Chemical fixation of carbon dioxide co-catalyzed by a combination of Schiff bases or phenols and organic bases

Article abstract of DOI:10.1002/ejoc.200400083

Binaphthyldiamino, ethyldiamino and cyclohexyldiamino Schiff bases can catalyze the reaction of epoxides with carbon dioxide in the presence of catalytic amounts of various organic bases to give the corresponding cyclic carbonates in high yields. The simplest binaphthyldiamino Schiff base, derived from the reaction of binaphthyldiamine with salicylaldehyde, gave the highest yield of cyclic carbonate. This catalytic system can be further simplified by use of a phenol instead of the Schiff base to give the corresponding cyclic carbonates in high yields as well. Mechanistic insights were obtained based on a deuterium labeling experiment, The reaction of aziridines with CO₂ and epoxide with CS₂ were also examined under the same reaction conditions. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejoc.200400083

FULL PAPER
Chemical Fixation of Carbon Dioxide Co-Catalyzed by a Combination of
Schiff Bases or Phenols and Organic Bases
Yu-Mei Shen,[a] Wei-Liang Duan,[b] and Min Shi*[a]
Keywords: Aziridines / Carbon dioxide fixation / Epoxides / Schiff bases
Binaphthyldiamino, ethyldiamino and cyclohexyldiamino
Schiff bases can catalyze the reaction of epoxides with car-
bon dioxide in the presence of catalytic amounts of various
organic bases to give the corresponding cyclic carbonates in
high yields. The simplest binaphthyldiamino Schiff base, de-
rived from the reaction of binaphthyldiamine with salicylal-
stead of the Schiff base to give the corresponding cyclic car-
bonates in high yields as well. Mechanistic insights were
obtained based on a deuterium labeling experiment. The re-
action of aziridines with CO2 and epoxide with CS2 were also
examined under the same reaction conditions.
dehyde, gave the highest yield of cyclic carbonate. This cata- ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
lytic system can be further simplified by use of a phenol in-
Germany, 2004)
Introduction
reaction using CrIII porphyrins as a catalyst.[10] In addition,
Floriani has reported that Co salen-type complexes can re-
act with carbon dioxide to afford a Co-CO2 salen-type com-
plex.[11] Later, Nguyen reported that ethyldiamino or cyclo-
hexyldiamino CrIII salen-type complex can efficiently cata-
lyze the reaction of epoxide with carbon dioxide to give the
five-membered cyclic carbonate in high turnover number
(TON) and turnover frequency (TOF).[12] These results
stimulated us to explore other CuII, ZnII, and CoII salen-
type complexes derived from binaphthyldiamino Schiff
bases to catalyze the reaction of epoxides with carbon di-
oxide.[13] Moreover, main group compounds such as alumi-
num porphyrins or salen-type aluminum complexes,[14] tin
compounds[15] and organoantimony compounds[16] are also
suitable to be used as a catalyst for the synthesis of cyclic
carbonates from epoxides with carbon dioxide. Several or-
ganic compounds, such as ammonium salts,[17] amines,[18]
halides,[19] alkali salt/phase transfer system,[20] guanidine or
cyanamide salts,[21] and phosphanes,[22] can also be used as
catalysts for the production of cyclic carbonates from the
reaction of epoxides with carbon dioxide.
Carbon dioxide is the earth’s most abundant carbon re-
source and is used by green plants and anaerobic bacteria
for chemical production on a massive scale. In contrast,
man’s industrial and laboratory utilization of carbon diox-
ide as a chemical feedstock is extremely small. During the
last two decades of the twentieth century, the chemical fix-
ation of carbon dioxide received much attention from the
viewpoint of carbon resources and environmental prob-
lems.[1] In particular, the fixation of carbon dioxide by tran-
sition metal catalysts has seen significant progress.[2Ϫ4] One
of the major successes is the utilization of epoxides and
carbon dioxide as the starting materials to prepare the cor-
responding five-membered cyclic carbonate in the presence
of a transition metal catalyst.[5,6] For example, De Pasquale
has reported a number of coordinatively unsaturated
nickel(0) complexes, such as Ni(PPh3)2 and Ni(PCy3)2, that
are excellent catalysts for this reaction.[7a,7b] Copper, tin and
tantalum systems also catalyze this reaction.[7c,7d] Kisch has
developed a catalyst system which can be applied at room
temperature and under normal pressure.[8] Vinyl ethylene
carbonate can be formed from the monoepoxide of
butadiene in 96% yield at room temperature, normal
pressure and with a reaction time of 15 minutes if
Pd(PPh3)4 is used as the catalyst.[9] Kruper performed this
While the advances have been significant, the develop-
ment of an efficient chemical process for the chemical fix-
ation of CO2 is still attracting much interest in view of the
so-called ‘‘sustainable society’’ and ‘‘green chemistry’’ con-
cepts. In the course of synthesis of the binaphthyldiamino
salen-type zinc() or copper() complexes[13] as catalysts for
the reaction of epoxide with CO2, we incidentally found
that the Schiff base 1 itself also can catalyze this reaction
efficiently in the presence of organic bases such as 4-(di-
methylamino)pyridine (DMAP), 1,8-diazabicyclo[5.4.0]un-
dec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO),
[a]
State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences
Shanghai 200032, China
Fax: ϩ86-21-6416-6128
E-mail: mshi@pub.sioc.ac.cn
[b]
East China University of Science and Technology
130 Mei Long Lu, Shanghai 200237, China
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
3080
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejoc.200400083
Eur. J. Org. Chem. 2004, 3080Ϫ3089

Chemical Fixation of Carbon Dioxide
FULL PAPER
or triethylamine (NEt3; Scheme 1).[23] Upon further investi- low the reaction to take place (Table 1, entries 1Ϫ4, 6 and
gation we confirmed that many common Schiff bases, in- 8Ϫ14).
cluding ethyldiamino Schiff bases or cyclohexyldiamino
These Schiff bases have poor solubilities in most organic
Schiff bases, and even phenols,[24] can catalyze the reaction solvents, although a small amount of organic solvent such
of epoxides with carbon dioxide to give the corresponding as CH2Cl2 or ClCH2CH2Cl is required to give the cyclic
cyclic carbonates in excellent yields under relatively mild carbonate 9a in higher yields. Among the organic bases
conditions in the presence of organic bases. Herein, we wish examined in this reaction DMAP or DBU showed the best
to report the full details of this unprecedented Schiff base results under similar conditions (Table 1, entries 1Ϫ8). We
or phenols and organic base co-catalyzed reaction of epox- found that with Schiff base 1 and DMAP as the catalysts
ides with carbon dioxide. The reaction of aziridines with in 5.0 mL of 1,2-dichloroethane (DCE) at 120 °C the cyclic
CO2 and epoxide with CS2 were also examined under the carbonate 9a could be obtained in 89% yield (Table 1, entry
same conditions with the same catalysts. Based on a deu- 6). The use of binaphthyldiamino Schiff bases 1Ϫ3 or cyclo-
terium labeling experiment, a plausible mechanism of this hexyldiamino Schiff base 6 as a catalyst in the presence of
novel catalytic system has been proposed.
DMAP gave the cyclic carbonate 9a in similarly high yields
(84Ϫ89%; Table 1, entries 6, 9, 10 and 13), while the steri-
cally hindered binaphthyldiamino Schiff base 4 decreased
the yield of cyclic carbonate 9a under the same conditions
(Table 1, entry 10). The ethyldiamino Schiff base 5 also has
lower reactivity. If the Schiff base has no phenolic hydroxyl
group, such as Schiff base 7, the yield of product is lower
under the same conditions (Table 1, entry 14). The best re-
action conditions are Schiff base 1 and DMAP as the co-
catalysts at 120 °C under a high pressure of CO2 (3.57 Mpa)
with 5 mL of solvent (DCE; Table 1, entry 6).
Scheme 1
Having optimized the reaction conditions, we then tried
the reaction of other epoxides with carbon dioxide in the
presence of 1 (1.0 mol %) and DMAP (2.0 mol %). These
results are summarized in Table 2, where we can see that
almost all of the terminal epoxides 8 react with carbon di-
oxide to give the corresponding cyclic carbonates 9 in good
to excellent yields with high selectivity (Table 2, entries
1Ϫ6). To the best of our knowledge, this is the first example
Results and Discussion
The binaphthyldiamino, ethyldiamino and cyclohexyldia-
mino Schiff bases 1Ϫ7 shown in Figure 1 were synthesized
according to the literature procedures.[25] The scope and
limitations of these catalysts under different reaction con-
ditions were carefully examined in the reaction of propylene
oxide (PO) 8a with CO2. The results are summarized in
Table 1. No reaction occurred when using either the Schiff
base or the organic base on its own (Table 1, entries 5 and
7). The presence of both Schiff base (0.1 mol %) and or-
ganic base (0.2 mol %) is therefore required in order to al-
Table 1. Reaction of propylene oxide with CO2 in the presence of
Schiff base and organic base
[a] Reaction conditions: PO (2.6 g, 45 mmol), solvent (5 mL), Schiff
base (0.045 mmol) and organic base (0.09 mmol). [b] Isolated yield.
The reaction time was 24 h. The reaction time was 48 h.
[c]
[d]
Figure 1. Structures of the Schiff bases
Eur. J. Org. Chem. 2004, 3080Ϫ3089
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3081

Y.-M. Shen, W.-L. Duan, M. Shi
FULL PAPER
where a Schiff base combined with an organic base can cat- phenol and an organic base is required in order to get a
alyze the reaction of various terminal epoxides with carbon high yield of cyclic carbonate 9a.
dioxide. More importantly, the catalysts are stable during
the reaction and can be easily recovered by distilling off the
formed cyclic carbonates 9 and then reused for the next
run of the same reaction without loss of efficiency (Table 2,
entry 7).
Scheme 2
Table 2. Reaction of various epoxides with CO2 in the presence of
Schiff Base 1 and DMAP[a]
The scope and limitations of both catalysts and reaction
conditions were also carefully examined. Many phenols
(phenol: pKa ϭ 10.0; m-nitrophenol: pKa ϭ 7.15; p-meth-
oxyphenol: pKa ϭ 10.21; binol: pKa ϭ 10.64; naphthol:
pKa ϭ 10.12) combined with organic bases (DMAP, DBU,
NEt3, or pyridine) are catalysts for this reaction. These re-
sults are summarized in Table 3. 4-(Dimethylamino)pyri-
dine (DMAP) is the best organic base (Table 3, entries 3,
7Ϫ10) and p-methoxyphenol is the most effective phenol
under otherwise identical reaction conditions (Table 3, en-
tries 1Ϫ6). These results suggest that both the pKa of the
phenol and the structure of the organic base play important
roles in this reaction; the combination of either an alcohol
or carboxylic acid with the organic base shows no reactivity.
We also examined the reaction system using p-toluenesul-
fonic acid as a co-catalyst with DMAP, but found that the
cyclic carbonate 9a was obtained in only 10% yield under
the same conditions as for DMAP and phenol. The best
combination is p-methoxyphenol (0.4 mol %) with DMAP
(0.4 mol %) in this reaction.
Table 3. Reaction of propylene oxide with CO2 in the presence of
phenol and organic base
[a]
Reaction conditions: epoxide (4.5 mmol), ClCH2CH2Cl (5 mL),
[b]
catalyst (0.045 mmol), DMAP (0.09 mmol).
Isolated yields.
[c]
Recovered catalysts were used.
Based on the above results, we decided that this catalytic
system could be simplified by use of phenol instead of the
Schiff bases 1Ϫ6 because only the phenolic hydroxy group
plays an important role in this reaction based on the results
shown in Table 1 (entries 7 and 14). Thus, we carried out
the reaction of epoxide 8a with CO2 in the presence of phe-
nol and organic base under similar conditions (Scheme 2).
We found that five-membered cyclic carbonate 9a could be
obtained in excellent yield in the presence of phenol (0.4
mol %) and organic base (0.4 mol %) from the reaction of
epoxide 8a with carbon dioxide under similar reaction con-
ditions (3.57 MPa CO2, 120 °C, 48 h; Scheme 2); phenol on
[a]
Reaction conditions: propylene oxide (PO) (2.6 g, 45 mmol),
CH2Cl2 (0.5 mL), phenol (0.18 mmol), organic base (0.18 mmol).
[b]
[c]
Isolated yield.
Moles of propylene carbonate produced per
[d]
[e]
mol of catalyst.
The reaction time was 24 h. Recovered cata-
its own gave no product. Therefore the presence of both lysts were used.
3082  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjoc.org
Eur. J. Org. Chem. 2004, 3080Ϫ3089

Chemical Fixation of Carbon Dioxide
FULL PAPER
Under the optimized reaction conditions (p-methoxyphe-
nol/DMAP, 3.57 MPa, 120 °C, 48 h), we examined the reac-
tions of other epoxides 8 with carbon dioxide. These results
are summarized in Table 4. We found that, by using 4
mol % of both p-methoxyphenol and DMAP, many mono-
substututed terminal epoxides can be quantitatively trans-
formed into the corresponding cyclic carbonates 9 (Table 4,
entries 1Ϫ6). The catalysts are stable during the reaction
and can be easily recovered by distilling off the formed cy-
clic carbonate 9a and then reused for the next run of the
same reaction with no loss of efficiency (Table 3, entry 11).
Scheme 3
Table 4. Reaction of epoxide with CO2 in the presence of p-meth-
oxyphenol and DMAP
Scheme 3, according to a literature procedure,[29] and util-
ized it as the substrate in the DMAP and phenol co-cata-
lyzed reaction of epoxides with CO2 (Scheme 3). The deut-
1
erated ethylene carbonate 12 formed was analyzed by H
NMR spectroscopy and the spectrum compared with those
of authentic samples prepared according to literature pro-
cedures (Scheme 4).[30,31] We found that deuterated ethylene
carbonate 12 was exclusively formed (the lower yield com-
pared to 8c may be caused by a secondary isotope effect).[32]
This result suggests that the formation of the cyclic carbon-
ate in our reaction system proceeds via path a as shown in
Scheme 5: the epoxy ring, activated by the phenol through
hydrogen bonding, is first opened by the amine (DMAP)
[a]
Reaction conditions: epoxides (4.5 mmol), CH2Cl2 (0.5 mL), p-
[b]
methoxyphenol (0.18 mmol), DMAP (0.18 mmol).
yield.
Isolated
Considering the reaction mechanism, Kim has shown, on
the basis of an X-ray crystal structure, that in the reaction
of epoxide with CO2 in the presence of ZnBr2 and pyridine,
the epoxy ring, activated by the Lewis acidic ZnBr2, is
opened by the pyridine.[26] Then, the zinc complexes
bridged by the alkoxypyridinium ion rapidly interact with
CO2 to give zinc carbonate species, which, in turn, react
with additional epoxides to regenerate the zinc complexes
and cyclic carbonates. However, it is also well-known that
an organic base can activate CO2 as a Lewis base[27] and
the zwitterion [R3NϩC(O)OϪ] can open the aziridinyl
ring.[28] In order to clarify the reaction mechanism, we syn-
thesized trans-deuterioethylene oxide 11, as shown in Scheme 4
Eur. J. Org. Chem. 2004, 3080Ϫ3089
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3083

Y.-M. Shen, W.-L. Duan, M. Shi
FULL PAPER
Scheme 5
and then reacts with CO2 to give the corresponding deuter- Lewis acid in the fixation of CO2.[2,6,33] Alcohols have low
ated ethylene carbonate 12. If the reaction proceeded via Lewis acidity and cannot activate CO2, whereas it is well-
path b, another deuterated ethylene carbonate 15, with the known that acids will react with organic bases to give a salt.
opposite configuration of deuterium atoms to 12, should be Only phenols with pKa’s of 7.0Ϫ10.5 can selectively activate
exclusively formed (Scheme 5).
CO2. m-Nitrophenol (pKa ϭ 7.15) can combine with or-
Based on the above results, in Scheme 6 we propose a ganic bases to some extent as well because of its higher
plausible mechanism for this chemical fixation reaction of acidity. Thus, it has the lowest activity for the chemical fix-
CO2. We believe that, in fact, this is a Lewis base (amine) ation of CO2 under our reaction conditions.
Using aziridines 16 as substrates,[34] we examined the re-
and Lewis acid (phenol; through hydrogen bonding) co-cat-
alyzed reaction system. The Lewis base and Lewis acid
work together to open the epoxy ring and then react with
CO2 to give the corresponding cyclic carbonate in a ring
opening and recyclization process. Previous reports also
suggest the parallel requirement of both Lewis base and
action with CO2 under our optimized conditions. We found
that the corresponding oxazolidines 17 were obtained in
moderate to good yields (Table 5, entries 1Ϫ5). For azirid-
ine 16a, the corresponding oxazolidine 17a was produced
in 90% yield (Table 5, entry 1). The configuration of 17a
was determined by X-ray crystallography (Figure 2).[35] For
aziridine 16b, two oxazolidines 17b-1 and 17b-2 were
formed in 86% yield in a 1:1 ratio (Table 5, entry
1
2).[34aϪ34f,36] Their structures were determined by H NMR
and 13C NMR spectroscopy. The aziridines 16cϪe fur-
nished the corresponding oxazolidines 17cϪe in moderate
yields (Table 5, entries 3Ϫ5).
Epoxide 8a can also react with carbon disulfide (CS2) to
give the corresponding oxathiolane-2-thione 18a in moder-
ate yield under the same conditions (Scheme 7). The reac-
tion of ethylene sulfide with CO2 under the same conditions
gave a complex mixture of products (Scheme 7).
In conclusion, we have found that cyclic carbonates 9 can
be obtained quantitatively (3.57 MPa of CO2 initial press-
ure; reaction temperature 120 °C) from the reaction of
epoxides 8 with carbon dioxide in the presence of a catalytic
amount of a Schiff base or a phenol and an organic base.
This is a very efficient organic Lewis acid (phenol) and
Lewis base (amine) co-catalyzed system without metal cata-
Scheme 6. Plausible reaction mechanism
3084
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 3080Ϫ3089

Chemical Fixation of Carbon Dioxide
FULL PAPER
Table 5. Reaction of aziridines with CO2 in the presence of p-meth-
oxyphenol and DMAP
Scheme 7
lyst; the cyclic carbonates 9 were obtained in excellent yields
as the sole product. In addition, aziridines 16 can react with
CO2 to give the corresponding oxazolidines 17 in moderate
to good yields under the same conditions. The reaction
mechanism has been determined on the basis of deuterium
labeling experiments. Efforts are currently underway to
elucidate the further mechanistic details of this reaction and
to identify systems enabling the carboxylation of other sub-
strates and subsequent transformations thereof.
Experimental Section
General Methods. Melting points are uncorrected. 1H and 13C
NMR spectra were recorded at 300 and 75 MHz, respectively. Mass
spectra were recorded by EI methods, and HRMS was measured
on a Finnigan MAϩ mass spectrometer. The organic solvents used
were dried by standard methods when necessary. All solid com-
pounds reported in this paper gave satisfactory CHN micro-
analyses. Commercially obtained reagents were used without
further purification. Schiff bases[25] and aziridines[37] were prepared
according to literature procedures. All reactions were monitored by
TLC with Huanghai GF254 silica-gel-coated plates. Flash column
chromatography was carried out using 300Ϫ400 mesh silica gel at
increased pressure.
[a]
Reaction conditions: epoxides (4.5 mmol), CH2Cl2 (0.5 mL), p-
[b]
methoxyphenol (0.18 mmol), DMAP (0.18 mmol).
yield.
Isolated
General Procedure for the Formation of Binaphthyl Schiff
Bases:[25a,25b] A mixture of 3,5-dichlorosalicylaldehyde (0.32 g,
1.67 mmol) and 1,1Ј-binaphthyl-2,2Ј-diamine (0.2 g, 0.7 mmol) in
ethanol (10 mL) was stirred at room temperature for 3 h. During
the reaction, the diimine Schiff base 1 formed precipitated as an
orange solid. The crude product was filtered off, washed with etha-
nol and recrystallized from dichloromethane/diethyl ether give an
orange crystalline solid (0.36 g, 81.2%).
1
Schiff base 1 is a known compound. H NMR (300 MHz, CDCl3,
TMS): δ ϭ 6.66 (d, J ϭ 8.2 Hz, 2 H, ArH), 6.78Ϫ6.80 (m, 2 H,
ArH), 7.17Ϫ7.29 (m, 8 H, ArH), 7.43Ϫ7.48 (m, 2 H, ArH), 7.63
(d, J ϭ 8.7 Hz, 2 H, ArH), 7.96 (d, J ϭ 8.5 Hz, 2 H, ArH), 8.10
(d, J ϭ 8.7 Hz, 2 H, ArH), 8.67 (s, 2 H, HCϭN). 12.10 (s, 2 H,
OH) ppm. The 1H NMR spectroscopic data are consistent with
those reported in the literature.[25c,25d]
1
Schiff base 2 is a known compound. H NMR (300 MHz, CDCl3,
TMS): δ ϭ 1.29 [s, 18 H, C(CH3)3], 6.64 (d, J ϭ 8.8 Hz, 2 H, ArH),
7.25Ϫ7.29 (m, 8 H, ArH), 7.41Ϫ7.46 (m, 2 H, ArH), 7.64 (d, J ϭ
8.8 Hz, 2 H, ArH), 7.94 (d, J ϭ 8.8 Hz, 2 H, ArH), 8.08 (d, J ϭ
8.8 Hz, 2 H, ArH), 8.71 (s, 2 H, HCϭN). 11.87 (s, 2 H, OH) ppm.
The 1H NMR spectroscopic data are consistent with those reported
in the literature.[25a,25b]
1
Schiff base 3 is a known compound. H NMR (300 MHz, CDCl3,
TMS): δ ϭ 7.12Ϫ7.32 (m, 8 H, ArH), 7.46Ϫ7.51 (m, 2 H, ArH),
7.60 (d, J ϭ 9.2 Hz, 2 H, ArH), 7.97 (d, J ϭ 7.9 Hz, 2 H, ArH),
Figure 2. ORTEP drawing of 17a
Eur. J. Org. Chem. 2004, 3080Ϫ3089
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3085

Y.-M. Shen, W.-L. Duan, M. Shi
FULL PAPER
8.12 (d, J ϭ 9.2 Hz, 2 H, ArH), 8.64 (s, 2 H, HCϭN), 12.77 (s, 2 (CϭO) ppm. MS (EI): m/z ϭ 164 [Mϩ]. C9H8O3: calcd. C 65.85,
1
H, OH), 11.87 (s, 2 H, OH). The H NMR spectroscopic data are
H 4.88; found C 65.91, H 5.02.
consistent with those reported in the literature.[25a,25b]
4-(3-Chloromethylphenyl)-1,3-dioxolan-2-one and 4-(4-chloromethyl-
phenyl)-1,3-dioxolan-2-one (9f): IR (neat): ν˜ ϭ 1801 (CϭO) cmϪ1
.
1
Schiff base 4 is a known compound. H NMR (300 MHz, CDCl3,
1H NMR (300 MHz, TMS, CDCl3): δ ϭ 4.36 (dd, J ϭ 8.6, 8.0 Hz,
1 H, CH), 4.62 (s, 2 H, CH2), 4.84 (dd, J ϭ 8.6, 8.0 Hz, 1 H, CH),
5.71 (dd, J ϭ 8.0, 8.0 Hz, 1 H, CH), 7.40Ϫ7.48 (m, 5 H, Ar) ppm.
13C NMR (75 MHz, CDCl3, TMS): δ ϭ 43.0, 71.3, 77.8, 126.1,
130.1, 136.2, 138.9, 177.8 (CϭO) ppm. MS (EI): m/z ϭ 212 [Mϩ],
HRMS (EI): calcd. for C10H9ClO3 212.0240; found 212.0241.
trans-1-Deuterio-1-hexene (10) and trans-1-deuterio-1,2-hexene
oxide (11) were prepared according to literature proceduers.[29]
TMS): δ ϭ 1.22 (s, 36 H, CMe3), 7.05 (d, J ϭ 1.5 Hz, 2 H, ArH),
7.24Ϫ7.49 (m, 6 H, ArH), 7.42Ϫ7.46 (m, 2 H, ArH), 7.56 (d, J ϭ
8.6 Hz, 2 H, ArH), 7.97 (d, J ϭ 8.0 Hz, 2 H, ArH), 8.03 (d, J ϭ
9.1 Hz, 2 H, ArH), 8.66 (s, 2 H, HCϭN), 12.72 (s, 2 H, OH). The
1H NMR spectroscopic data are consistent with those reported in
the literature.[25e]
Schiff bases 5؊7 are also known compounds.[25f,25g] Their physical
and spectroscopic data are consistent with those reported in the
literature.
threo-1-Deuterio-1,2-hexanediol (13): This compound was prepared
from trans-1-deuterio-1-hexene (10) by a Sharpless dihydroxylation
reaction.[30] trans-1-Deuterio-1-hexene (255 mg, 3.0 mmol) was ad-
ded at 0 °C to a solution of K3Fe(CN)6 (2.96 g, 9.0 mmol), K2CO3
(1.24 g, 9.0 mmol), MeSO2NH2 (285 mg, 3.0 mmol), hydroquini-
dine 1,4-phthalazinediyl diether (DHQD)2PHAL (23 mg, 0.03
mmol), and K2OsO2(OH)4 (4 mg, 0.011 mmol) in tBuOH/H2O
(1:1; 30 mL) and the mixture was vigorously stirred for 11 h at 0
°C. The reaction was then quenched by slow addition of Na2SO3
(4.2 g, 33.3 mmol). After stirring for 0.5 h at room temperature, the
mixture was filtered. The solvent was removed from the filtrate
under reduced pressure and the residue was extracted with EtOAc
(3 ϫ 20 mL). The extracted organic layer was washed with 5%
H2SO4 (20 mL) and brine (40 mL), then dried over anhydrous
MgSO4. The solvent was removed under reduced pressure and the
residue was purified by silica gel column chromatography (eluent:
petroleum ether/EtOAc, 2:1) to give the corresponding diol 13 as a
colorless oil. 280 mg (79%). IR (neat): ν˜ ϭ 3369, 2931, 2151, 1466,
Representative Procedure for the Coupling Reaction of Epoxide with
Carbon Dioxide: A 100 mL stainless-steel pressure reactor was
charged with binaphthyldiamino Schiff base
1
(22 mg,
0.045 mmol), propylene oxide (0.26 g, 45 mmol), DMAP (11 mg,
0.09 mmol), and ClCH2CH2Cl (5 mL). The reaction vessel was
placed under a constant pressure of carbon dioxide for 5 min to
allow the system to equilibrate and then heated to 120 °C for 48 h.
The vessel was then cooled to ambient temperature, the pressure
released, and the contents transferred to a 50 mL round-bottomed
flask. Unchanged substrate and solvent were removed in vacuo,
and the residue was purified by silica gel column chromatography
(eluent: petroleum ether/EtOAc, 1:4) to give the cyclic carbonate
as a colorless liquid.
4-Methyl-1,3-dioxolan-2-one (9a): This is a known compound.[38]
IR (neat): ν˜ ϭ 1800 (CϭO) cmϪ1 1H NMR (300 MHz, TMS,
.
CDCl3): δ ϭ 1.51 (d, J ϭ 6.2 Hz, 3 H, CH3), 4.04 (t, J ϭ 8.1 Hz,
1 H, CH), 4.57 (t, J ϭ 8.1 Hz, 1 H, CH), 4.84Ϫ4.91 (m, 1 H, CH)
ppm. 13C NMR (75 MHz, CDCl3, TMS): δ ϭ 19.34, 70.83, 73.85,
155.33 (CϭO) ppm.
1
1061 cmϪ1. H NMR (300 MHz, TMS, CDCl3): δ ϭ 0.91 (t, J ϭ
6.9 Hz, 3 H, CH3), 1.25Ϫ1.43 (m, 6 H, -CH2CH2CH2-), 2.50 (br.
s, 1 H, OH), 3.41 (d, J ϭ 7.5 Hz, 1 H, CHD), 3.72 (m, 1 H, CH)
ppm. 13C NMR (75 MHz, CDCl3, TMS): δ ϭ 14.0, 22.7, 27.8, 32.7,
66.2 (t, JC,D ϭ 20.18 Hz), 72.2 ppm. MS (EI): m/z (%) ϭ 87 (33.7)
[Mϩ Ϫ HCDOH].
4-Ethyl-1,3-dioxolan-2-one (9b): IR (neat): ν˜ ϭ 1798 (CϭO) cmϪ1
.
1H NMR (300 MHz, TMS, CDCl3): δ ϭ 1.0 (t, J ϭ 7.1 Hz, 3 H,
CH3), 1.74Ϫ1.95 (m, 2 H, CH2), 4.14 (dd, J ϭ 8.1, 7.1 Hz, 1 H,
CH), 4.54 (t, J ϭ 8.1 Hz, 1 H, CH), 4.64Ϫ4.78 (m, 1 H, CH) ppm.
13C NMR (75 MHz, CDCl3, TMS): δ ϭ 9.2, 27.6, 69.8, 78.8, 155.9
(CϭO) ppm. MS (EI): m/z ϭ 117 [Mϩ ϩ 1]. HRMS (EI): calcd.
for C5H8O3 116.0473; found 116.0465.
erythro-1-Deuterio-1,2-hexanediol (14): This compound was pre-
pared from trans-1-deuterio-1,2-hexene oxide (11) by a Jacobsen
reaction.[31] H2O (90 µL, 5.0 mmol) was added in one portion to a
solution of racemic Co(salen) (15 mg, 0.025 mmol), HOAc (6.0 µL,
0.1 mmol) and trans-1-deuterio-1,2-hexene (325 mg, 3.2 mmol) at 0
°C and the mixture was vigorously stirred for 16 h at 0 °C. The
organic product was extracted with diethyl ether (3 ϫ 20 mL). The
extracted organic layer was washed with water (20 mL) and brine
(40 mL), then dried over anhydrous MgSO4. The solvent was re-
moved under reduced pressure and the residue was purified by sil-
ica gel column chromatography (eluent: petroleum ether/EtOAc,
2:1) to give the corresponding diol 14 as a colorless oil. Yield:
4-Butyl-1,3-dioxolan-2-one 9c. IR (neat): ν˜ ϭ 1800 (CϭO) cmϪ1
.
1H NMR (300 MHz, TMS, CDCl3): δ ϭ 0.95 (t, J ϭ 7.1 Hz, 3 H,
CH), 1.20Ϫ1.54 (m, 4 H, CH2), 1.60Ϫ2.0 (m, 2 H, CH2), 4.09 (dd,
J ϭ 8.1, 7.4 Hz, 1 H, CH), 4.54 (t, J ϭ 8.1 Hz, 1 H, CH), 4.65Ϫ4.80
(m, 1 H, CH) ppm. 13C NMR (75 MHz, CDCl3, TMS): δ ϭ 14.0,
22.5, 26.6, 33.7, 69.7, 77.4, 155.5 (CϭO) ppm. MS (EI): m/z ϭ 144
[Mϩ]. HRMS (EI): calcd. for C7H12O3 144.0786; found 144.0789.
309 mg (81%). IR (neat): ν˜ ϭ 3317, 2932, 2169, 1466, 1085 cmϪ1
.
1H NMR (300 MHz, TMS, CDCl3): δ ϭ 0.91 (t, J ϭ 6.9 Hz, 3 H,
CH3), 1.26Ϫ1.47 (m, 6 H, -CH2CH2CH2-), 2.67 (br. s, 2 H, OH),
3.64 (d, J ϭ 7.5 Hz, 1 H, CHD), 3.70 (m, 1 H, CH) ppm. 13C
NMR (75 MHz, CDCl3, TMS): δ ϭ 14.0, 22.7, 27.8, 32.8, 66.3 (t,
JC,D ϭ 21.0 Hz), 72.3 ppm. MS (EI): m/z (%) ϭ 87 (30.71) [Mϩ
Ϫ HCDOH].
4-Chloromethyl-1,3-dioxolan-2-one (9d): IR (neat): ν˜ ϭ 1801 (Cϭ
1
O) cmϪ1. H NMR (300 MHz, TMS, CDCl3): δ ϭ 3.71Ϫ3.82 (m,
2 H, CH2), 4.43 (dd, J ϭ 8.6, 5.5 Hz, 1 H, CH), 4.61 (t, J ϭ 8.6
Hz, 1 H, CH), 4.94Ϫ5.02 (m, 1 H, CH) ppm. 13C NMR (75 MHz,
CDCl3, TMS): δ ϭ 44.1, 66.6, 74.3, 154.4 (CϭO) ppm. MS (EI):
m/z ϭ 136 [Mϩ]. HRMS (EI): calcd. for C4H5ClO3 135.9927;
found 135.9915.
trans-4-Butyl-5-deuterio-1,3-dioxolane-2-one (12):
A mixture of
4-Phenyl-1,3-dioxolan-2-one (9e): M.p. 50Ϫ51 °C. IR (neat): ν˜ ϭ
threo-1-deuterio-1,2-hexanediol (13; 238 mg, 2.0 mmol), K2CO3
(28 mg, 0.2 mmol) and (EtO)2CϭO (15 mL) was heated to reflux
1
1814 (CϭO) cmϪ1. H NMR (300 MHz, TMS, CDCl3): δ ϭ 4.36
(t, J ϭ 8.6 Hz, 1 H, CH), 4.82 (t, J ϭ 8.6 Hz, 1 H, CH), 5.68 (t, (at 135 °C) for 5 h. The unchanged (EtO)2CϭO was removed under
J ϭ 8.6 Hz, 1 H, CH), 7.27Ϫ7.46 (m, 5 H, Ar) ppm. 13C NMR reduced pressure and the residue was purified by silica gel column
(75 MHz, CDCl3, TMS): δ ϭ 71.1, 125.8, 129.1, 129.6, 135.7, 154.8 chromatography (eluent: petroleum ether/EtOAc, 6:1) to give 12 as
3086
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 3080Ϫ3089

Chemical Fixation of Carbon Dioxide
FULL PAPER
a colorless oil. Yield: 192 mg, 66%. IR (neat): ν˜ ϭ 1801 (CϭO) 4-Ethyloxazolidin-2-one (17e): Colorless oil. IR (CHCl3): ν˜ ϭ 1751
cmϪ1. 1H NMR (300 MHz, TMS, CDCl3): δ ϭ 0.93 (t, J ϭ 7.2 Hz, (CϭO) cmϪ1. 1H NMR (300 MHz, TMS, CDCl3): δ ϭ 0.99 (d, J ϭ
3 H, CH3), 1.33Ϫ1.45 (m, 4 H, -CH2CH2-), 1.68Ϫ1.85 (m, 2 H, 7.2 Hz, 3 H, CH3), 1.66 (dq, J ϭ 7.2, 7.2 Hz, 2 H, CH2), 3.80Ϫ3.91
CH2), 4.07 (d, J ϭ 6.9 Hz, 1 H, CHD), 4.72 (m, 1 H, CH) ppm.
13C NMR (75 MHz, CDCl3, TMS): δ ϭ 13.8, 22.2, 26.4, 33.5, 69.2
(t, JC,D ϭ 23.78 Hz), 77.1, 155.2 (CϭO) ppm. MS (EI): m/z (%) ϭ
145 (0.93) [Mϩ]. HRMS (EI) calcd. for C7H11DO3 145.0848;
found 145.0910.
(m, 1 H, CH), 4.08 (dd, J ϭ 8.4, 5.7 Hz, 1 H, CH), 4.52 (dd, J ϭ
8.4, 8.4 Hz, 1 H, CH), 5.96 (s, 1 H, NH) ppm. 13C NMR (75 MHz,
CDCl3, TMS): δ ϭ 9.4, 28.3, 54.1, 70.2, 160.9 (CϭO) ppm. MS
(EI): m/z ϭ 116 [Mϩ]. HRMS (EI): calcd. for C5H9NO2 115.0633;
found 115.0650.
5-Methyl-1,3-oxathiolane-2-thione (18a): Colorless oil. IR (CHCl3):
cis-4-Butyl-5-deuterio-1,3-dioxolane-2-one (15): This compound was
prepared in the same manner as described above from erythro-1-
deuterio-1,2-hexanediol (14) as a colorless oil. Yield: 190 mg, 65%.
ν˜ ϭ 1438 (CϭS) cmϪ1 1H NMR (300 MHz, TMS, CDCl3): δ ϭ
.
1.64 (d, J ϭ 7.2 Hz, 3 H, CH3), 3.73 (dd, J ϭ 11.9, 7.6 Hz, 1 H,
CH2), 4.02 (dd, J ϭ 11.9, 5.4 Hz, 1 H, CH), 4.46Ϫ4.60 (m, 1 H,
CH) ppm. 13C NMR (75 MHz, CDCl3, TMS): δ ϭ 19.3, 50.4, 55.5,
228.3 (CϭS) ppm. MS (EI): m/z ϭ 134 [Mϩ]. HRMS (EI): calcd.
for C4H6OS2 133.9860; found 133.9857.
IR (neat): ν˜ ϭ 1801 (CϭO) cmϪ1 1H NMR (300 MHz, TMS,
.
CDCl3): δ ϭ 0.92 (t, J ϭ 7.2 Hz, 3 H, CH3), 1.33Ϫ1.44 (m, 4 H,
-CH2CH2-), 1.68Ϫ1.85 (m, 2 H, CH2), 4.52 (dt, J ϭ 7.8, 1.2 Hz, 1
H, CHD), 4.69 (m, 1 H, CH) ppm. 13C NMR (75 MHz, CDCl3,
TMS): δ ϭ 13.6, 22.1, 26.3, 33.3, 69.1 (t, JC,D ϭ 22.95 Hz), 77.1,
155.2 (CϭO) ppm. MS (EI): m/z (%) ϭ 146 (3.36) [Mϩ ϩ 1].
HRMS (EI) calcd. for C7H11DO3 145.0848; found 145.0910.
Acknowledgments
We thank the State Key Project of Basic Research (Project 973)
(No. G2000048007), Shanghai Municipal Committee of Science
and Technology, and the National Natural Science Foundation of
China for financial support (20025206, 203900502, and 20272069).
4-Benzyloxazolidin-2-one (17a): M.p. 72Ϫ74 °C. IR (CHCl3): ν˜ ϭ
1
1753 (CϭO) cmϪ1. H NMR (300 MHz, TMS, CDCl3): δ ϭ 2.88
(dd, J ϭ 6.7, 8.6 Hz, 2 H), 4.05Ϫ4.18 (m, 2 H, CH2), 4.47 (t, J ϭ
8.6 Hz, 1 H, CH), 5.41 (s, 1 H, NH), 7.13Ϫ7.38 (m, 5 H, Ar) ppm.
13C NMR (75 MHz, CDCl3, TMS): δ ϭ 41.4, 53.8, 69.1, 127.3,
129.0, 129.1, 136.0, 159.8 (CϭO) ppm. MS (EI): m/z ϭ 177 [Mϩ].
C10H11NO2: calcd. C 67.80, H 6.21, N 7.91; found C 67.47, H 6.32,
N 7.77%.
[1] [1a]
A. Behr, in Catalysis in C1 Chemistry (Ed.: W. Keim), Re-
idel, Dordrecht, 1983. [1b] The Rio Declaration, United Nations
Conference on Environment and Development, Rio de Janeiro,
June 3Ϫ14, 1992. [1c] Green Chemistry (Eds.: P. T. Anastas, T. C.
Williamson), ACS Symposium Series 626; American Chemical
Society; Washington, DC, 1996.
4-Phenyloxazolidin-2-one (17b-1): M.p. 136Ϫ138 °C. IR (CHCl3):
1
ν˜ ϭ 1752 (CϭO) cmϪ1. H NMR (300 MHz, TMS, CDCl3): δ ϭ
[2] [2a]
[2b]
V. Amarnath, A. D. Broom, Chem. Rev. 1977, 77, 183.
4.21 (dd, J ϭ 8.6, 7.0 Hz, 1 H), 4.76 (dd, J ϭ 8.6, 8.6 Hz, 1 H),
4.98 (dd, J ϭ 8.6, 7.0 Hz, 1 H), 5.69 (s, 1 H, NH), 7.34Ϫ7.46 (m,
5 H, Ar) ppm. 13C NMR (75 MHz, CDCl3, TMS): δ ϭ 56.6, 72.8,
126.3, 129.1, 129.4, 139.7, 160.0 (CϭO) ppm. MS (EI): m/z ϭ 163
[Mϩ]. C9H9NO2: calcd. C 66.25, H 5.56, N 8.58; found C 66.31, H
5.56, N 8.59.
S. Inoue, Y. Yamazaki, Organic and Bio-organic Chemistry of
Carbon Dioxide, Kodansha Ltd., Tokyo, 1982.
A. Behr, Carbon Dioxide Activation by Metal Complexes, VCH,
Weinheim, Germany, 1988.
[3]
[4]
[5]
D. H. Gibson, Chem. Rev. 1996, 96, 2063.
A. A. G. Shaikh, S. Sivaram, Chem. Rev. 1996, 96, 951.
[6] [6a]
D. J. Darensbourg, M. W. Holtcamp, Coord. Chem. Rev.
[6b]
1996, 153, 155.
H. S. Kim, J. J. Kim, B. G. Lee, O. S. Jung,
5-Phenyloxazolidin-2-one (17b-2): M.p. 98Ϫ99 °C. IR (CHCl3): ν˜ ϭ
H. G. Jang, S. O. Kang, Angew. Chem. Int. Ed. 2000, 39, 4096.
1
1752 (CϭO) cmϪ1. H NMR (300 MHz, TMS, CDCl3): δ ϭ 3.56
[6c]
H. Kawanami, Y. Ikushima, Chem. Commun. 2000, 2089.
A. Fujita, Catal. Lett. 2002, 79, 95.
[6d]
(dd, J ϭ 8.4, 8.0 Hz, 1 H, CH), 3.98 (dd, J ϭ 8.4, 8.4 Hz, 1 H,
CH), 5.64 (dd, J ϭ 8.4, 8.0 Hz, 1 H, CH), 5.84 (s, 1 H, NH),
7.35Ϫ7.47 (m, 5 H, Ar) ppm. 13C NMR (75 MHz, CDCl3, TMS):
δ ϭ 48.6, 78.2, 126.0, 129.1, 129.1, 138.7, 160.6 (CϭO) ppm. MS
(EI): m/z ϭ 163 [Mϩ]. C9H9NO2: calcd. C 66.25, H 5.56, N 8.58;
found C 65.74, H 5.63, N 8.5%.
[7] [7a]
R. J. De Pasquale, J. Chem. Soc., Chem. Commun. 1973,
157. [7b] R. J. De Pasquale, U. S. Patent 3,748,345. [7c]J. E. Back-
vall, O. Karlsson, S. O. Ljunggren, Tetrahedron Lett. 1980, 21,
4985. [7d] H. Matsuda, A. Ninagawa, R. Nomura, T. Tsuchida,
[7e]
Chem. Lett. 1979, 73.
K. Yamaguchi, K. Ebitani, T. Yosh-
ida, H. Yoshida, K. Kaneda, J. Am. Chem. Soc. 1999, 121,
[7f]
4526.
T. Yano, H. Matsui, T. Koike, H. Ishiguro, H. Fujih-
4-Isopropyloxazolidin-2-one (17c): Colorless oil. IR (CHCl3): ν˜ ϭ
ara, M. Yoshihara, T. Maeshima, Chem. Commun. 1997, 1129.
1
1755 (CϭO) cmϪ1. H NMR (300 MHz, TMS, CDCl3): δ ϭ 0.91
[8] [8a]
M. Ratzenhofer, H. Kisch, Angew. Chem. Int. Ed. Engl.
(d, J ϭ 6.9 Hz, 3 H, CH3), 0.97 (d, J ϭ 6.9 Hz, 3 H, CH3),
1.65Ϫ1.80 (m, 1 H, CH), 3.63 (ddd, J ϭ 8.7, 6.3, 0.9 Hz, 1 H, CH),
4.15 (dd, J ϭ 8.7, 6.3 Hz, 1 H, CH), 4.46 (dd, J ϭ 8.7, 8.7 Hz, 1
H, CH), 6.42 (s, 1 H, NH) ppm. 13C NMR (75 MHz, CDCl3,
TMS): δ ϭ 17.9, 18.2, 32.9, 58.6, 68.8, 160.6 (CϭO) ppm. MS
(EI): m/z ϭ 129 [Mϩ]. HRMS (EI): calcd. for C6H11NO2 129.0790;
found 129.0774.
[8b]
1980, 19, 317.
1986, 119, 1090.
123, 277.
H. Kisch, R. Millini, I.-J. Wang, Chem. Ber.
[8c]
W. Dumler, H. Kisch, Chem. Ber. 1990,
[9]
T. Fujinami, T. Suzuki, M. Namiya, Chem. Lett. 1985, 199.
W. J. Kruper, D. V. Dellar, J. Org. Chem. 1995, 60, 725.
S. Gambarotta, F. Arena, C. Floriani, P. F. Zanazzi, J. Am.
Chem. Soc. 1982, 104, 5082.
R. L. Paddock, S. T. Nguyen, J. Am. Chem. Soc. 2001, 123,
11498 and references cited therein.
[10]
[11]
[12]
[13]
4-Isobutyloxazolidin-2-one (17d): Colorless oil. IR (CHCl3): ν˜ ϭ
Y.-M. Shen, W.-L. Duan, M. Shi, J. Org. Chem. 2003, 68, 1559
and references cited therein.
1
1751 (CϭO) cmϪ1. H NMR (300 MHz, TMS, CDCl3): δ ϭ 0.92
(d, J ϭ 6.9 Hz, 3 H, CH3), 0.93 (d, J ϭ 6.9 Hz, 3 H, CH3),
1.30Ϫ1.42 (m, 1 H, CH), 1.43Ϫ1.65 (m, 2 H, 2CH), 3.85Ϫ4.02 (m,
2 H, 2CH), 4.50 (dd, J ϭ 7.8, 7.8 Hz, 1 H, CH), 6.71 (s, 1 H, NH)
ppm. 13C NMR (75 MHz, CDCl3, TMS): δ ϭ 22.2, 23.2, 25.0, 44.7,
51.2, 71.0, 160.8 (CϭO) ppm. MS (EI): m/z ϭ 143 [Mϩ]. HRMS
(EI): calcd. for C7H13NO2 143.0946; found 143.0930.
[14] [14a]
[14b]
N. Takeda, S. Inoue, Bull. Chem. Soc. Jpn. 1978, 51, 3564.
[14c]
T. Aida, S. Inoue, J. Am. Chem. Soc. 1983, 105, 1304.
D.-J. Ji, X.-B. Lu, R. He, Appl. Catal. A: General 2000, 203,
329.
[14d]
X.-B. Lu, Y.-Z. Pan, D.-F. Ji, R. He, Chin. Chem.
Lett. 2000, 11, 589.
[15] [15a]
J. Harada, A. Kimura, S. Tagami, K. Watanabe, Jpn. Pat-
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 3087
Eur. J. Org. Chem. 2004, 3080Ϫ3089
www.eurjoc.org

Y.-M. Shen, W.-L. Duan, M. Shi
FULL PAPER
ent 76,19,722 (17,2,1976); Chem. Abstr. 1976, 85, 32452v.
bridge Crystallographic Data Centre, 12, Union Road, Cam-
bridge CB2 1EZ, UK; Fax: ϩ44-1223-336033; E-mail: deposit-
@ccdc.cam.ac.uk].
[15b]
J. Harada, A. Kimura, Y. Takeshita, K. Watanabe, H.
Sugahara, Jpn. Patent 76,141,871 (7,12,1976); Chem. Abstr.
1978, 87, 38863t. [15c]H. Matsuda, A. Ninagawa, R. Nomura, T.
Tsuchida, Chem. Lett. 1979, 573. [15d] Mitsubishi Petrochemical
Co., Jpn. Kokai Tokyo Koho 57,183,784 (12,11,1982); Chem.
Abstr. 1984, 100, 51588p.
[24]
Previously we reported the phenol and organic base co-cata-
lyzed chemical fixation of carbon dioxide with terminal epox-
ides to form cyclic carbonates in a short communication: Y.-M.
Shen, W.-L. Duan, M. Shi, Adv. Synth. Catal. 2003, 345, 337.
[16] [16a]
[25] [25a] G. M. Chen, F. H. Chen, C. H. Zhou, Chem. J. Chin. Univ.
1995, 16, 216; Chem. Abstr. 1996, 123, 101213k. [25b] C.-W. Ho,
W.-C. Cheng, M.-C. Cheng, S.-M. Peng, H.-F. Cheng, C.-M.
H. Matsuda, A. Ninagawa, R. Nomura, T. Tsuchida,
[16b]
Chem. Lett. 1979, 1261.
R. Nomura, A. Ninagawa, H.
Matsuda, J. Org. Chem. 1980, 45, 3735.
[17] [17a]
[17b]
Y. Deng, T. Peng, New. J. Chem. 2001, 25, 639.
V.
Che, J. Chem. Soc., Dalton Trans. 1996, 405 and references
[25c]
Calo, A. Nacci, A. Monopoli, A. Fanizzi, Org. Lett. 2002, 4,
cited therein.
H. Sakiyama, N. Okawa, N. Oguni, Bull.
[17c]
[25d]
2561.
L. N. He, H. Yasuda, T. Sakakura, Green. Chem.
Chem. Soc. Jpn. 1992, 65, 606.
M. Shi, C.-J. Wang, A.
2003, 5, 92. [17d] H. Kawanami, A. Sasaki, K. Matsui, Y. Ikush-
ima, Chem. Commun. 2003, 896.
S. C. Chan, Tetrahedron: Asymmetry 2001, 12, 3105.
N.
[25e]
Takenaka, Y. Huang, V. H. Rawal, Tetrahedron 2002, 58, 8299.
[25f]
[18]
N. Kise, H. Oike, E. Okazaki, M. Yoshimoto, T. Shono, J.
Y. Fujita, T. Morimura, T. Nakano, Jpn. Patent 7,201,625
[25g]
Org. Chem. 1995, 60, 3980.
Soc. 1970, 92, 5861.
H. S. Kim, J. J. Kim, B. G. Lee, O. S. Jung, H. G. Jang, S.
O. Kang, Angew. Chem. Int. Ed. 2000, 39, 4096. [26b] H. S. Kim,
J. J. Kim, S. D. Lee, M. S. Lah, D. Moon, H. G. Jiang, Chem.
Eur. J. 2003, 9, 678.
U. Downing, J. Am. Chem.
(17,1,1972); Chem. Abstr. 1972, 76, 85406d.
[19] [19a] N. Kihara, N. Hara, T. Endo, J. Org. Chem. 1993, 58, 6198.
[26] [26a]
[19b] T. Iwasaki, N. Kihara, T. Endo, Bull. Chem. Soc. Jpn. 2000,
[19c]
73, 713.
W. C. Mills, U. S. Patent 2,907,771 (6,10,1959);
[19d]
Chem. Abstr. 1960, 54, 3205f.
Y. Fujita, T. Morimura, T.
Nakano, Jpn. Patent 7,236,738 (14,9,1972); Chem. Abstr. 1972,
[19e]
[27]
77, 139417z.
S. Fumasoni, F. Pochetti, Rass. Chim. 1975,
It is well-known that organic bases (R2NH) can coordinate to
27, 23; Chem. Abstr. 1975, 83, 113625q.
G. Rokicki, W. Kuran, B. Pogorzelska-Marciniak, Monatsh.
Chem. 1984, 115, 205.
CO2 to give an R2NCO2Ϫ complex. See: [27a] S. Inoue, Y. Yama-
[20]
zaki, Organic and Bio-organic Chemistry of Carbon Dioxide,
[27b]
Kodansha Ltd., Tokyo, 1982, p. 31.
M. Abla, J.-C. Choi,
[27c]
[21] [21a]
T. Sakakura, Chem. Commun. 2001, 2238.
M. George, R.
G.m.b.H. Erdölchemie, French Patent 1,543,832
(25,10,1968); Chem. Abstr. 1970, 72, 12085f. [21b] G. Schnuchel,
L. Bruns, O. Juebermann, DOS, 1,543,555 (6,3,1975); Chem.
Abstr. 1975, 83, 2170A.
G. Weiss, J. Am. Chem. Soc. 2001, 123, 10393. Very recently a
molecular complex of DBU and CO2 was isolated: E. R. Perez,
M. O. Silva, V. C. Costa, U. P. Rodrignes-Filho, D. W. Franco,
Tetrahedron Lett. 2002, 43, 4091.
[22] [22a]
Y. Fujita, T. Morimoto, T. Takanoichi, Jpn. Patent
7,322,702 (7,7,1973); Chem. Abstr. 1973, 79, 146007k. [22b] M. J.
Green, PCT Int. Appl. WO 84,03,701 (27,9,1984); Chem. Abstr.
1985, 102, 166729u.
[28] [28a]
[28b]
T. Kagiya, T. Matsuda, Polym. J. 1971, 2, 398.
W. A .
Rokichi, D. Romanowslca, J. Polym. Sci., Polym. Chem. Ed.
[28c]
1979, 17, 2003.
L. D. Field, W. J. Shaw, P. Turner, Chem.
[23]
Commun. 2002, 46.
In one experiment on the use of the recovered binaphthyldiam-
ino salen-type ZnII catalyst in the same reaction of epoxide
with CO2, we incidentally found that the binaphthyldiamino
Schiff base itself, derived from the decomposition of the ZnII
metal catalyst, can also catalyze this reaction to give the corre-
sponding cyclic carbonate in the presence of organic base, al-
though it is not as effective as the ZnII metal catalyst. We con-
firmed that the decomposition of binaphthyldiamino salen-
type ZnII catalyst produces the corresponding Schiff base on
the basis of X-ray diffraction.
[29] [29a]
V. H. Krauledat, H. H. Brintzmger, Angew. Chem. Int. Ed.
Engl. 1990, 29, 1412. [29b] G. Wilke, H. Muller, Ann. 1958, 618,
267.
2524.
[29c]
P. S. Skell, P. K. Freeman, J. Org. Chem. 1964, 29,
M. D. Refrik, R. D. J. Froese, J. D. Goddard, H. H.
[29d]
Pham, M. F. Pippert, A. L. Schwan, J. Am. Chem. Soc. 1995,
[29e]
117, 184.
A. L. Schwan, M. R. Roche, J. F. Gallagher, G.
Ferguson, Can. J. Chem. 1994, 72, 312.
K. P. Vanheesche, K. B. Sharpless, J. Org. Chem. 1996, 61,
7978.
[30]
[31]
S. E. Schaus, B. D. Brandes, J. F. Larrow, M. Tokunaga, K. B.
Hansen, A. E. Gould, M. E. Furrow, E. N. Jacobsen, J. Am.
Chem. Soc. 2002, 124, 1307.
[32] [32a] For a review of secondary isotope effects see: E. A. Halevi,
[32b]
Prog. Phys. Org. Chem. 1963, 1, 109.
A. J. Streitwieser, R.
H. Jagow, R. C. Fahey, S. Suzuki, J. Am. Chem. Soc. 1958,
80, 2326.
[33] [33a]
K. Yamaguchi, K. Ebitani, T. Yoshida, H. Yoshida, K.
[33b]
Kaneda, J. Am. Chem. Soc. 1999, 121, 4526.
Matsui, T. Koike, H. Ishiguro, H. Fujihara, M. Yoshihara, T.
T. Yano, H.
Maeshima, Chem. Commun. 1997, 1129.
[34] [34a]
K. Soga, S. Hosoda, H. Nakamura, S. Ikeda, J. Chem.
[34b]
Soc., Chem. Commun. 1976, 617.
H. Matsuda, A. Nina-
[34c]
gawa, H. Hasegawa, Bull. Chem. Soc. Jpn. 1985, 58, 2717.
T. Nomura, T. Nakano, S. Nishio, S. Ogawa, A. Ninagawa, H.
[34d]
Matsuda, Chem. Ber. 1989, 122, 2407.
M. R. Banks, J. I.
G. Cadogan, L. Gosney, K. G. Hodgson, D. E. Thomsen, J.
Chem. Soc., Perkin Trans. 1 1991, 961. [34e] P. Tascedda, E. Du-
nach, Chem. Commun. 2000, 449. [34f] H. Kawanami, Y. Ikush-
ima, Tetrahedron Lett. 2002, 43, 3841.
Crystal data for 2: empirical formula: C42H40N2O2; molecular
mass: 604.76; color, habit: colorless, prismatic; crystal system:
monoclinic; lattice type: primitive; lattice parameters: a ϭ
˚
˚
˚
22.365(2) A, b ϭ 14.6279(16) A, c ϭ 12.1375(13) A, α ϭ 90°,
3
[35]
˚
β ϭ 120.187(2)°, γ ϭ 90°, V ϭ 3432.3(6) A ; space group: Cc;
Z ϭ 4; Dcalcd. ϭ 1.170 g/cm3; F000 ϭ 1288; diffractometer: Ri-
gaku AFC7R; residuals: R, Rw: 0.0366, 0.0502. CCDC-217653
contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cam-
Crystal data of 17a: empirical formula: C10H11NO2; molecular
weight: 177.20; color, habit: colorless, prismatic; crystal dimen-
sions: 0.20 ϫ 0.20 ϫ 0.30 mm; crystal system: monoclinic; lat-
˚
tice type: primitive; lattice parameters: a ϭ 5.895(1) A, b ϭ
3
˚
˚
˚
8.771(1) A, c ϭ 8.769(2) A, β ϭ 91.98(2)°, V ϭ 453.1(2) A ;
space group: P21 (no. 4); Z ϭ 2; Dcalcd. ϭ 1.299 g/cm3; F000
ϭ
3088
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org Eur. J. Org. Chem. 2004, 3080Ϫ3089

Chemical Fixation of Carbon Dioxide
FULL PAPER
188; diffractometer: Rigaku AFC7R; residuals: R, Rw: 0.066,
0.086.
Ungureanu, C. Bologa, S. Chayor, A. Mamn, Tetrahedron Lett.
[36b]
1999, 40, 5315.
I. Ungureanu, P. Klota, A. Mann, Angew.
Chem. Int. Ed. 2000, 39, 4615. See also ref. 34e.
CCDC-178964 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Centre, 12, Union Road,
Cambridge CB2 1EZ, UK; Fax: ϩ44 1223 336033; E-mail:
deposit@ccdc.cam.ac.uk].
The formation of 17b-2 may be attributed to the reaction of a
1,3-dipole derived from phenylaziridine with CO2 in the pres-
ence of phenol as it is known that phenylaziridine can react
[37] [37a]
M. M. EI-Abadelah, S. S. Sabri, A. A. Jarrar, M. H. Abu
[37b]
Zarga, J. Chem. Soc., Perkin Trans. 1 1979, 2881.
H. Rub-
instein, B. Feibush, E. Cil-Av, J. Chem. Soc., Perkin Trans. 2
[37c]
1973, 2094.
J. X. Xu, Tetrahedron: Asymmetry 2002, 13,
1129.
[36]
[38] [38a]
W. J. Kruper, D. V. Dellar, J. Org. Chem. 1993, 58,
1945Ϫ1948. [38b] A. Baba, T. Nozaki, H. Matsuda, Bull. Chem.
Soc. Jpn. 1987, 60, 1552Ϫ1554.
with an olefin to give a cyclized product via a formal [3ϩ2]
Received February 9, 2004
[36a]
dipolar cycloaddition in the presence of a Lewis acid.
I.
Eur. J. Org. Chem. 2004, 3080Ϫ3089
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3089