Rhodium (I)-catalyzed reductive cyclocarbonylation of internal alkynes: Atom-economic process for synthesis of 2-cyclopenten-1-ones, 5-alkylidenefuran-2(5H)-ones and indan-1-ones

Article abstract of DOI:10.1002/chem.200802462

The reductive cyclocarbonylation of internal alkynes with carbon monoxide catalyzed by [{RhCl(CO)₂}₂]/CO(NH₂)₂ in the presence of water has been investigated. Dialkyl alkynes underwent a reductive [2+2+1] cycloc

Full text of DOI:10.1002/chem.200802462

FULL PAPER
DOI: 10.1002/chem.200802462
Rhodium(I)-Catalyzed Reductive Cyclocarbonylation of Internal Alkynes:
Atom-Economic Process for Synthesis of 2-Cyclopenten-1-ones,
5-Alkylidenefuran-2ACTHNUTRGNE(NUG 5H)-ones and Indan-1-ones
Qiufeng Huang[a] and Ruimao Hua*[a, b]
Abstract: The reductive cyclocarbony-
lation of internal alkynes with carbon
monoxide catalyzed by [{RhCl(CO)2}2]/
the cases of diarylacetylenes used, both
trans-2-cyclopenten-1-ones and 5-alky-
ing group on the benzene ring en-
hanced the formation of 5-alkylidene-
furan-2(5H)-ones. On the other hand,
lidenefuran-2
N
ACHTUNGTRENNUNG
CO
(NH2)2 in the presence of water has
and the presence of electron-withdraw-
ortho-substituted diarylacetylenes un-
derwent a reductive [4+1] cyclocarbo-
nylation to produce selectively indan-1-
ones in good yields.
been investigated. Dialkyl alkynes un-
derwent a reductive [2+2+1] cyclocar-
bonylation to afford selectively cis-2-
cyclopenten-1-ones in high yields. In
Keywords: alkynes · carbonylation ·
homogeneous catalysis · rhodium
Introduction
penten-1-ones are versatile polyfunctional intermediates for
synthesis of a wide variety of natural compounds.[7] Accord-
ing to the retrosynthetic analysis, the most straightforward
and atom-economic route for the synthesis of 2-cyclopenten-
1-ones is the direct reductive cyclocarbonylation of two mol-
ecules of internal alkynes with one molecule of CO and one
molecule of H2 (Scheme 1).
Transition-metal-catalyzed cycloaddition of alkyne, alkene,
and carbon monoxide (Pauson–Khand reaction) can theo-
retically provide an efficient synthetic method for cyclopen-
tenone derivatives,[1] but most of the reported work has fo-
cused on either the intramolecular cyclocarbonylation of
enyne with carbon monoxide to furnish bicyclic cyclopente-
nones[2] or the three-component intermolecular cyclocarbo-
nylation limited to the use of strained cyclic alkenes such as
norbornene,[2g,h,n,o,3] 2,5-norbornadiene,[2h,o,3b,4] or ethylene.[5]
Multisubstituted 2-cyclopenten-1-ones are considered as
an important class of compounds, since not only can the
structures of 2-cyclopenten-1-ones be found in a large varie-
ty of natural products and in many important class of phys-
iological and biological active compounds,[6] but also 2-cyclo-
Scheme 1. Reductive [2+2+1] cyclocarbonylation of alkynes with CO
In view of the versatile activity of rhodium complexes in
(cyclo)carbonylation of unsaturated compounds with carbon
monoxide[8] and our recent reports on the rhodium-cata-
lyzed double hydroaminocarbonylation of terminal
[a] Dr. Q. Huang, Prof. Dr. R. Hua
Department of Chemistry, Tsinghua University
Innovative Catalysis Program
Key Laboratory of Organic Optoelectronics &
Molecular Engineering of Ministry of Education
Beijing 100084 (P. R. China)
Fax : (+86)10-62771149
E-mail: ruimao@mail.tsinghua.edu.cn
AHCTUNGTRENNUNG
alkynes,[9] [2+2+1+1] cyclocarbonylation of two molecules
of internal alkynes with two molecules of CO,[10] we decided
to explore the possibility of the selectively synthesizing
[b] Prof. Dr. R. Hua
tetraACTHUNRTGNEUNGsubstituted 2-cyclopenten-1-ones by intermolecular re-
State Key Laboratory of Elemento-Organic Chemistry
Nankai University, Tianjin 300071 (P. R. China)
ductive [2+2+1] cyclocarbonylation of alkynes with CO
catalyzed by rhodium complexes in the presence of water.[11]
In this paper, we report our new findings that
[{RhCl(CO)2}2]/H2NCONH2 is an efficient catalyst system
for the reductive cyclocarbonylation of internal alkynes with
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200802462. It contains general
1
experimental procedure, characterization data, copies of H,
13C NMR charts of all products, and the X-ray diffraction data of 4d.
Chem. Eur. J. 2009, 15, 3817 – 3822
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3817

CO to afford cis- or trans-2-cyclopenten-1-one, 5-alkylidene-
furan-2(5H)-ones, and indan-1-ones depending on the
nature of internal alkynes used.
(63%), as well as the selectivity of 2a (2a/3a 82:18)
(Table 1, entry 5). Furthermore, the addition of PhNH2 and
PhCONH2 led to a much greater increase of the yield and
selectivity of 2a (Table 1, entries 6 and 7), and the best re-
sults (96% GC yield) and the highest selectivity for 2a (2a/
3a 98:2) were obtained by addition of urea (Table 1,
ACHTUNGTRENNUNG
Results and discussion
entry 8). Although [RhCl(CO)ACTHNUGRTNEUNG(dppp)]/urea also showed
The reductive carbonylation of 4-octyne (1a) was initially
chosen as a model reaction to establish the optimum reac-
tion conditions as summarized in Table 1. When a mixture
high catalytic activity to afford the comparable yield of 2-
cyclopenten-1-ones, the selectivity for the formation of 2a
was somewhat low (Table 1, entry 9).
A brief study of the influence of solvents disclosed that
the polar and hydrophilic solvent of DMF was also a good
solvent for the present reaction to give 2-cyclopenten-1-ones
in 92% GC yield (2a/3a 96:4). In 1,4-dioxane, 2-cyclopent-
en-1-ones were obtained in 43% GC yield (2a/3a 95:5), and
the use of relatively less polar or nonpolar solvents such as
n-hexane, toluene, di-n-butyl ether resulted in no formation
of 2-cyclopenten-1-ones. One of the reasons is likely due to
the low solubility of urea in these solvents.
The present reductive cyclocarbonylation can be applied
to a variety of internal alkynes as summarized in Table 2.
Likewise 1a, other aliphatic internal alkynes such as 3-
hexyne (1b) and 5-decyne (1c) also underwent the reductive
[2+2+1] cyclocarbonylation to afford the respective ad-
ducts 2b and 2c in high yields with high selectivity (Table 2,
entries 1 and 2).
Table 1. Rhodium(I)-catalyzed reductive cyclocarbonylation of 4-octyne
with carbon monoxide.[a]
Entry
Catalyst (mol%)
[RhCl(PPh3)3] (2)
[RhCl(CO)(PPh3)2] (2)
[RhCl(CO)(dppp)] (2)
[{RhCl(CO)2}2] (1)
[{RhCl(CO)2}2] (1)
[{RhCl(CO)2}2] (1)
[{RhCl(CO)2}2] (1)
[{RhCl(CO)2}2] (1)
RhCl(CO)(dppp) (2)
Additive
Yield [%][b]
2a/3a[c]
1
G
E
–
35
97:3
2
N
G
–
–
–
30
20
50
63
90
80
90:10
95:5
64:36
82:18
84:16
95:5
3[d]
4
5
6
7
Et3N
PhNH2
PhCONH2
8
N
CO
CO
N
96(90)
93
98:2
82:18
9[d]
N
[a] Reaction conditions: alkyne (1.0 mmol), [{RhCl(CO)2}2] (0.01 or
0.02 mmol), additive (0.1 mmol), H2O (40 mL), CO (0.5 MPa), DMSO
(1.0 mL) at 130 8C for 15 h. [b] GC yield of 2a and 3a (isolated yield). [c]
Determined by GC of the reaction mixture. [d] dppp=1,5-bis(diphenyl-
phosphino)pentane.
Table 2. Rhodium(I)-catalyzed reductive cyclocarbonylation of internal
alkyne with carbon monoxide.[a]
of 1a (1 mmol), [RhClACHTUNGTRNEUGN(PPh3)3] (0.02 mmol) and H2O (40 mL,
Entry
R
Yield [%][b]
of 2+3
2/3[c]
Yield [%][b]
of 4
ca. 2.2 mmol) in DMSO (1.0 mL) under CO (0.5mPa) in an
autoclave was heated with stirring at 1308C for 15 h, 1a was
converted in 76% yield. The analyses of the reaction mix-
ture revealed that the reductive [2+2+1] cyclocarbonyla-
tion of 1a occurred to produce 2,3,4,5-tetra-n-propyl-2-
cyclopenten-1-ones 2a and 3a in 35% GC yield, and the re-
action proceeded with excellent stereoselectivity to give cis-
configured adduct 2a in 97% selectivity (Table 1, entry 1).
The competitive reaction under the reaction conditions is
the hydrogenation of 1a giving cis- and trans-4-octene (32%
1
2
3
4
5
6
7
Et 1b
n-Bu 1c
Ph 1d
2-naphthyl 1e
p-MeC6H4 1 f
p-ClC6H4 1g
3,4-F2C6H3 1h
87
93
45
34
55
31
<5
2b/3b 99:1
2c/3c 93:7
2d/3d <1:99
2e/3e <1:99
2 f/3 f <1:99
2g/3g <1:99
4d 30
4e 25
4 f 10
4g 24
4h 65
[a] Reaction conditions: alkyne (1.0 mmol), [{RhCl(CO)2}2] (0.01 mmol),
CO(NH2)2 (0.1 mmol), H2O (40 mL), CO (0.5 MPa), DMSO (1.0 mL) at
AHCTUNGTRENNUNG
GC yield).[12] [RhCl(CO)
ACHTUNTRGENNUG(PPh3)2] and [RhCl(CO)ACHTUNTGREN(NUGN dppp)]
130 8C for 15 h. [b] Isolated yield. [c] Determined by GC of the reaction
mixture.
(dppp=1,5-bis(diphenylphosphino)pentane) also showed
the catalytic activity to give the desired products in low
yields (Table 1, entries 2 and 3). However, when
[{RhCl(CO)2}2] was employed, which is a phosphine ligand-
free complex, a moderate yield (50%) of the desired 2-
cyclopenten-1-ones was formed with a ratio of cis-2a and
trans-3a of 64:36 (Table 1, entry 4).[13] To improve both the
yield and selectivity of 2-cyclopenten-1-ones, the effect of
the additives on the [{RhCl(CO)2}2] catalyst was examined,
and found that the addition of catalytic amount of organic
bases was effective. For example, the addition of 10 mol%
of Et3N resulted in a considerable increase of the yield
The reaction manner of diarylacetylenes was different
from those of dialkylacetylenes, since the formation of both
trans-2-cyclopenten-1-ones[13] and 5-alkylidenefuran-2
ACHTUNGTRENNUNG(5H)-
ones was observed for the reductive cyclocarbonylation of a
variety of diarylacetylenes bearing either electron-donating
or electron-withdrawing groups on benzene ring, and in
theses cases, no cis-2-cyclopenten-1-ones could be deter-
mined. For example, the reaction of diphenylacetylene (1d)
afforded trans-2,3,4,5-tetraphenyl-2-cyclopenten-1-one (3d)
and
5-[1,2-diphenyleth-(E)-ylidene]-3,4-diphenylfuran-2-
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Carbonylation Reactions
FULL PAPER
A
Furthermore, attempted reactions of electron-deficient in-
ternal alkynes, such as dimethyl acetylenedicarboxylate and
methyl phenylpropiolate, failed. Although such types of al-
kynes were mostly converted, the (cyclo)trimers of alkynes
were formed in quantitative yields confirmed by GC and
GC-MS analysis of the reaction mixtures.
(Table 2, entry 3). The structure and configuration of 4d
were confirmed by X-ray crystallography (Figure 1).[14] It is
apparent that 4d is resulted from a novel and highly selec-
Because the formation of alkenes was observed as a by-
product in the present carbonylation of alkynes, the most
plausible means for the formation of 2-cyclopenten-1-one 2
or 3 is considered to be from the intermolecular Pauson–
Khand reaction of CO with alkyne and alkene. In an at-
tempt to gain insight into this proposed mechanism, the re-
action of 1 f, cis-stilbene, and CO was performed in the pres-
ence of [{RhCl(CO)2}2]/COACHTNUGTRENUNG(NH2)2 without addition of water
[Eq. (1)]. However, the analysis of the reaction mixture dis-
closed that cis-stilbene did not co-react with 1 f and only 3 f
and 4 f were formed. Therefore, the Pauson–Khand reaction
mechanism for the formation of 2 or 3 can be ruled out.
Figure 1. Molecular structure of 4d. Hydrogen atoms are omitted for
clarity,
On the basis of the above-mentioned results and known
rhodium chemistry, a rational mechanism for the formation
of 2-cyclopenten-one is depicted in Scheme 2. It involves the
tive multicomponent coupling reaction of two molecules of
1d, two molecules of CO, and one molecule of hydrogen.
Di-(2-naphthyl)acetylene (1e) proceeded in
a similar
manner to give the corresponding adducts 3e and 4e in
somewhat low total yields (Table 2, entry 4).
The nature of the substituents on phenyl ring showed
great effect on the reactivity of diarylacetylenes, as well as
the product distribution. It was found that the electron-rich
diarylacetylenes not only showed a higher reactivity for the
reductive cyclocarbonylation to afford a mixture of carbony-
lated products, but also favored the selective formation of 3.
For example, the reaction of 1 f, which is an electron-rich di-
arylacetylene, afforded the carbonylated products in 65%
total isolated yield, 55% of 3 f and 10% of 4 f (3 f/4 f 85:15;
Table 2, entry 5). The use of electron-deficient diarylacety-
lene 1g resulted in a considerable low yield of carbonylated
products (55%), and, in this case, the ratio of 3g and 4g
was 57:43 (Table 2, entry 6). These results indicate that the
electron-deficient diarylacetylenes favor the formation of 5-
alkylidene furanone derivatives. Indeed, under the same re-
action conditions, the reaction of 1h, which has two CF3
electron-withdrawing groups on the phenyl ring, selectively
gave 4h (65%) as major product, and only small amount of
2-cyclopenten-1-one was determined in the reaction mixture
(Table 2, entry 7).
Scheme 2. Proposed mechanism for [2+2+1] cyclocarbonylation of
alkyne with CO.
reaction of [{RhCl(CO)2}2] with urea to form the coordina-
tively unsaturated monomeric intermediate A,[15] which un-
dergoes oxidative coupling with alkynes to form rhodacyclo-
pentadiene intermediate B, and subsequent insertion of CO
and the formation of cyclopentadienone-coordinated rhodi-
um intermediate C, followed by selective hydrogenation to
afford 2 and/or 3. The rhodacyclopentadiene complex B
from the reaction of rhodium complex with alkynes,[16] and
cyclopentadienone-coordinated complex C[17] have been well
studied. Furthermore, rhodium-catalyzed selective hydroge-
We have also examined the present cyclocarbonylation
employing aryl- and alkyl-substituted unsymmetrical inter-
nal alkynes, and the reactions occurred with low selectivity
to give a mixture of cyclocarbonylated products leading to
unsuccessful separation.
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3819

R. Hua and Q. Huang
Table 3. Rhodium(I)-catalyzed reductive cyclocarbonylation of ortho-
nation of C-type compounds to 2-cyclopenten-1-one has
been also reported.[18]
substituted diaryl acetylene.[a]
Entry Substrate
Product
Yield
[%][b]
To confirm that the hydrogen for the present reductive
carbonylation is generated in situ from the reaction of CO
with H2O, we repeated the reductive cyclocarbonylation of
1d by addition of deuterated water. As expected, a high
deuterated cyclopentenone could be obtained [Eq. (2)].
1
59
52
2
3
65
50
4
5
As described above, the diarylacetylenes with para- (1 f
and 1g), or para- and meta-substituents (1h) underwent the
reductive cyclocarbonylative reaction to afford 2-cyclopent-
en-1-ones and 5-alkylidenefuranones. We believe that the
similar reductive cyclocarbonylation will become difficult
when ortho-substituted diarylacetylenes are employed, be-
cause the high steric repulsion between two ortho-substitut-
ed aryl groups must be unfavorable for the formation of the
analogue of 2-cyclopenten-1-ones or 5-alkylidenefuranones.
Therefore, it is interesting to examine the carbonylation of
ortho-substituted diarylacetylenes under the similar reaction
conditions. As shown in Equation (3), when 1,2-di(4-chloro-
2-methylphenyl)acetylene (1i) was subjected to the reaction
conditions indicated in Table 2, neither 2-cyclopenten-1-ones
nor 5-alkylidenefuranones was formed. Instead, 6-chloro-4-
methyl-2-(4-chloro-2-methylphenyl)indan-1-one (5i) was ob-
tained in 31% isolated yield, accompanied with the forma-
tion of a mixture of (Z/E)-1,2-di(4-chloro-2-methylphenyl)-
40
(5m:5m’
1:1)
[a] Reaction conditions: alkyne (1.0 mmol), [{RhCl(CO)2}2] (0.01 mmol),
CO(NH2)2 (0.1 mmol), H2O (40 mL), CO (0.5 MPa), NMP (1.0 mL) at
AHCTUNGTRENNUNG
140 8C for 15 h.
entry 1). Under these reaction conditions, the reactions of
1,2-di(2-methylphenyl)acetylene (1j), 1,2-di(1-naphthyl)-
AHCTUNGTREGaNNUN cetylene (1k) and 1,2-di(9-phenanthryl)acetylene (1 L) af-
forded the corresponding substituted indan-1-ones in moder-
ate yields (Table 3, entries 2–4). In addition, the reaction of
unsymmetrical diarylated acetylene (1m) produced two
indan-1-ones in a ratio of 1:1 in 40% total isolated yield
(Table 3, entry 5).
ACHTUNGTRENNUNG
ethene in 40% isolated yield.[12]
It is worth noting that [Co2(CO)8] or [Co2(CO)8]/PR3 also
showed catalytic activity for the reductive carbonylation of
diarylacetylenes to afford indanones under harsh reaction
conditions (2208C, 100 atm).[19] As described above, the
present rhodium(I)-catalyzed procedure seems to be greatly
affected by the steric nature of aryl groups, since only ortho-
substituted diarylacetylenes underwent the reductive cyclo-
carbonylation to give indanones; the reactions of para- and
meta-substituted diarylacetylenes produce trans-2-cyclopent-
en-1-ones and 5-alkylidenefuran-2ACTHNUTRGNEU(GN 5H)-ones.
It is apparent that the formation of indan-1-ones results
from the reductive cyclocarbonylation of one molecule of
diarylacetylene with one molecule of CO and one molecule
of H2, namely called [4+1] cycloaddition reaction. A pro-
posed mechanism for the formation of indan-1-ones involv-
After further optimizing the reaction conditions, the yield
of 5i could be improved to 59% by using NMP (NMP=N-
methyl-2-pyrrolidinone) as solvent to replace DMSO and in-
creasing the reaction temperature to 1408C (Table 3,
À
ing the oxidative addition of ortho-C H bond in the aromat-
ic ring of diarylacetylenes[20] is shown in Scheme 3.
3820
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Chem. Eur. J. 2009, 15, 3817 – 3822

Carbonylation Reactions
FULL PAPER
and CH2Cl2 (1:0–1:1)] to afford 2a (112.5 mg, 0.45 mmol, 90%) as yellow
viscous oil. The GC analysis of the reaction mixture disclosed the forma-
tion of 2a in 96% GC yield. 1H NMR (300 MHz, CDCl3): d=2.52–2.42
(m, 2H), 2.29–2.00 (m, 4H), 1.67–1.57 (m, 4H), 1.43–1.25 (m, 8H), 0.98–
0.84 ppm (m, 12H); 13C NMR (75 MHz, CDCl3): d=211.9, 175.5, 139.9,
50.9, 46.7, 35.5, 35.0, 30.6, 25.3, 22.0, 20.9, 20.3, 20.2, 14.5, 14.4, 14.3,
14.1 ppm; GCMS: m/z (%): 250 (3) [M]+, 235 (1), 221 (9), 208 (47), 179
(100), 166 (19), 138 (7), 107 (4), 95 (5), 79 (5), 67 (4); IR (KBr): n˜ =
1687 cmÀ1 (CO).
A typical experimental procedure for the reductive cyclocarbonylation of
1,2-di(4-chloro-2-methylphenyl)acetylene (1i) with CO (Table 3, entry 1):
1,2-Di(4-chloro-2-methylphenyl)acetylene (1i; 275.0 mg, 1.0 mmol), CO-
AHCTNUERTGGUN(NN NH2)2 (6.0 mg, 0.1 mmol), H2O (40 mL, ca. 2.2 mmol), [{RhCl(CO)2}2]
(3.9 mg, 0.01 mmol) and NMP (1.0 mL) were placed in a 25 mL autoclave
under a flow of nitrogen. Carbon monoxide was then introduced at an in-
itial pressure of 0.5 MPa at room temperature, and the autoclave was
heated in oil bath at 1408C with stirring for 15 h. After work-up and iso-
lation as described above, 5i was isolated (180.0 mg, 0.59 mmol, 59%) as
yellow solid. 1H NMR (300 MHz, CDCl3): d=7.53 (s, 1H), 7.35 (s, 1H),
7.11 (s, 1H), 7.01 (d, J=8.2 Hz, 1H), 6.77 (d, J=8.2 Hz, 1H), 3.99 (dd,
J=8.2, 4.5 Hz, 1H), 3.48 (dd, J=17.5, 8.2 Hz, 1H), 2.84 (dd, J=4.3,
17.5 Hz, 1H), 2.27 (s, 3H), 2.23 ppm (s, 3H); 13C NMR (75 MHz,
CDCl3): d=205.2, 150.5, 138.7, 137.7, 137.6, 136.8, 135.5, 134.4, 132.8,
130.7, 128.8, 126.6, 121.6, 50.7, 34.1, 20.0, 17.8 ppm; GCMS: m/z (%): 304
(100) [M]+, 289 (9), 269 (84), 202 (35), 189 (50), 178 (75), 153 (23), 115
(39), 101 (47), 89 (37), 77(18), 63 (18); IR (KBr): n˜ =1713 cmÀ1 (CO);
Scheme 3. Proposed mechanism for [4+1] cyclocarbonylation of ortho-
substituted diaryl alkyne with CO.
Conclusion
We have investigated the reductive cyclocarbonylation of in-
ternal alkynes with carbon monoxide catalyzed by
[{RhCl(CO)2}2]/COACHTUNGTRENNUNG(NH2)2 in the presence of water to afford
various cyclocarbonylated products depending on the nature
of internal alkynes:
AHCTUNGTRENNUNG
1) Dialkylacetylenes underwent the reductive [2+2+1]
ACHTUNGTRENNUNGcyclocarbonylation to give cis-2-cyclopenten-1-ones in
high yields with excellent selectivity.
2) Reductive cyclocarbonylation of diarylacetylenes pro-
duced both trans-2-cyclopenten-1-ones and 5-alkylidene-
Acknowledgement
This project was supported by National Natural Science Foundation of
China (project no. 20473043).
furan-2
ACHTUNGTRENNUNG
favored the formation of 5-alkylidenefuran-2ACHTUNGTRENNUNG
3) Reductive cyclocarbonylation of diarylacetylenes with
ortho-substituent on the benzene ring afforded selective-
ly indan-1-ones in good yields through a reductive [4+1]
cyclocarbonylation.
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the merits of easily available starting materials and one-pot
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Experimental Section
A typical experimental procedure for the reductive cyclocarbonylation of
4-octyne (1a) with CO (Table 1, entry 8): 4-Octyne (1a; 110.0 mg,
1.0 mmol), COACHTUNGTRENNUNG(NH2)2 (6.0 mg, 0.1 mmol), H2O (40 mL, ca. 2.2 mmol),
[{RhCl(CO)2}2] (3.9 mg, 0.01 mmol) and DMSO (1.0 mL) were placed in
a 25 mL autoclave under a flow of nitrogen. Carbon monoxide was then
introduced at an initial pressure of 0.5 MPa at room temperature, and
the autoclave was heated in oil bath at 1308C with stirring for 15 h. After
the autoclave was cooled to room temperature, CO was released slowly,
and the crude reaction mixture was diluted with CH2Cl2 (4.0 mL) and
ACHTUNGTRENNUNGcyclohexane (4.0 mL), and then n-docosane (93.0 mg, 0.3 mmol) was
added as an internal standard for GC analysis. After GC and GC-MS
analyses of the reaction mixture, volatiles were removed under a reduced
pressure, and the residue was subjected to silica gel column chromatogra-
phy [eluting with cyclohexane and then with a mixture of cyclohexane
Chem. Eur. J. 2009, 15, 3817 – 3822
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www.chemeurj.org
3821

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Received: November 25, 2008
Published online: February 19, 2009
3822
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Chem. Eur. J. 2009, 15, 3817 – 3822