the utility of TAPS 1
for CO2 transformation to cyclic carbonates under atmospheric
pressure. Various terminal epoxides were converted into corꢀ
responding 5ꢀmembered cyclic carbonates with good to excelꢀ
lent yields, including highly enantioꢀenriched carbonates. The
origin of the unique behavior of 1 has been identified by
mechanistic studies, and the results suggested that the epoxide
adduct of TAPS would be an active species for the CO2 fixaꢀ
tion. As often encountered, serendipity as well as rational deꢀ
sign of catalyst played an important role in the catalysis develꢀ
opment. Efforts to cultivate functions of TAPS as fascinating
catalysts will be reported in due course.
ASSOCIATED CONTENT
Supporting Information
Experimental procedures (PDF), spectroscopic data for all new
compounds (PDF), and crystallographic data for 1a (CIF). This
material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Authors
*Eꢀmail: ytoda@shinshuꢀu.ac.jp (Y.T.)
*Eꢀmail: sugahio@shinshuꢀu.ac.jp (H.S.)
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work was partially supported by the Japan Society for the
Promotion of Science (JSPS) through a GrantꢀinꢀAid for Research
Activity Startꢀup (Grant No. JP15H06242). We gratefully
acknowledge Dr. Kenji Yoza (Bruker AXS) for Xꢀray analysis.
9
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(12) No conversion of 2a was observed in the absence of TAPS 1a
under the same reaction conditions. Detailed optimization of reaction
conditions is shown in Supporting Information.
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tions in Scheme 3b.
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