Rhodium(I)-n-heterocyclic carbene-catalyzed addition of sodium tetraphenylborate to ketones to form tertiary alcohols

Article abstract of DOI:10.3987/COM-14-13092

Rhodium complexes ([Rh(COD)(NHC)Cl]) were synthesized by the reaction of bis(1,3-dialkylperhydrobenzimidazolin-2-ylidene) with [RhClCOD]2 in toluene and characterized by elemental analysis, ¹H NMR, ¹³C NMR and IR spectroscopy. These complexes were used as catalysts for the addition of sodium tetraphenylborate to aromatic ketones and corresponding tertiary alcohols were obtained in good yields.

Full text of DOI:10.3987/COM-14-13092

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HETEROCYCLES, Vol. 89, No. 11, 2014
HETEROCYCLES, Vol. 89, No. 11, 2014, pp. 2562 - 2571. © 2014 The Japan Institute of Heterocyclic Chemistry
Received, 26th September, 2014, Accepted, 31st October, 2014, Published online, 4th November, 2014
DOI: 10.3987/COM-14-13092
RHODIUM(I)-N-HETEROCYCLIC CARBENE-CATALYZED ADDITION
OF SODIUM TETRAPHENYLBORATE TO KETONES TO FORM
TERTIARY ALCOHOLS
a
a,
b
Beyhan Yiğit, Murat Yiğit, * and İsmail Özdemir
a
Department of Chemistry, Faculty of Science and Art, Adıyaman University,
02040 Adıyaman, Turkey
b
Department of Chemistry, Faculty of Science and Art, Inönü University,
44260 Malatya, Turkey
Corresponding author; e-mail: myigit@adiyaman.edu.tr
Abstract – Rhodium complexes ([Rh(COD)(NHC)Cl]) were synthesized by
the reaction of bis(1,3-dialkylperhydrobenzimidazolin-2-ylidene) with
1
13
[
2
RhClCOD] in toluene and characterized by elemental analysis, H NMR, C
NMR and IR spectroscopy. These complexes were used as catalysts for the
addition of sodium tetraphenylborate to aromatic ketones and corresponding
tertiary alcohols were obtained in good yields.
INTRODUCTION
The additions of carbon nucleophiles to carbon heteroatom multiple bonds catalyzed by transition metal
complexes are recognized to be an extremely important tool for carbon-carbon bond formation in organic
synthesis and the addition products are important intermediates for the synthesis of biologically and
1
-7
pharmaceutically active compounds. The addition of aryl and alkenylboronic acids to aldehydes
8
catalyzed by rhodium complexes were initially reported by Miyaura’s group in 1998 and in the following
years, this transformation have attracted many chemists’ interest. There have been reports on the addition
of arylboronic acids to aldehydes giving diarylmethanols or chiral diarylmethanols, which is catalyzed by
9
-14
15-21
22,23
24
25-31
Rh,
Pd,
Cu,
Fe and Ni
complexes. Among these complexes, rhodium and palladium
32
catalysts are well works. In 2001, Fürstner and Krause reported the use of rhodium-carbene complexes

HETEROCYCLES, Vol. 89, No. 11, 2014
2563
formed in situ as catalysts in the arylation of aldehydes and, in subsequent years, rhodium-carbene
1
0, 33-43
complexes as catalysts were used by other groups.
arylboron compounds to aldehydes. However, use of ketones as substrates are quite limited due to lesser
Much progress have been seen in the addition of
1
2,44-47
reactivity of ketones toward the nucleophlic addition.
arylboronic acids and tetraaryl borates have proved to be effective arylating reagents in rhodium
Recently, arylboron compounds including
4
8-50
catalysis.
Rhodium-catalyzed arylation of ketones for tertiary alcohols by sodium tetraphenylborate as
5
1
52
effective nucleofiles was achieved by Miura’s group in 2006. In the same year, Feringa et al. reported
the first rhodium-catalyzed asymmetric 1,2-addition of arylboronic acids to trifluoroacetophenones for the
synthesis of trifluoromethyl substituted tertiary alcohols with high yields and good enantioselectivities up
to 83%. Recently, Buesking and Ellman have demonstrated the Rh-catalyzed addition of α-sulfonamido
trifluoroborates to trifluoromethyl ketones for the asymmetric synthesis of vicinal amino alcohols with
5
3
good diasteroselectivity.
We have previously reported the rhodium-catalyzed addition of phenylboronic acid to aldehydes and
54
sodium tetraphenylborate to C-N triple bond. Herein, we wish to report the synthesis of rhodium(I)
complexes bearing perhydrobenzimidazolin-2-ylidene ligands and their use as catalyst in the addition of
sodium tetraphenylborate to aromatic ketones.
RESULTS AND DISCUSSION
The tetraaminoethenes 1 used as the source of carbene were synthesized by deprotonation of the
1
,3-dialkylperhydrobenzimidazolium salts with sodium hydride in dry and degassed tetrahydrofuran
5
5
according to the procedures reported by Lappert.
The reaction of bis(1,3-dialkylperhydro-
2
complex proceeded smoothly in refluxing
benzimidazolin-2-ylidene) with the binuclear [RhCl(COD)]
toluene to give the RhCl(COD)(1,3-dialkylperhydrobenzimidazolin-2-ylidene) complexes as
yellow-orange crystalline solids in 76-89% yields (Scheme 1). The rhodium complexes (2a-d) are very
1
stable against to air and moisture in the solid state. The complexes (2a-d) have been fully identified by H
1
3
and C- NMR spectroscopy, FTIR and elemental analysis. They show a characteristic υ
(NCN)
band at
-1
13
1
485, 1496, 1515, 1507 and 1511 cm for 2a, 2b, 2c and 2d, respectively. The C- NMR chemical shifts,
which provide a useful diagnostic tool for metal carbene complexes, show that Ccarbene is substantially
deshielded. The resonance of the carbene carbon of rhodium complexes were observed as a doublet at
1
03
13
2
13.64 (2a), 219.52 (2b), 219.45 (2c), 219.55 (2d) ppm and coupling constants J( Rh- C) were 47.3
(
2a, 2b, 2d), 48.0 (2c) Hz and these values were similar to those found for other rhodium(I) carbene
3
9,56
complexes.

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HETEROCYCLES, Vol. 89, No. 11, 2014
Scheme 1. Synthesis of rhodium-carbene complexes (2a-d)
The phenylation of ketones to tertiary alcohols were carried out using sodium tetraphenylborate as phenyl
source with rhodium(I) carbene complexes as catalysts and ammonium chloride as promoter. Arylboronic
acids can be used as aryl sources, but less effective than sodium tetraphenylborate. The use of sodium
tetraphenylborate instead of arylboronic acids allowed elimination of the addition of base such as CsF in
5
7
Suzuki-Miyaura type cross-coupling catalyzed by rhodium complex. Ammonium salts such as
tetrapropylammonium bromide and tetrabutylammonium bromide as a promoter have long been known to
5
8
improve the efficiency of Heck coupling. Although the role of NH
4
Cl is not clear for the phenylation of
5
1
ketones, use of NH Cl as an additive has been significantly raised the product yield from 47 up to 96%.
4
4
The catalytic experiments were carried out using 0.5 mmol ketone, 0.25 mmol NaBPh , 0.005 mmol 2a-d,
o
0
.5 mmol NH
4
Cl and 5 mL o-xylene at 120 C for 25 h. The conversion of the product was monitored by
GC. The results of the catalytic phenylation of acetophenone, o-methoxyacetophenone,
p-fluoroacetophenone, p-chloroacetophenone and p-methylacetophenone are summarized in Table 1.

HETEROCYCLES, Vol. 89, No. 11, 2014
2565
Table 1. Rhodium-carbene catalyzed reaction of sodium tetraphenylborate with ketones
a-c
Entry
R
Catalyst
2a
Yield %
99
1
2
3
4
5
6
7
8
9
H
H
2b
2c
83
H
86
H
2d
2a
92
o-OMe
o-OMe
o-OMe
o-OMe
p-Cl
p-Cl
p-Cl
p-Cl
p-F
91
2b
2c
72
75
2d
2a
82
98
1
1
1
1
1
1
1
1
1
1
2
0
1
2
3
4
5
6
7
8
9
0
2b
2c
87
93
2d
2a
97
96
p-F
2b
2c
90
p-F
94
p-F
2d
2a
92
p-Me
p-Me
p-Me
p-Me
a
87
2b
2c
69
76
2d
81
Reaction conditions: Isolated yield (purity of yield checked by NMR and GC).
b
c
o
All reactions were monitored by TLC. 120 C, 25 h.
The treatment of sodium tetraphenylborate with aromatic ketones bearing electron-withdrawing group
such as Cl, F and unsubstituted (Table 1, entries 9-16, 1-4) gave corresponding tertiary alcohols in high

2566
HETEROCYCLES, Vol. 89, No. 11, 2014
yields under these conditions. Use of aromatic ketone bearing electron-donating group such as OMe and
Me slightly decreased the yields under the same conditions (entries 5-8 and 17-20). The synthesized
complexes were employed as catalyst for the addition of sodium tetraphenylborate to ketones. Among the
tested complexes, the complex 2a bearing N,N’-(4-methylbenzyl)perhydrobenzimidazolylidene ligand is
highly efficient in the addition of sodium tetraphenylborate to ketones (Table 1, entries 1, 5, 9, 13). This
results demonstrated that rhodium(I) N-heterocyclic carbene complexes as catalyst were significantly
5
1
increased the yields, but the reaction conditions were not improved compared to literature.
CONCLUSION
In summary, four novel Rh-NHC complexes have been synthesized and characterized. All complexes are
stable toward air and moisture in the both solid state and solution. We have demostrated the first use of
these complexes as a catalyst in the addition of sodium tetraphenylborate to aromatic ketones to produce
tertiary alcohols. The complexes showed high activity in these addition reactions. Among them, complex
2
a is the most active complex. Further studies on chiral carbene complexes and asymmetric version of
this process are in progress.
EXPERIMENTAL
All reactions for the preparation of 1-2 were carried out under an atmosphere of argon in flame-dried
glassware by using standart Schlenk techniques. The solvents used were purified by distillation over the
drying agents indicated and were transferred under an atmosphere of argon: THF, Et
2
O (Na/K alloy),
was synthesized according to
published procedure. H and C NMR spectra were recorded by using a Varian AS 400 Merkur
5
9
2 2 4 2
CH Cl (P H10), hexane, toluene (Na). The complex [RhCl(COD)]
1
13
1
13
spectrometer operating at 400 MHz ( H), 100 MHz ( C) in CDCl with tetramethylsilane as an internal
3
reference. Chemical shifts () are given in ppm relative to TMS, coupling constants (J) in hertz. FTIR
-1
spectra were recorded as KBr pellets in the range 400-4000 cm on a Mattson 1000 spectrophotometer
-1
(
wavenumbers, cm ). GC spectra were recorded on an Agilent 6890 N GC system by GC-FID with an
HP-5 column of 30 m length, 0.32 mm diameter and 0.25 m film thickness. Melting points were
measured in open capillary tubes with an electrothermal-9200 melting point apparatus and uncorrected.
Elemental analyses were performed at Inönü University research center.
General procedure for the preparation of tetraaminoalkenes (1).
A suspension of the imidazolinium salt (10 mmol) and sodium hydride (15 mmol) in THF (20 mL) was
stirred at room temperature for 12 h under an argon atmosphere, then heated under reflux for 4 h. The
mixture was cooled and volatiles were removed in vacuo. Toluene (20 mL) was added and filtered.

HETEROCYCLES, Vol. 89, No. 11, 2014
2567
Filtrate was concentrated to half of the initial volume and hexane (10 mL) was added. Upon cooling,
white crystals were obtained. The tetraaminoalkenes were not characterized due to their sensitivity
towards oxygen and moisture.
General procedure for the preparation of the rhodium-carbene complexes (2a-d).
A solution of bis(1,3-dialkylperhydrobenzimidazolin-2-ylidene) (1) (0.40 mmol) and [RhCICOD]
mmol) in toluene (15 mL) was heated under reflux for 2 h. Upon cooling to room temperature,
yellow-orange crystals of 2a-d were obtained. The crystals were filtered, washed with Et O (3x15 mL)
2
(0.40
2
2 2 2
and dried under vacuum. The crude product was recrystallized from CH Cl /Et O.
4
Chloro(
2a).
Yield: 0.20 g, 87%, mp 206 C. IR(cm ) : 1485 (NCN), H NMR (CDCl ) : 1.02-1.23 (m, 4H,

-1,5-cyclooctadiene){1,3-bis(4-methylbenzyl)perhydrobenzimidazolin-2-ylidene}rhodium(I)
(
o
-1
1
3
-
-
(
N-CHCH CH CH CH CH-N-); 1.43-1.65 (m, 4H, -N-CHCH CH CH CH CH-N-); 2.37-2.46 (m, 2H,
2
2
2
2
2
2
2
2
N-CHCH
2
CH
2
CH
2
CH
2
CH-N-); 7.17 (d, 4H, J = 8.0 Hz, CHarom); 7.47 (d, 4H, J = 8.0 Hz, CHarom); 4.46
-Ar); 6.33 (d, 2H, J = 14.4 Hz, -N-CH -Ar); 2.3 (s, 6H, Ar-CH -p); 3.37 (m,
H, COD-CH); 5.02 (m, 2H, COD-CH); 1.90 (m, 4H, COD-CH ); 2.29 (m, 4H, COD-CH
CDCl CH CH CH CH-N-); 21.38
d, 2H, J = 14.4 Hz, -N-CH
2
2
3
1
3
2
2
2
). C NMR
(
(
(
(
(
(
3
) : 213.64 (d, JRh-Carbene = 47.3 Hz, Ccarbene); 21.35 (-N-CHCH
2
2
2
2
-N-CHCH
-N-CHCH
-N-CHCH
2
2
2
CH
CH
CH
2
2
2
CH
CH
CH
2
2
2
CH
CH
CH
2
2
2
CH-N-);
CH-N-);
23.48
52.15
(-N-CHCH
2
2
CH
2
2
CH
2
2
CH
CH
2
2
CH-N-);
CH-N-);
24.00
52.94
(-N-CHCH
CH
CH
CH-N-); 127.58 (Ar-C); 128.97 (Ar-C); 129.49 (Ar-C); 129.63 (Ar-C); 133.16
Ar-C); 134.45 (Ar-C); 137.33 (Ar-C); 137.49 (Ar-C); 68.08 (-N-CH -Ar); 68.22 (-N-CH -Ar); 18.80
2
2
Ar-CH
3
-p); 19.53 (Ar-CH
3
-p); 68.81 (d, JRh-C = 14.4 Hz, COD-CH); 99.71 (d, JRh-C = 6.1 Hz, COD-CH);
); 33.00 (COD-CH ); 33.08 (COD-CH ). Anal. Calcd for
2
8.80 (COD-CH
2
); 28.94 (COD-CH
2
2
2
C
31
H
40
N
2
ClRh: C, 64.30; H, 6.96; N, 4.84. Found: C, 64.46; H, 6.72; N, 4.58.
4
Chloro( -1,5-cyclooctadiene){1,3-bis(2,3,4-trimethoxybenzyl)perhydrobenzimidazolin-2-ylidene}-
rhodium(I) (2b).
o
-1
1
Yield 0.24 g, 83%, mp 192 C. IR(cm ) : 1496 (NCN), H NMR (CDCl
3
) : 0.92-1.18 (m, 4H,
CHN); 2.82-2.89 (m, 2H,
CHN); 6.69 (d, 1H, J = 8.8 Hz, CHarom); 6.72 (d, 1H, J = 8.8 Hz, CHarom); 7.33 (d,
-Ar); 5.75
NCHCH
2
CH
2
CH
2
CH
2
2
2 2 2 2
CHN); 1.46-1.68 (m, 4H, NCHCH CH CH CH
NCHCH
2
CH
2
CH
2
CH
1
H, J = 8.8 Hz, CHarom); 7.48 (d, 1H, J = 8.8 Hz, CHarom); 4.92 (d, 1H, J = 15.2 Hz, -N-CH
2
(
d, 1H, J = 15.2 Hz, -N-CH -Ar); 5.73 (d, 1H, J = 15.6 Hz, -N-CH -Ar); 6.08 (d, 1H, J = 15.6 Hz,
2
2
-
N-CH
2
-Ar); 3.83 (s, 3H, -OCH
3
); 3.85 (s, 3H, -OCH
3
3 3
); 3.87 (s, 3H, -OCH ); 3.88 (s, 3H, -OCH ); 3.94 (s,

2568
HETEROCYCLES, Vol. 89, No. 11, 2014
3
H, -OC
.28 (m, 4H, COD-CH
CH CH CH-N-); 24.40 (-N-CHCH
8.61 (-N-CHCH CH CH CH-N-); 46.79 (-N- HCH
H
3
); 3.95 (s, 3H, -OC
H
3
); 3.43 (m, 2H, COD-C
H
); 5.01 (m, 2H, COD-C
) : 219.52 (d, JRh-Carbene = 47.3 Hz, Ccarbene); 24.14
CH CH CH-N-); 28.23 (-N-CH CH CH CH CH-N-);
CH CH CH CH-N-); 47.33 (-N-CHCH CH CH CH H-N-);
2
H); 1.88 (m, 4H, COD-CH );
1
3
2
2
). C NMR (CDCl
3
(
-N-CHCH
2
C
H
2
2
2
2
2
C
H
2
2
C
H
2
2
2
2
2
2
2
2
C
H
2
C
2
2
2
2
2
2
2
2
C
1
07.65 (Ar-C); 107.94 (Ar-C); 122.93 (Ar-C); 123.94 (Ar-C); 124.52 (Ar-C); 128.88 (Ar-C); 141.85
(
Ar-C); 142.18 (Ar-C); 151.05 (Ar-C); 151.74 (Ar-C); 153.01 (Ar-C); 153.11 (Ar-C); 67.93 (-N-CH -Ar);
2
6
2 3 3 3 3
8.44 (-N-CH -Ar); 56.14 (-OCH ); 61.02 (-OCH ); 61.08 (-OCH ); 61.35 (-OCH ); 69.01 (d, JRh-C =
1
4.5 Hz, COD-CH); 99.74 (d, JRh-C = 6.1 Hz, COD-CH); 28.99 (COD-CH ); 29.14 (COD-CH ); 32.69
2
2
2 2 48 2 6
(COD-CH ); 33.30 (COD-CH ). Anal. Calcd for C35H N ClO Rh: C, 57.50; H, 6.62; N, 3.83. Found C,
5
7.64; H, 6.78; N, 3.95.
4
Chloro(
2c).
Yield 0.19 g, 76%, mp 218 C. IR(cm ) : 1515 (NCN), H NMR (CDCl

-1,5-cyclooctadiene){1,3-bis(4-ethoxybenzyl)perhydrobenzimidazolin-2-ylidene}rhodium(I)
(
o
-1
1
3
) : 0.81-0.97 (m, 4H,
CHN); 2.74-2.82 (m, 2H,
CHN); 6.80 (d, 4H, J = 8.4 Hz, CHarom); 7.34 (d, 4H, J = 8.4 Hz, CHarom); 4.70 (d,
-Ar); 5.69 (d, 1H, J = 15.2 Hz, -N-CH -Ar); 5.04 (d, 1H, J = 14.8 Hz,
-Ar); 6.05 (d, 1H, J = 14.8 Hz, -N-CH -Ar); 1.33 (t, 6H, J = 7.2 Hz, -OCH CH -p); 3.96 (quar, 4H,
= 5.2 Hz, -OC CH ); 3.34 (m, 2H, COD-C ); 4.94 (m, 2H, COD-C ); 1.81 (m, 4H, COD-C ); 2.20
NCHCH
2
CH
2
CH
2
CH
2
2
2 2 2 2
CHN); 1.38-1.54 (m, 4H, NCHCH CH CH CH
NCHCH
2
CH
2
CH
2
CH
1
H, J = 15.2 Hz, -N-CH
2
2
-
N-CH
2
2
2
3
J
H
2
3
-
p
H
H
H
2
1
3
(
m, 4H, COD-C
H
2
). C NMR (CDCl
3
)
: 219.45 (d,
J
Rh-C = 48.0 Hz,
C
carbene); 24.13 (-N-CHCH
2
C
H
2
CH
2
CH
2
CH-N-);
2
4.38 (-N-CHCH
2
CH
2
C
H
2
CH
2
CH-N-); 28.78 (-N-CH
C
H
2
CH
2
CH
2
CH
2
CH-N-); 28.84 (-N-CHCH
2
CH
2
CH
CH CH-N-);
2 2
5
3.63 (-N-CHCH
2
CH
2
CH
2
CH
2
CH-N-); 53.95 (-N-CHCH
2
CH
2
CH
2
CH
2
CH-N-); 114.62 (Ar-C); 114.69
-Ar);
8.40 (-N-CH -Ar); 15.09 (OCH CH -p); 63.64 (OCH CH -p); 69.20 (d, J = 14.5 Hz, COD-CH); 99.83
(
Ar-C); 129.22 (Ar-C); 129.45 (Ar-C); 129.49 (Ar-C); 130.05 (Ar-C); 158.53 (Ar-C); 68.15 (-N-CH
2
6
2
2
3
2
3
(
d, J = 6.1 Hz, COD-CH); 29.45 (COD-CH
2
2 2 2
); 29.48 (COD-CH ); 32.86 (COD-CH ); 33.10 (COD-CH ).
Anal. Calcd for C33H N ClO Rh: C, 62.02; H, 6.94; N, 4.38. Found: C, 62.21; H, 6.78; N, 4.54.
44 2 2
4
Chloro(
2d)
Yield 0.27 g, 89%, mp 176 C. IR(cm ) : 1511 (NCN), H NMR (CDCl

-1,5-cyclooctadiene){1,3-bis(4-benzyloxybenzyl)perhydrobenzimidazolin-2-ylidene}rhodium(I)
(
o
-1
1
3
) : 0.85-1.02 (m, 4H,
NCHCH CH CH CH CHN); 1.46-1.63 (m, 4H, NCHCH CH CH CH CHN); 2.84-2.92 (m, 2H,
2
2
2
2
2
2
2
2
NCHCH
2
CH
2
CH
2
CH
2
CHN); 6.95 (m, 9H, CHarom); 7.38 (m, 9H, CHarom); 4.70 (d, 1H, J = 15.2 Hz,
-
N-CH -Ar); 5.74 (d, 1H, J = 15.2 Hz, -N-CH -Ar); 5.15 (d, 1H, J = 15.2 Hz, -N-CH -Ar); 6.15 (d, 1H, J
2 2 2

HETEROCYCLES, Vol. 89, No. 11, 2014
2569
=
15.2 Hz, -N-CH
2
-Ar); 5.05 (s, 2H, -O-CH
2
-Ar); 5.06 (s, 2H, -O-CH
2
-Ar); 3.41 (m, 2H, COD-CH); 5.02
1
3
(
m, 2H, COD-CH); 1.88 (m, 4H, COD-CH ); 2.27 (m, 4H, COD-CH ). C NMR (CDCl ) : 219.55 (d,
2
2
3
J
Rh-C = 47.3 Hz, Ccarbene); 24.12 (-N-CHCH
2
CH
CH-N-);
CH-N-); 53.88 (-N-CHCH
28.18 (Ar-C); 128.79 (Ar-C); 129.28 (Ar-C); 129.53 (Ar-C); 129.86 (Ar-C); 130.57 (Ar-C); 137.27
Ar-C); 158.48 (Ar-C); 67.89 (-N-CH -Ar); 68.21 (-N-CH -Ar); 68.34 (-O-CH -Ar); 70.30 (-O-CH -Ar);
9.25 (d, JRh-C = 14.5 Hz, COD-CH); 99.90 (d, JRh-C = 6.9 Hz, COD-CH); 29.41 (COD-CH ); 29.47
2
CH
28.86
CH
2
CH
2
CH-N-); 24.37 (-N-CHCH
2
CH
2
CH
2
CH
2
CH-N-);
2
8.74
(-N-CHCH
2
CH
2
CH
2
CH
2
2 2 2 2
(-N-CHCH CH CH CH CH-N-);
53.62
(
-N-CHCH
2
CH CH CH
2
2
2
2
2
CH
2
CH CH-N-); 115.05(Ar-C); 127.73 (Ar-C);
2
1
(
2
2
2
2
6
2
2 2 2 48 2 2
(COD-CH ); 32.85 (COD-CH ); 33.10 (COD-CH ). Anal. Calcd for C43H N ClO Rh: C, 67.67; H, 6.34;
N, 3.76. Found: C, 67.82; H, 6.52; N, 3.86.
General procedure for rhodium-carbene catalyzed reaction of sodium tetraphenylborate with
acetophenone
o
In a schlenk tube was placed NH
4
Cl (27 mg, 0.5 mmol), which was then dried 150 C in vacuo for 2 h.
Then sodium tetraphenylborate (85.5 mg, 0.25 mmol), substituted ketones (0.5 mmol), rhodium carbene
catalyst (0.005 mmol), o-xylene (5 mL) were added and the resulting mixture was heated for 25 h at 120
o
4
C, cooled to ambient temperature, exracted with EtOAc (30 mL). After drying over MgSO the organic
phase was evaporated and the residue was purified by flash chromatography (hexane/EtOAc, 5/1).
Isolated yield is checked by NMR and GC, all reactions were monitored by TLC.
ACKNOWLEDGEMENTS
This research was supported by the Adıyaman University Research Fund (FEFBAP/2012-0006).
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