DOI: 10.1002/cssc.
200900060
The Free-Radical Chemistry of Polyethylene Glycol:
Organic Reactions in Compressed Carbon Dioxide
Jin-Quan Wang, Liang-Nian He,* Cheng-Xia Miao, and Jian Gao[a]
The thermal oxidative degradation of polyethylene glycol
(PEG) is known to occur in an oxygen atmosphere at elevated
temperatures. In this study, PEG radicals assumed to result
from thermal oxidative degradation are successfully applied, in
combination with compressed CO2, to initiate a range of free-
radical reactions, such as selective formylation of primary and
secondary aliphatic alcohols, oxidation of benzylic alcohols,
benzylic C=C bond cleavage, and benzylic sp3 C H oxidation,
demonstrating enormous synthetic potential in a cost-efficient,
practically useful, and environmentally friendly manner; not re-
Introduction
Polyethylene glycol (PEG) and its derivatives are commonly
considered to be inexpensive, thermally stable, toxicologically
innocuous, and environmentally benign media for chemical re-
actions and phase-transfer catalysts,[1] and have an almost neg-
ligible vapor pressure. On the other hand, the thermal degra-
dation of PEG has also been reported,[2] because in the pres-
ence of oxygen at elevated temperatures (over 70 8C) PEG is
susceptible to oxidative attack by free radicals. PEG and
oxygen can react to form PEG peroxide in excess air through
what is known as a random chain scission process, leading to
the formation of many low-molecular-weight oxygenated
products of great complexity, which would seem difficult to
make use of in organic synthesis. In this context, its perfor-
mance as a thermal energy storage system would decline
owing to thermal degradation of PEG. Nonetheless, PEG can
be effectively used as a phase-change material by merely
adding antioxidants or excluding oxygen. However, free radi-
cals from the thermal degradation of PEG have, to the best of
our knowledge, not yet been applied to organic transforma-
tions. Developing the thermal oxidative degradation of PEG
into a viable synthetic protocol would be appealing from the
perspective of sustainable chemistry.
Compressed CO2 has been considered as an alternative sol-
vent for organic synthesis, offering economical and environ-
mental benefits owing to its favorable properties and readily
tunable solvent parameters.[3] In particular dense CO2 appears
to be an ideal solvent for use in oxidation and free-radical re-
actions. Unlike almost any other organic solvent CO2 can not
be oxidized further and, hence, the use of CO2 as a reaction
medium eliminates byproducts originating from solvents. At
the same time, with its excellent mass- and heat-transfer prop-
erties dense CO2 provides a safe reaction environment for
aerobic oxidations. Consequently, a novel chemistry aimed at
ChemSusChem 2009, 2, 755 – 760  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
quiring any catalyst or additional free-radical initiator. We find
that both PEG and molecular oxygen are prerequisites in order
to perform these reactions smoothly. Given that dense CO2 is
immune to free-radical chemistry; it is an ideal solvent for such
reactions. As a result, compressed CO2 allows reactions initiat-
ed by PEG radicals to be tuned by subtly adjusting reaction pa-
rameters such as the CO2 pressure, thereby enhancing the
product selectivity. By attaining a high selectivity towards the
desired products this methodology is practical for organic syn-
theses.
enhancing the selectivity towards desired products as well as
improving reactivity and ease of product separation can be es-
tablished when utilizing dense CO2 as a reaction medium.
In our continuing effort towards developing sustainable pro-
cesses for organic synthesis by using PEG/dense CO2 biphasic
catalysis,[1d–h] we introduce herein a conceptual method that
originates from the free-radical chemistry of PEG following
thermal degradation, in conjunction with the use of dense
CO2. We hypothesize that PEG radicals, assumed to be generat-
ed by thermal oxidative degradation of PEG,[2b] can be utilized
to initiate free-radical reactions in an efficient, viable, and envi-
ronmentally benign manner. In this regard our initial work
started with investigating the reactivity of alcohols in the PEG/
O2/CO2 system, as depicted in Figure 1, path a.
Results and Discussion
Formylation of hexadecanol
Hexadecanol was chosen as a model compound for a prelimi-
nary study. Fortuitously, when the reaction of hexadecanol
with PEG-1000 (i.e., PEG with a molecular mass of 1000 Da)
was carried out in the presence of dioxygen (2.5 MPa) and CO2
(13.5 MPa) at 100 8C for 12 h, the formylated product hexadec-
yl formate 1 a was obtained in 68 % isolated yield along with
[a] J.-Q. Wang, Prof. L.-N. He, C.-X. Miao, J. Gao
State Key Laboratory and Institute of Elemento-Organic Chemistry
Nankai University
Tianjin 300071 (PR China)
Fax: (+ 86) 22-23504216
E-mail: heln@nankai.edu.cn
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.200900060.
755
 L.-N. He et al.

Figure 1. The structural formulae and proposed pathways of organic reactions initiated by PEG radicals generated by thermal oxidative degradation.

palmitic acid 1 b (15 %), and 15 % intact hexadecanol was re- tion of PEG. Nevertheless, a higher temperature (120 8C) more
covered (Table 1, entry 5). This is understandable as the main strongly favored the oxidation reaction compared with a tem-
product is produced via formylation of alcohol with formic perature of 100 8C, resulting in an increase in the yield of pal-
acid generated in situ during the degradation of PEG, as previ- mitic acid (Table 1, entries 4–6).
ously reported,[2d, e] whereas oxidation of the alcohol to carbox-
ylic acid could also occur, presumably through a PEG radical
mechanism.[2b, c] We found that both PEG and molecular Influence of CO2 pressure
oxygen are prerequisites for performing these reactions
The influence of the CO2 pressure on the formylation of hexa-
smoothly (Table 1, entries 1–3). Notably, the temperature has a
decanol was also investigated. As shown in Figure 2, the CO2
drastic influence on the reaction. The reaction yielded only the
pressure can play a crucial role in boosting the desired reac-
starting material at 80 8C, implying that an elevated tempera-
tion as well as noticeably improving the selectivity towards for-
ture (100 8C) is required to induce thermal oxidative degrada-
mylation, and thus could allow this approach to be much
more practically viable in organic synthesis. In the absence of
Table 1. Selective formylation of hexadecanol induced by degradation of
PEG in PEG/O2/CO2.[a]

Entry T [8C] Conv. [%][b] Yield of 1 a [%][b] Yield of 1 b [%][b]

1[c] 100 0 0 0
2[d] 100 0 0 0
3[e] 100 0 0 0
4 80 0 0 0
5 100 85 68 15
6 120 91 65 22

[a] Reaction conditions: hexadecanol (0.46 g, 1.93 mmol), PEG-1000 (0.7 g,

Figure 2. Effect of CO2 pressure on the formylation of hexadecanol. ~: Con-
0.7 mmol), 2.5 MPa O2, 13.5 MPa CO2, 12 h. [b] Yields determined by GC.
version; &: yield. Reaction conditions: hexadecanol (0.46 g, 1.93 mmol), PEG
[c] In the absence of PEG and O2. [d] Without adding PEG. [e] Without O2.
(0.7 g, 0.7 mmol), 2.5 MPa O2, 100 8C, 12 h.

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The Free-Radical Chemistry of Polyethylene Glycol

CO2 the reaction proved sluggish, with only 53 % selectivity to-

wards the formate and less than 20 % conversion (Figure 2). An
appropriate CO2 pressure significantly enhances the reaction
rate, probably by what is known as the “CO2 expansion of a
liquid” effect,[1b] and apparently improves the selectivity to-
wards formate. The optimal CO2 pressure was found to be ca.
14 MPa.

Influence of PEG molecular mass

Figure 3. Recycling of PEG. ~: Conversion; &: yield. Reaction conditions: iso-
The molecular mass of the PEG also had a remarkable influ- butyl alcohol (0.14 g, 1.93 mmol), PEG (2 g, 2 mmol), 2.5 MPa O2,
ence on the reaction, as shown in Table 2. The conversion dra- pO2 + pCO2 = 16 MPa, 100 8C, 12 h.
matically decreased when the molecular mass of PEG was
higher than 6000 (Table 2, entries 1–4); specifically in the case
of PEG-20 000, the reaction did not occur at all under other- ed in situ by thermal degradation to initiate a broad range of
substrates, and to seek feasible applications in a variety of re-
actions.[5–7] As shown in Table 3, a series of primary and secon-
Table 2. Effect of PEG molecular mass on the selective formylation of dary aliphatic alcohols were selectively converted to the corre-
hexadecanol.[a] sponding formates 1 c–g in moderate to high yields (entries 1–
Entry Compound Conv. [%][b] Yield of Yield of 6) whereas the tertiary aliphatic alcohol remained unchanged
1 a [%][b] 1 b [%][b] (entry 7), probably because of steric hindrance.
1 PEG-300 77 55 20
Moreover, this procedure also proved applicable to the oxy-
2 PEG-4000 70 49 17 genation of benzylic alcohols. Benzylic alcohol was preferen-
3 PEG-6000 21 16 4 tially oxidized to benzoic acid 1 h (89 %) and benzaldehyde 1 i
4 PEG-20000 0 0 0 (1 %) alongside with 4 % the formylated product (Figure 1,
5 Dimethyldiglycol 56 29 22
6 PEG-dimethyl ether 88 57 30
path b). Substituted benzylic alcohols capable of stabilizing the
(MW = 1000) radical intermediate (Figure 1, c) proceeded to completion
with excellent yields of the carbonyl compounds 1 h–k
[a] Reaction conditions: hexadecanol (0.46 g, 1.93 mmol), PEG (0.7 g),
2.5 MPa O2, 6.5 MPa CO2, 12 h. [b] Determined by GC. (Table 3, entries 8–11), while with substrates bearing electron-
withdrawing groups only the starting material was recovered
(entries 12 and 13).

wise identical conditions, presumably because of increased

limitations on the mass transport of gaseous oxygen in the
highly viscous, long-chain PEG.[4] In addition, PEGs with pro-
tected hydroxyl groups also proved effective (Table 2, entries 5
and 6).
Recycling of PEG
Another practical feature of this approach is the facile separa-
tion of the products from the reaction mixture, and the re-
maining PEG could be further reused. The procedure for recy-
cling PEG involved extraction with either supercritical carbon
dioxide (scCO2) or with ether, and the PEG was readily reused
without further purification. In the case of isobutyl alcohol, the
results showed that PEG could be recycled for at least five
times with retention of reaction activity, as shown in Figure 3.
It is also worth mentioning that the optimal conversion to the
formate was observed upon altering the molar equivalents of
PEG to 0.36 (see Supporting Information).
Substrate scope
Further studies focused on extending the substrate scope of
this method by probing the ability of the PEG radicals generat-
Benzylic C=C cleavage and benzylic sp3 C H oxidation
When this protocol was further expanded to unsaturated ben-
zylic alcohols (Figure 1, paths d and e), typically, cinnamic alco-
hol gave full conversion in total 55 % yield of benzoic acid and
benzaldehyde (entry 6). Our previous work[1e] also showed that
the PdCl2-mediated oxidation of styrene using a biphasic su-
percritical (sc)CO2/PEG system dominantly gave benzaldehyde
2 a (entry 1). Those results suggested that cleavage of the ben-
zylic C=C double bond may be involved in this procedure, and
thus encouraged us to explore its potential utility in benzylic
C=C cleavage reactions to establish the generality of this con-
cept.
In this study, the reaction of styrene with PEG/O2 was
chosen as a benchmark system to allow reaction optimization.
It was anticipated that in this system PEG, oxygen, and a
proper temperature (80 8C; Table 4, entries 1–3, 5) are indispen-
sable to realize benzylic C=C cleavage reactions. We also found
that the predominant product can be varied between the alde-
hyde and the carboxylic acid through tuning of the CO2 pres-
sure (Table 4, entry 4 and Figure 4). Notably, prolonged reac-
tion time or higher oxygen concentrations favors deeper oxi-
dation, resulting in significant increase in the yield of benzoic
acid (entry 1 vs. entries 7, 8). After roughly screening the reac-

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 L.-N. He et al.

ther exploit PEG radical-initiated

Table 3. Selective formylation of primary and secondary aliphatic alcohols and oxidation of benzylic alcohols
induced by oxidative degradation of PEG in PEG/O2/CO2.[a] benzylic sp3 C-H oxidations with
this concept.
Entry Substrate Product Conv. [%][b] Yield [%][b] Substrates able to be favora-
ble for forming relatively stable
1 1c 83 67
radical g (Figure 1) showed high
reactivity and selectively gave a
2 85 68
ketone as a major product 3 e-g
(entries 9–11, Table 5), and par-
3 1d 85 72[c]
ticularly fluorene effected nearly
full conversion to afford a
4 1e 88 66
ketone product in 88 % yield.
Even simple benzylic substrates
5 1f 83 72
successfully underwent benzylic
sp3 C-H oxidations to generate
6 1g 83 67[c]
the oxidized products in notable
7 – 0 0 high selectivity although low re-
8[d]
PhCH2OH PhCOOH 1h 97 89
activity so far (entries 12–13).
9 4-MeO-PhCH2OH 4-MeO-PhCHO 1i 60 53
10[e] PhCH(OH)Me PhC(O)Me 1j 100 90
11[e] PhCH(OH)Ph PhC(O)Ph 1k 100 93
Mechanistic considerations
12 4-NO2-C6H4CH2OH – 0 0
13 2-NO2-C6H4CH2OH – 0 0 Based on the aforementioned
[a] Reaction conditions unless otherwise mentioned: substrate (1.93 mmol), PEG-1000 (0.7 g, 0.7 mmol), findings concerning the applica-
2.5 MPa O2, pO2 + pCO2 = 16 MPa, 100 8C, 12 h. [b] Isolated yield. [c] Determined by GC. [d] 120 8C, [e] 120 8C, tion of this concept to a broad
24 h.
spectrum of organic reactions, a

Table 4. Oxidation of styrene induced by oxidative degradation of PEG in

PEG/O2/CO2.[a]

Entry T [8C] Conv. [%][b] Yield of benzal- Yield of benzoic

dehyde [%][b] aicd [%][b]
1 80 96 34 46
2[c] 80 0 0 0
3[d] 80 0 0 0
Figure 4. The influence of CO2 pressure on C=C bond cleavage of styrene ~:
4[e] 80 100 10 55
Conversion; *: selectivity to aldehyde; &: selectivity to acid. Reaction condi-
5 70 0 0 0
tions: styrene (0.2 g, 1.93 mmol), PEG (0.7 g, 0.7 mmol), 2.5 MPa O2, 80 8C,
6 90 100 9 68
12 h.
7[f] 80 100 20 60
8[g] 80 100 10 72

[a] Reaction conditions unless otherwise notified: styrene (0.2 g,

1.93 mmol), PEG-1000 (0.7 g, 0.7 mmol), 2.5 MPa O2, 13.5 MPa CO2, 12 h.
[b] Determined by GC. [c] Without adding PEG. [d] In the absence of O2.
[e] In absence of CO2. [f] 3 MPa O2. [g] 24 h.
tion parameters, styrene gave almost full conversion (entry 2,
Table 5), furnishing the benzylic C=C cleaved products com-
posed of benzaldehyde 2 a (34 %) and benzoic acid (46 %).
Among para-substituted styrenes, product distribution be-
tween acid and aldehyde depended on the identity of the sub-
stituent (entries 2–5). Nevertheless, C=C bond in cyclohexene
remained intact, and the reaction gave rise to cyclohex-2-
enone 2 d and cyclohex-2-enol 3 d as main products (entry 8),
implying allylic sp3 C-H oxidation could easily proceed in PEG/
O2/CO2 system. Inspired by those findings, we intrigued to fur-
plausible mechanism may involve PEG radicals formed in situ
during thermal degradation of PEG. A proposed mechanistic
scheme is outlined in Figure 1, with details in Figure S4 (see
Supporting Information). The reaction of PEG with oxygen is
prone to generating PEG radicals,[2b] which are supposed to
further form acetic acid or initiate substrates to generate rela-
tively stable radicals such as b–g (Figure 1), depending on the
substrate structure. As anticipated, benzylic or allylic substrates
could be favorable for forming benzylic or allylic radicals and
thus predominately undergo oxidation, such as oxidation of
benzylic alcohols, benzylic C=C cleavage reactions, and benzyl-
ic/allylic sp3 C H oxidation; whereas aliphatic alcohols could
preferentially go through the formylating pathway. The pro-
posed free-radical mechanism is also supported by the follow-
ing facts (see Supporting Information): radical species detected

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The Free-Radical Chemistry of Polyethylene Glycol

Table 5. Benzylic C=C cleavage reactions of styrene and substituted styrene, and benzylic sp3 C H oxidation induced by oxidative degradation of PEG in
PEG/O2/CO2.[a]

Entry Substrate Conv. [%][c] Product Yield [%][c] Product Yield [%][c]
1[d] PhCH=CH2 100 PhCHO 2a 85 PhCOOH 4
2 PhCH=CH2 96 PhCHO 2a 34 PhCOOH 46
3 4-Me-C6H4CH=CH2 82 4-Me-C6H4CHO 2b 34 4-Me-C6H4COOH 3a 32
4[e] 4-Cl-C6H4CH=CH 100 4-Cl-C6H4CHO 2c 8 4-Cl-C6H4COOH 3b 79
5 4-MeO-C6H4CH=CH2 93 4-MeO-C6H4CHO 77 4-MeOC6H4COOH 3c 11
6 100 PhCHO 2a 30 PhCOOH 25

7 46 PhCHO 2a 24 PhCOOH 10

8[f] 42 2d 9 3d 28

9[g] 75 2e 20 3e 54[b]

10[g] 93 2f 2 3f 88

11[g] 69 2g 2 3g 65[b]

12[g] PhCH2CH3 36 PhCH(OH)CH3 2h 3 PhC(O)CH3 20[b]

13[h] PhCH3 13 PhCH2OH 2i <1 PhCOOH 11

[a] Reaction conditions (unless indicated otherwise): substrate (1.93 mmol), PEG-1000 (0.7 g, 0.7 mmol), 2.5 MPa O2, pO2 + pCO2 = 16 MPa), 80 8C, 12 h.
[b] Isolated yields. [c] Determined by GC. [d] Substrate (2.6 mmol), PdCl2 (27 mg, 0.15 mmol), PEG-300 (2 mL, 2.2 mmol), 3 MPa O2, 60 8C, 24 h. [e] 100 8C.
[f] 100 8C, pO2 + pCO2 = 10 MPa. [g] 120 8C, pO2 + pCO2 = 10 MPa. [h] CoACHTUNGRE(OAc)2 (10 mg, 0.057 mmol), 3 MPa O2, pO2 + pCO2 = 10 MPa, 100 8C, 24 h.

by electron paramagnetic resonance experiments (Figure S1),
the production of trace amounts of formylated products of the
degraded PEG (Figure S2), a broadening distribution of the mo-
lecular weight of PEG (Figure S3), generation of a peroxide in-
termediate as detected by a KI/starch test, and the suppressing
effect of TEMPO (2,2,6, 6-tetramethyl-piperidine-1-oxyl) on the
reactions (see Table S2).
Conclusions
The findings introduced here provide useful guidelines for fur-
ther developing the free-radical chemistry of PEG following
thermal oxidative degradation, so that PEG/oxygen could
become a useful and versatile free-radical initiator for organic
reactions with enormous synthetic potential. This methodology
would offer metal-free, cost-effective access to synthetically
useful transformations with an environmentally friendly charac-
ter in comparison with traditional processes.[5–7] Current appli-
cations include the selective formylation of primary and secon-
dary aliphatic alcohols, oxidation of benzylic alcohols, benzylic
C=C cleavage reactions, and benzylic sp3 C H oxidation. Fur-
ther applications of the present protocol to other reactions are
in progress. Given more time for in-depth investigations, the
free-radical chemistry of PEGs will surely become an even
more powerful tool for organic synthesis and find its place in
many more industrial applications to establish sustainable and
economically competitive processes.
Experimental Section
Safety warning: Experiments that use large amounts of compressed
gases, especially molecular oxygen and supercritical fluids, are po-
tentially hazardous and must only be carried out by using the ap-
propriate equipment and under rigorous safety precautions. In par-
ticular, CO2 is introduced into the substrate-loaded reactor before
oxygen is added. To avoid an explosive regime the following order
should be used: substrate > CO2 > oxygen. Moreover, the oxygen
content should not exceed 14 vol % when CO2 is used as a reaction
medium.
General information: The substrates were purchased from J&KCHE-
MICA. Carbon dioxide with a purity of 99.99 % was commercially
available. The other organic and inorganic compounds from Tianjin
Guangfu Fine Chemical Research Institute were used without fur-
ther purification except for the solvents, which were distilled prior
to use by known methods. NMR spectra were recorded on a
Bruker 300 or Varian 400 spectrometer in CDCl3. 1H and 13C NMR
chemical shifts (d) are given in ppm relative to TMS. 1H and 13C
positive chemical shifts (d) in ppm are downfield from tetramethyl-
silane (CDCl3 : dC = 77.0 ppm; residual CHCl3 in CDCl3 : dH =
7.26 ppm). ESI-MS were recorded on a Thermo Finnigan LCQ Ad-
vantage spectrometer in ESI mode with a spray voltage of 4.8 kV.
GC-MS were measured on a Finnigan HP G1800 A. GC analyses
were performed on a Shimadzu GC-2014 equipped with a capillary

ChemSusChem 2009, 2, 755 – 760  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 759

column (RTX-5, 30 m  0.25 mm) using a flame-ionization detector.
Column chromatography was performed by using silica gel 200–
300 mesh with ethyl acetate/petroleum as eluent. The EPR experi-
ments were performed on a Bruker EMX-6 under the following
conditions: microwave frequency 9.86 GHz, microwave power
20.0 mW, center field 3520 G, magnetic field range 3520 G, modula-
tion amplitude 2.00 G, time constant 10.24 ms, and receiver gain
2.00e + 005.
General procedure for PEG/oxygen-induced reactions in compressed
CO2 : A mixture of substrate (1.93 mmol) and PEG-1000 (0.7 g,
0.7 mmol) was placed in a 25 mL autoclave equipped with an inner
glass tube. 3 MPa CO2 and 2.5 MPa O2 were sequentially intro-
duced into the autoclave and heated to the reaction temperature.
The final pressure was adjusted to the desired pressure at the reac-
tion temperature by introducing the necessary amount of CO2. The
mixture was stirred continuously for the designed reaction time.
The reaction mixture was cooled and quenched by adding triphe-
nylphosphine (1.01 g, 3.86 mmol). Products were then extracted
with diethyl ether (4 mL) and analyzed by gas chromatography.
The residue mixture was purified by column chromatography on
silica gel to afford the product. The structure and the purity of the
products were further identified by using NMR and MS techniques.
The NMR data were consistent with those reported in the litera-
ture,[8] and in good agreement with the assigned structures (see
Supporting Information).
Work-up procedures for recycling PEG; extraction with scCO2 : After
reaction, dense CO2 at 25 8C and 15 MPa was flushed through the
liquid PEG phase for 8 h with a flow-rate of ca. 0.5 mL min 1. The
products were collected from the gas stream in two serial traps
kept at 30 8C. After almost all small molecules except the PEG
and its analogues were extracted the PEG was reused without fur-
ther purification.
Extraction with ether: After the addition of ether (3  3 mL) to the
mixture obtained upon completion of the reaction, the solvent
system was cooled to 10 to 20 8C and the ether phase contain-
ing the products was separated by simple decantation. The com-
bined extracts were dried over magnesium sulphate and concen-
trated in vacuo to give the product. We conducted further reac-
tions by the addition of successive portions of the substrate to the
PEG followed by stirring under identical reaction conditions.
Acknowledgements
Financial support from the National Nature Science Foundation
of China (Grant Nos. 20421202, 20672054 and 20872073), the 111
project (B06005), and the Tianjin Natural Science Foundation is
gratefully acknowledged.
Keywords: formylation · oxygenation · polyethylene glycol ·
radical reactions · supercritical fluids
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Received: February 23, 2009
Published online on June 30, 2009
ChemSusChem 2009, 2, 755 – 760