Cyclopropanation of alkenes catalyzed by metallophthalocyanines

Article abstract of DOI:10.1016/j.molcata.2005.10.014

Metallophthalocyanines bearing substituents especially electron-withdrawing substituents are found to be efficient catalysts for cyclopropanation of alkenes with EDA. The influences of reaction conditions have been studied, leading to the highest yield of

Full text of DOI:10.1016/j.molcata.2005.10.014

Journal of Molecular Catalysis A: Chemical 246 (2006) 49–52
Cyclopropanation of alkenes catalyzed by metallophthalocyanines
Hui-Hua Liua, Yi Wanga, Yuan-Jie Shub, Xiang-Ge Zhoua,c,∗, Jiang Wua, Sheng-Yong Yana
a Institute of Homogeneous Catalysis, College of Chemistry, Sichuan University, Chengdu 610064, China
b Institute of Chemical Materials, CAEP, Mianyang 621900, China
c State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China
Received 26 August 2005; received in revised form 10 October 2005; accepted 13 October 2005
Available online 22 November 2005
Abstract
Metallophthalocyanines bearing substituents especially electron-withdrawing substituents are found to be efficient catalysts for cyclopropanation
of alkenes with EDA. The influences of reaction conditions have been studied, leading to the highest yield of 91% for styrene by using fluoro-
substituted ruthenium–phthalocyanine complex.
© 2005 Elsevier B.V. All rights reserved.
Keywords: Cyclopropanation; Metallophthalocyanine; Catalyst; Fluoro-substituted
1. Introduction
transition metal catalyzed synthetic transformation and recent
progress in oxidation catalyzed by metallophthalocyanines [14],
herein is reported the first example of catalytic cyclopropanation
of olefins by modified phthalocyanine complexes.
Transition metal complex-mediated cyclopropanation of
alkenes with diazo compounds is one of the most attractive meth-
ods for the efficient and selective construction of synthetically
and biologically important cyclopropanes [1]. Among the wide
variety of catalytic systems [2], metalloporphyrin based cata-
lysts are studied in detail owing to their excellent selectivity
and highly catalytic activities, along with biological relevance
[3]. Rhodium porphyrin complex was firstly introduced into this
capacity by Callot et al. [4], and was later significantly explored
by Kodadek [5], Woo and co-workers [6]. The central metal ions
were then expanded to osmium, iron, ruthenium and others [7].
Meanwhile, asymmetric cylopropanation and mechanism were
disclosed by Goss et al. [8–11].
On the other hand, metallophthalocyanines have attracted a
great deal of research interests for many years because of their
intense coloration and diverse redox chemistry associated with
both 18␲-electron system of the phthalocyanine ring and central
atom [12], which are structurally similar to metalloporphyrins
[13]. Moreover, Pc complexes are easier accessible, more sta-
ble to degradation than porphyrin analogues. However, low
solubility of Pc complex in common organic solvents retards
its application in catalysis. In continuation to our studies on
2. Experimental
2.1. Materials and instruments
All chemicals were purchased from Aldrich or Lancaster and
used as received unless otherwise noted. Solvents and substrates
were purified by standard procedures before use. All the phthalo-
cyanine complexes were prepared according to the methods
∗
Corresponding author.
E-mail address: zhouxianggescu@126.com (X.-G. Zhou).
1381-1169/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2005.10.014

50
H.-H. Liu et al. / Journal of Molecular Catalysis A: Chemical 246 (2006) 49–52
described in the literature [15–19]. Among them, 5-FeCl and
5-Cu have never been reported [20].
1H NMR spectra were measured on a Bruker DPX300 spec-
trometer by using tetramethylsilane (TMS) as an internal stan-
dard, the chemical shifts are relative to TMS. Infrared spectra
(KBr) were recorded on NEXUS-670 FT-IR spectrometer. Ele-
mental analyses were performed on a Carlo Erba 1106 instru-
ment. GC measurements were carried out on a HP model 5890
series II chromatograph equipped with a flame ionization detec-
tor. Mass spectra were recorded on a Finnigan MAT 95 Mass
spectrometer.
Scheme 1.
2-Fe as catalyst shown in Scheme 1, and the results were listed
in Table 1.
AsshowninTable1, runningthereactionsinvarioussolvents,
disclosed of either yield or trans:cis selectivity a dependence on
the nature of them. In normal organic solvents, trans configu-
ration products predominated over cis with the highest ratio of
6:1 in methanol and the lowest yield as 23% (entry 3). In ion
liquid, on the contrary, the main product was in cis configura-
tion (entry 5). Among the solvents examined, aprotic solvent
dichloromethane is superior to others with 78% yield.
For the reaction temperature, lower temperature than 25 ◦C
decreased reaction rate, while yields remained almost the same
(entries 1, 6 and 7). When the temperature increased from 25
to 40 ◦C, yield decreased significantly from 78 to 39%, which
is different from recently reported results of Cu-Pc catalysis in
xylene [21].
The effect of the amount of catalyst used was also studied,
when 0.1, 0.2, 1 or 2% catalyst was used, cyclopropane could
be obtained in the yields of 56, 78, 80 or 80%, respectively. The
trans:cis selectivity varied slightly from 2.2 to 2.5. The results
suggested that more catalyst used than 0.2% was not necessary.
From the results obtained, the reaction conditions were opti-
mized to be dichloromethane as solvent, 25 ◦C as reaction tem-
perature and 0.2% catalyst was used for further studies.
2.2. Preparation of 5-FeCl and 5-Cu
4-(3-Trifluoromethylphenoxy)-phthalonitrile (0.2 g, 0.7
mmol), 1-pentanal (5 mmol) and DBU (0.3 mL) were mixed
and stirred at 50 ◦C for 10 min in an argon atmosphere and
then 0.018 g (0.015 mmol) of anhydrous iron chloride was
added. The suspension was slowly brought to boiling over 2 h
followed by refluxing for 40 h. The reactant was cooled down
and 10 mL of methanol was added. The deep green product
was filtered, washed with hydrochloric acid (5%, 30 mL) and
then small amount of methanol (ca. 10 mL). The crude product
was extracted with methanol in a Soxhlet extractor and purified
by column chromatography (silica gel and toluene). The blue
fraction was collected, evaporated under vacuum to give deep
blue powder. Yield: 0.18 g (62%). IR (cm−1): 1614, 1598,
1491, 1457, 1414 (C F), 1330 (C F), 1288, 1240 (Ar O Ar),
1158, 1066, 960, 895, 792, 654. MS (FAB): 1244 (M+•), 1209
(M–Cl). Anal calculated for C60H28N8O4ClF12Fe: C, 50.58;
H, 1.97; N, 7.87. Found: C, 50.15; H, 1.92; N, 7.48.
5-Cu was prepared according to the method described as 5-
FeCl except that CuCl2 was used instead of FeCl3 to give deep
green solid. Yield: 0.15 g (57%). IR (cm−1): 1620, 1594, 1491,
1457, 1414 (C F), 1320 (C F), 1288, 1228 (Ar O Ar), 1162,
1064, 960, 888, 750, 652. MS (FAB): 1217(M+•). Anal calcu-
lated for C60H28N8O4F12Cu: C, 59.21; H, 2.30; N, 9.21. Found:
C, 58.82; H, 2.43; N, 8.89.
3.2. Cyclopropanation of styrene catalyzed by different
metallophthalocyanines
As usual, the catalytic activity of Pc complexes is strongly
dependent upon both central metal and ligands. In our research,
2.3. General procedure for catalytic cyclopropanation of
alkenes
Table 1
Influences of reaction conditionsa
Entry
Condition
Yield
(%)b
Conversion
(%)
Trans:cisb
In a typical procedure of catalytic cyclopropanation: a solu-
tion of EDA (1.5 mmol) in dichloromethane (5 mL) was added
slowly to a solution of olefine (1 mmol) and metallophthalo-
cyanine (2 ␮mol) in dichloromethane (5 mL) over 2 h at room
temperature under argon. The mixture was then stirred for an
additional 2 h. After removal of the catalysts by flash chromatog-
raphy on a short column of silica gel, the results were determined
by GC.
1
2
3
4
25 ◦C, CH2Cl2
CH3CN
CH3OH
78
40
23
63
51
69
63
72
2.4
1.9
6.0
3.0
Toluene
5
52
95
0.67
6
7
8
CH2Cl2, −25 ◦Cc
0 ◦Cd
40 ◦C
80
76
39
46
58
39
2.0
2.1
2.6
3. Results and discussion
a
Reactions were performed with a cat.:styrene:EDA molar ratio of 1:500:750,
for 4 h at room temperature.
3.1. Optimization of reaction conditions
b
Determined by GC (column: SE-30).
10 h was needed for the completion of reaction.
6 h was needed for the completion of reaction.
c
The influences of reaction conditions such as temperature,
solvents and amount of catalyst used were optimized by using
d

H.-H. Liu et al. / Journal of Molecular Catalysis A: Chemical 246 (2006) 49–52
51
Table 2
15 different phthalocyanine complexes including five different
Pc ligands were applied for the catalytic cyclopropanation of
styrene, and the results were listed in Table 2.
Cyclopropanation of olefins with EDA using different metallophthalocyanine as
catalysts
Entry
Cat.
Yield (%)
Conversion (%)
Trans:cis
In general, time course experiments for reaction catalyzed
by metallophthalocyanines revealed that the reaction proceeded
smoothly without an induction period. As shown in Table 2,
Fe, Cu and Ru complexes exhibited high catalytic abilities with
moderate yields from 59 to 75% when the same ligand of non-
substitutedphthalocyaninewasused, whileonlysmallamountof
productwasobtainedbyusingNiorMncomplexes(entries1–5).
Aroused from the literature that solubility of metallophthalo-
cyanine was an important factor during catalysis, we modified
metallophthalocyanines with substituents. Indeed, substituted
ligand especially with electron-withdrawing groups benefited
to the reactions and the highest yields as 91 and 90% could
be obtained with 3-Ru and 5-FeCl as homogeneous catalysts,
respectively (entries 12 and 14), which were much higher than
the yields of 71 or 77% by Rh or Ru porphyrinato analogues.
Thus, the excellent yields indicated 3-Ru and 5-FeCl to
be highly robust toward catalytic cyclopropanation reactions.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1-Fe(III)Cl
1-Mn(II)
1-Ni(II)
1-Cu(II)
1-Ru(III)Cl
2-Fe(II)
62
4
8
51
90
88
68
79
75
95
64
70
76
68
88
73
99
89
2.4
1.6
1.5
1.2
1.9
2.1
1.5
1.8
1.5
5.0
2.8
3.2
2.8
2.0
4.5
59
75
78
13
12
55
89
86
91
80
90
65
2-Mn(II)
2-Ni(II)
2-Cu(II)
3-Fe(III)Cl
3-Cu(II)
3-Ru(II)
4-Fe(II)
5-Fe(III)Cl
5-Cu(II)
Reactions were performed in CH2Cl2 at room temperature for 4 h with a
cat.:styrene:EDA molar ratio of 1:500:750.
Table 3
Catalytic cyclopropanation by 3-Ru
Entry
1
Substrate
Product
Yield (%)
91
Trans:cis
3.2
2
3
4
90
88
88
5.2
4.8
5.3
5
6
82
86
5.8
4.5
7
8
81
83
4.0
5.0
9
67
62
–
–
10

52
H.-H. Liu et al. / Journal of Molecular Catalysis A: Chemical 246 (2006) 49–52
Because of the simpler procedure of preparation, 3-Ru was
selected for other substrates.
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4. Conclusion
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metry 149 (2003) 837.
Metallophthalocyanines were found to be efficient catalysts
for the cyclopropanation of a variety of alkenes. Substituted
especially electron-withdrawing substituted phthalocya-
nine complexes exhibited excellent catalytic abilities. The
highest yield of 91% for styrene was obtained by using
fluoro-substituted ruthenium–phthalocyanine complex.
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Acknowledgements
We thank Sichuan University and State Key Laboratory of
Coordination Chemistry of Nanjing University for financial
support.
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