Catalytic ring opening of acetylcyclopropane by water and alcohols under the action of copper or palladium salts

Article abstract of DOI:10.1023/A:1014010907818

The possibility of the cleavage of the C-C bond in acetylcyclopropane (ACP) under the action of water or alcohols in the presence of copper or palladium salts was demonstrated for the first time. At 175-180 °C, the reactions proceeded regioselectively wit

Full text of DOI:10.1023/A:1014010907818

1242
Russian Chemical Bulletin, International Edition, Vol. 50, No. 7, pp. 1242—1247, July, 2001
Catalytic ring opening of acetylcyclopropane by water and alcohols
under the action of copper or palladium salts
U. M. Dzhemilev,a R. I. Khusnutdinov,a« A. M. Atnabaeva,a Z. S. Muslimov,a
R. I. Parfenova,a and Yu. V. Tomilovb«
aInstitute of Petrochemistry and Catalysis, Academy of Sciences of Republic Bashkortostan,
Ufa Research Center of the Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347 2) 31 2750. E-mail: ink@anrb.ru
bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5328 E-mail: tom@cacr.ioc.ac.ru
The possibility of the cleavage of the C—C bond in acetylcyclopropane (ACP) under the
action of water or alcohols in the presence of copper or palladium salts was demonstrated for
the first time. At 175—180 °C, the reactions proceeded regioselectively with the cleavage of
the C(1)—C(2) bond in the cyclopropane ring. The reaction of ACP with water afforded
5-hydroxypentan-2-one, bis(3-acetylpropyl) ether, and furan compounds, whereas the reac-
tions with alcohols proceeded selectively to form 5-alkoxypentan-2-ones. The yields of the
latter depend on the nature and structure of the alcohol, the maximum values (98%) being
achieved in the case of primary alcohols.
Key words: acetylcyclopropane, catalysis, copper and palladium salts, hydrolysis, alco-
holysis, 5-hydroxypentan-2-one and its derivatives.
It is known that the cyclopropane ring possessing
lysts for this reaction, we studied the reactions of ACP
with water and alcohols under the action of Cu and Pd
salts and complexes, which are widely used in homoge-
neous catalytic conversions of hydrocarbons and unsat-
urated compounds.
partial π character can be coordinated to transition
metals, which results in the activation of σ bonds of the
ring and promotion of chemical transformations involv-
ing the cleavage of the C—C bonds. Because of this,
examples of the preparation of cyclopropane complexes
with transition metals stable under the normal condi-
tions are scarce.1 Generally, these complexes are un-
stable and either undergo cyclopropyl-allylic isomeriza-
tion2 (skeletal rearrangement in the case of polycyclic
cyclopropane-containing structures3) or are converted
into metallacyclobutanes.4
Studies on the cyclopropane ring opening by differ-
ent organic reagents under the conditions of metal-
complex catalysis have been carried out in recent years.
In particular, ring opening by alcohols under the action
of platinum complexes is of substantial synthetic inter-
est.5 Palladium complexes catalyze analogous reactions
of silyloxycyclopropanes with acyl, aryl, and vinyl ha-
lides.6 The reactions with trialkylalanes are catalyzed by
nickel complexes.7 The cyclopropane ring opening in
acetylcyclopropane (ACP, 1) and its derivatives per-
formed under conditions of acid catalysis with addition
of water8 or hydrogen halides9 resulted in derivatives of
γ-acetopropyl alcohol, γ-halo ketones, and β,γ-dihalo
ketones.
Results and Discussion
Copper and palladium salts (CuBr2, CuCl2•2H2O,
and PdCl2) (0.5 mol.%) exhibited the highest catalytic
activity and selectivity. The reactions were carried out
in an autoclave at 175—180 °C for 8—30 h. Under the
above-mentioned conditions, ACP reacts with H2O with
the cleavage of the C(1)—C(2) bond to form 5-hydroxy-
pentan-2-one (2) and 6-oxaundecane-2,10-dione (3).
In the reactions involving CuBr2, CuCl2•2H2O, or
PdCl2 as catalysts, compound 3 was obtained in 64, 58,
or 40% yields, respectively.
In spite of the drastic conditions (175—180 °C), the
reaction of ACP with water proceeded regioselectively.
Apparently, the formation of ether 3 involved two stages.
In the first stage, the cyclopropane ring underwent
hydrolytic scission. In the second stage, the resulting
alcohol 2 added analogously at the C(1)—C(2) bond of
the next ACP molecule. It should be noted that the
reaction mixture contained hydroxy ketone 2 along with
compounds of the tetrahydrofuran series, viz., 2-methyl-
tetrahydrofuran-2-ol (4) and 2-methyl-2-(4-oxopentyl-
oxy)tetrahydrofuran (5), which were formed due to
With the aim of developing a regioselective proce-
dure for the cleavage of the C—C bond in cyclopro-
panes and constructing selective metal-complex cata-
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1185—1189, July, 2001.
1066-5285/01/5007-1242 $25.00 ©ꢀ2001 Plenum Publishing Corporation

Russ.Chem.Bull., Int.Ed., Vol. 50, No. 7, July, 2001
1243
Catalytic ring opening of acetylcyclopropane
Scheme 1
MeCO(CH2)3O(CH2)3COMe
3
H
H
L
1
O
M+
O
Cat.
COMe
+ H2O
MeCO(CH2)3OH
180 °C
2
1
Me
+2, –H2O
+H2O, –2
+2, –H2O
+H2O, –2
Me
Me
Cat. = CuBr2, CuCl2•2H2O, PdCl2
OH
O(CH2)3COMe
O
O
4
5
Scheme 2
mutual conversions and could not be separated by frac-
tional distillation10 (Scheme 1). The existence of com-
pounds 2, 4, and 5 was confirmed by 1H and 13C
spectroscopy. The total yield of these compounds
was ∼30%.
Cat.
COMe + ROH
MeCO(CH2)3OR
7a—l
175—180 °C
6a—l
1
The yield of compound 3 could not be increased by
increasing the reaction time after complete conversion
of ACP due apparently to the existence of the equilib-
rium between the open and cyclic forms 2, 4, and 5
(cf. Ref. 10). The ratio between ether 3 and a mixture of
compounds 2 + 4 + 5 in the reaction mixture remained
virtually unchanged (∼2 : 1). However, this ratio de-
pended substantially on the amount of water used in this
reaction. The molar ratio 1 : H2O = 1 : 5 appeared to be
optimum. With CuBr2 as a catalyst, the yield of ether 3
was 64%. In the case of a tenfold excess of H2O, the
yield of ether 3 decreased to ∼20%. When the 1 : H2O
ratio was reduced to 1 : 2, the reaction proceeded more
slowly and the reaction time should be increased to 25 h
to obtain ether 3 in satisfactory yield. However, the
yield of compound 3 under these conditions was at most
55% with a simultaneous increase in the yields of com-
pounds 4 and 5.
Taking into account the formation of hydroxy ke-
tone 2 and its possible involvement in the ring opening
of the ACP molecule, it was of interest to study the
reactions of ACP with alcohols under the action of Cu
and Pd salts. The use of monohydric alcohols (6a—l) in
the reactions with ACP made it possible to prepare a
series of 5-alkoxypentanon-2-ones (7a—l). The yields of
the latter depended on both the nature of the alcohol
and the reaction conditions (Scheme 2). Nevertheless,
regioselective ring opening with the cleavage of the
C(1)—C(2) bond was observed in all cases.
Cat. = CuBr2, CuCl2•2H2O, PdCl2
R = Me (a); Et (b); Pr (c); Pri (d); Bu (e); C5H11 (f); CHEt2 (g);
C6H13 (h); C10H21 (i); PhCH2 (j); PhCHMe (k); CH2CF2CHF2 (l)
decreased in the following series (the yield of 7à is given
in parentheses): CuBr2 (99%) > CuCl2•2H2O (95%) >
CuSO4•5H2O (92%) > (CF3SO3Cu)2•C6H6 (89%). For
palladiums compounds, the following series was ob-
tained: PdCl2 (98%) > K2[PdCl4] (20%) > PdCl2•2PPh3
(13%) > Pd2(DBA)3•CHCl3 (10%). The yields of
alkoxypentanones 7 were the highest in the case of
lower alcohols (7à, 98%) and decreased as the length of
the chain and the degree of branching of the alkyl
radicals increased (Table 1). The duration of the reac-
tion depends also on the nature of the alcohol and the
catalyst. Thus the reaction of ACP with methanol in the
presence of CuBr2 as a catalyst proceeded four times
more rapidly than that with the use of PdCl2. In the
latter case, the reaction should be performed in a 1 : 5
alcohol—water medium because the rate of alcoholysis
of ACP in the absence of H2O decreases sharply.
The studies of the reactions of ACP with alcohols
demonstrated that the latter were partially converted
into dialkyl ethers under the reaction conditions, their
content being increased as the length of the alkyl radical
in the alcohol increased. In this connection, we at-
tempted to inhibit their formation by varying solvents
and found that the use of diethyl ether (the molar ratio
1 : 6 : Et2O = 1 : 1 : 3) was actually favorable for the
reduction in the portion of dialkyl ethers. It should be
noted that an analogous effect was not observed in the
case of dibutyl ether, THF, or dioxane.
The reactions of ACP with alcohols are efficiently
catalyzed by salts and complexes of copper (CuBr2,
CuCl2•2H2O, CuSO4•5H2O, or (CF3SO3Cu)2•C6H6)
and palladium (PdCl2, K2[PdCl4], PdCl2•2PPh3, or
Pd2(DBA)3•CHCl3). The catalytic activity of copper
compounds in a model reaction of ACP with MeOH
It is appropriate to use diethyl ether as the solvent in
the reactions with alcohols beginning with butanol be-

1244
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 7, July, 2001
Dzhemilev et al.
Table 1. Dependence of the yields of compounds 7a—l and
9a,b on the structure of the alcohol
dibenzyl ether in ∼30% yield regardless of the presence
or absence of diethyl ether.
The formation of the expected ether 7k in the reac-
tion of ACP with α-phenylethyl alcohol was accompa-
nied by dehydration as a side reaction giving rise to
styrene in 60% yield.
In the presence of copper- or palladium-containing
catalysts, ACP reacted with 1,2-ethylene glycol (8à) or
1,3-propylene glycol (8b) to give 5-(2-hydroxyethoxy)- or
5-(3-hydroxypropoxy)pentan-2-ones (9a,b), respectively
(Scheme 3). However, the latter were obtained in yields
of at most 40% due to the competitive formation of
diethylene glycol or dipropylene glycol, respectively.
ROH
t/h
Reaction
product
Yield (%)
CuBr2 PdCl2
CuBr2 PdCl2
6a
6b
6c
6d
6e
6f
6
6
8
8
8
10
10
10
10
10
8
25
25
25
30
25
25
25
33
40
18
12
10
8
7a
7b
7c
7d
7e
7f
99
77
73
32
75
47
34
76
52
47
6
98
75
65
29
63
45
22
60
43
36
4
6g
6h
6i
7g
7h
7i
6j
6k
6l
7j
7k
7l
Scheme 3
6
6
6
32
37
32
31
39
38
8a
8b
9a
9b
Cat.
8
1 + HO(CH2)nOH
MeCO(CH2)3O(CH2)nOH
180 °C
Note. The molar ratio ACP
: ROH : H2O : CuBr2 (or
8a,b
9a,b
PdCl2) : Et2O = 1 : 1 : 5 : 0.005 : 3; the temperature was 180 °C.
Cat. = CuBr2, CuCl2•2H2O, PdCl2
n = 2 (a), 3 (b)
cause the reactions with MeOH, EtOH, and PrOH
afforded the corresponding ethers in yields of no higher
than 1—3%. On the contrary, benzyl alcohol gave
The optimum temperature for the reactions of ACP
with water or alcohols lies in a narrow range of
Table 2. Data from elemental analysis of the compounds synthesized
CompoundB.p./
°C
(p/Torr)
Found
Calculatedformula
Molecular
(%)
C
H
5-Methoxypentan-2-one (7a)
91—94
(100)
82—85
(40)
81—84
(8)
120—123
(10)
121—125
(6)
140—143
(17)
120—122
(10)
111—114
(2)
62.05
62.07
64.80
64.61
66.54
66.67
66.73
66.67
68.62
68.35
69.98
69.77
69.63
69.77
70.90
70.97
74.23
74.38
75.23
75.00
75.50
75.73
44.58
44.44
57.76
57.53
59.82
60.00
10.36
10.34
10.75
10.77
11.13
11.11
11.14
11.11
11.36
11.39
11.67
11.62
11.64
11.62
11.81
11.83
12.64
12.40
8.35
8.33
8.72
8.74
5.53
5.55
9.57
9.59
9.96
C6H12O
5-Ethoxypentan-2-one (7b)
C7H14O2
C8H16O2
C8H16O2
C9H18O2
C10H20O2
C10H20O2
C11H22O2
C15H30O2
C12H16O2
C13H18O2
C8H12F4O2
C7H17O3
C8H16O3
5-Propoxypentan-2-one (7c)
5-Isopropoxypentan-2-one (7d)
5-Butoxypentan-2-one (7e)
5-Pentyloxypentan-2-one (7f)
5-(Pentan-3-yl)oxypentan-2-one (7g)
5-Hexyloxypentan-2-one (7h)
5-Decyloxypentan-2-one (7i)
—
5-Benzyloxypentan-2-one (7j)
122—124
(3)
158—162
(2)
110—114
(30)
5-(1-Phenylethoxy)pentan-2-one (7k)
5-(2,2,3,3-Tetrafluoropropoxy)pentan-2-one (7l)*
5-(2-Hydroxyethoxy)pentan-2-one (9a)
5-(3-Hydroxypropoxy)pentan-2-one (9b)
—
—
10.00
* Found (%): F, 35.05. Calculated (%): F, 35.19.

Russ.Chem.Bull., Int.Ed., Vol. 50, No. 7, July, 2001
1245
Catalytic ring opening of acetylcyclopropane
Table 3. 1H and 13C NMR spectral data for the compounds synthesized (CDCl3)
Compound
δ
1H
13C
3
4
5
1.77 (m, 2 H, H(4)); 2.11 (s, 3 H, Me);
2.43 (t, 2 H, H(3)); 3.59 (t, 2 H, H(5));
3.88 (s, 1 H, OH)
29.9 (Me); 208.8 (Ñ=O);
40.8 (Ñ(3)); 24.6 (Ñ(4));
60.0 (Ñ(5))
MeCOCH2CH2CH2OH
(2)
1
4
5
3
1.72 (m, 4 H, H(4)); 2.05 (s, 6 H, Me);
2.41 (t, 4 H, H(3)); 3.29 (t, 4 H, H(5))
29.9 (Me); 208.6 (C=O);
40.4 (C(3)); 23.9 (C(4));
68.9 (C(5))
(MeCOCH2CH2CH2)2O
(3)
2
3,4
5
1.33 (s, 3 Í, Me); 1.87 (m, 2 Í, Í(4));
2.44 (m, 2 Í, Í(3)); 3.66—3.86 (m, 2 Í,
Í(5)); 5.10 (s, 1 H, OH)
97.1 (C(2)); 37.1 (C(3));
26.0 (C(4)); 67.7 (C(5));
14.9 (Me)
MeC(OH)(CH2)2CH2
O
(4)
2
1.36 (s, 3 H, Me); 1.57—1.98 (m, 6 H,
H(4,7,8)); 2.08 (s, 3 H, H(1)); 2.35
(t, 2 H, H(3)); 3.36 (t, 2 H, H(5));
3.80 (m, 2 H, H(9))
29.9 (Ñ(1)); 208.1 (Ñ=O);
40.5 (Ñ(3)); 24.6 (Ñ(4));
62.3 (Ñ(5)); 107.2 (Ñ(6));
37.9 (Ñ(7)); 26.2 (Ñ(8));
67.7 (Ñ(9)); 22.1 (Me)
1
3
4
5
6
7,8
9
MeCOCH2CH2CH2OC(Me)(CH2)2CH2
O
(5)
1
3
4
5
1.76 (m, 2 H, H(4)); 2.01 (s, 3 H, Me);
2.45 (t, 2 H, H(3)); 3.30 (t, 2 H, H(5));
3.21 (s, 3 H, OMe)
29.8 (Me); 208.0 (C=O);
39.1 (C(3)); 23.9 (C(4));
70.9 (C(5)); 57.4 (OMe)
MeCOCH2CH2CH2OMe
(7a)
1
3
4
5
6
7
1.14 (t, 3 H, H(7)); 1.78 (t, 2 H, H(4));
2.11 (s, 3 H, Me); 2.51 (m, 2 H, H(3));
3.38 (t, 4 H, H(5), H(6))
29.7 (Me); 207.9 (C=O);
40.2 (C(3)); 24.8 (C(4));
69.0 (C(5)); 66.1 (C(6));
15.3 (C(7))
MeCOCH2CH2CH2OCH2CH3
(7b)
1
3
4
5
6
7
8
0.63 (t, 3 H, H(8)); 1.17—1.70 (m, 4 H,
H(4), H(7)); 1.90 (s, 3 H, Me); 2.26
(m, 2 H, H(3)); 3.14 (m, 4 H, H(5), H(6))
29.4 (Me); 207.9 (C=O);
39.9 (C(3)); 23.7 (C(4));
72.1 (C(5)); 69.3 (C(6));
22.6 (C(7)); 10.2 (C(8))
MeCOCH2CH2CH2OCH2CH2CH3
(7c)
1
3
4
5
6
7
1.10 (d, 6 H, H(7)); 1.17 (m, 2 H, H(4));
2.16 (s, 3 H, Me); 2.46 (m, 2 H, H(3));
3.46 (m, 2 Í, H(5)); 3.70 (m, 1 H, H(6))
29.9 (Me); 208.7 (C=O);
40.5 (C(3)); 24.3 (C(4));
71.3 (Ñ(5)); 66.9 (C(6));
22.1 (C(7))
MeCOCH2CH2CH2OCHMe2
(7d)
1
3
4
5
6
7,8
9
0.90 (t, 3 H, H(9)); 1.16—1.91 (m, 6 H,
H(4), H(7), H(8)); 2.15 (s, 3 H, Me);
2.53 (m, 2 H, H(3)); 3.41 (m, 4 H,
H(5), H(6))
29.0 (Me); 208.0 (C=O);
40.4 (C(3)); 24.0 (C(4));
70.6 (C(5)); 66.7 (Ñ(6));
31.8 (C(7)); 19.4 (C(8));
13.9 (C(9))
MeCOCH2CH2CH2OCH2(CH2)2CH3
(7e)
1
3
4
5
6
7—9
10
0.77 (t, 3 H, H(10)); 1.24—1.31 (m, 8 H,
H(4), H(7), H(8), H(9)); 2.03 (s, 3 H,
Me); 2.47 (m, 2 H, H(3)); 3.28 (m, 4 H,
H(5), H(6))
29.4 (Me); 208.4 (C=O);
40.3 (C(3)); 23.9 (C(4));
70.9 (C(5)); 69.6 (C(6));
29.8 (C(7)); 28.4 (C(8));
22.5 (C(9)); 14.0 (C(10))
MeCOCH2CH2CH2OCH2(CH2)3CH3
(7f)
1
3
4
5
6
7
8
0.89 (t, 6 H, H(8)); 1.73 (m, 6 H, H(4),
H(7)); 1.96 (s, 3 H, Me); 2.35 (m, 2 H,
H(3)); 3.23 (m, 2 H, H(5)); 3.57 (m,
1 H, H(6))
29.7 (Me); 208.2 (C=O);
40.2 (C(3)); 23.8 (C(4));
69.3 (C(5)); 66.8 (C(6));
23.7 (C(7)); 14.9 (C(8))
MeCOCH2CH2CH2OCH(CH2CH3)2
(7g)
1
3
4
5
6
7—10 11
0.83 (t, 3 H, H(11)); 1.24—1.77 (m, 10 H,
H(4), H(7), H(8) H(9), H(10)); 2.10
(s, 3 H, Me); 2.45 (m, 2 H, H(3)); 3.40
(m, 4 H, H(5), H(6))
29.7 (Me); 208.6 (C=O);
40.4 (C(3)); 24.0 (C(4));
69.9 (C(5)); 69.7 (C(6));
31.8 (C(7)); 30.0 (C(8));
25.2 (C(9)); 22.7 (C(10));
14.1 (C(11))
MeCOCH2CH2CH2OCH(CH2)4CH3
(7h)
(to be continued)

1246
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 7, July, 2001
Dzhemilev et al.
Table 3 (continued)
Compound
δ
1H
13C
1
3
4
5
6
7—14
15
0.81 (t, 3 H, H(15)); 1.20—1.85 (m, 18 H,
H(4), H(7), H(8), H(9), H(10), H(11),
H(12), H(13), H(14)); 2.08 (s, 3 H, Me);
2.46 (m, 2 H, H(3)); 3.34 (t, 2 Í, H(5),
H(6))
29.0 (Me); 208.4 (C=O);
40.4 (C(3)); 24.0 (C(4));
71.0 (C(5)); 69.7 (C(6));
32.0 (C(7)); 30.0 (C(8));
29.9 (C(9)); 29.8 (C10);
29.6 (C(11)); 29.6 (C(12));
26.2 (C(13)); 22.7 (C(14));
14.1 (Ñ(15))
MeCOCH2CH2CH2OCH(CH2)8CH3
(7i)
3
4
5
6
1.77 (m, 2 H, H(4)); 2.01 (s, 3 H, Me);
2.44 (m, 2 H, H(3)); 3.37 (t, 2 H, H(5));
4.36 (s, 2 H, H(6)); 7.21 (s, 5 H, Ph)
29.8 (Me); 208.4 (C=O);
40.2 (C(3)); 23.8 (C(4));
69.2 (C(5)); 72.7 (C(6));
127.5, 128.3; 138.36 (Ñ6Í5)
MeCOCH2CH2CH2OCH2Ph
(7j)
3
4
5
6
7
1.32 (d, 3 H, H(7)); 1.45 (m, 2 H, H(4));
2.13 (s, 3 H, Me); 2.44 (m, 2 H, H(3));
3.29 (t, 2 H, H(5)); 5.17 (q, 1 H, H(6));
7.31 (m, 5 H, Ph)
29.9 (Me); 208.6 (C=O);
40.0 (C(3)); 24.2 (C(4));
67.7 (C(5)); 78.4 (C(6));
126.2, 127.4, 128.4, 144.0
(Ñ6Í5); 24.1 (C(7))
MeCOCH2CH2CH2OCH(Me)Ph
(7k)
1
3
4
5
6
7
8
1.82 (m, 2 Í, Í(4)); 2.02 (s, 3 Í, Ìå);
2.20 (m, 2 Í, Í(3)); 3.04—3.80 (m, 4 Í,
Í(5), H(6)); 5.00—6.30 (m, 1 Í, Í(8))
29.0 (Me); 207.7 (C=O);
39.0 (C(3)); 30.0 (C(4));
71.0 (C(5)); 67.2 (C(6));
97.2—125.6 (m, Ñ(7), C(8))
MeCOCH2CH2CH2OCH2CF2CF2H
(7l)
3
4
5
6
7
1.96 (s, 3 Í, Me); 1.65 (m, 2 Í, Í(4));
2.35 (m, 2 Í, Í(3)); 3.00–3.52 (m, 6 Í,
Í(5), H(6), H(7)); 2.85 (s, 1 H, OH)
29.6 (Me); 208.7 (C=O);
39.9 (C(3)); 23.6 (C(4));
69.8 (C(5)); 69.2 (C(6));
71.2 (C(7))
MeCOCH2CH2CH2OCH2CH2OH
(9a)
3
4
5
6
7
8
1.99 (s, 3 Í, Me); 1.50—1.80 (m, 4 Í,
Í(4), H(7)); 2.80—3.60 (m, 2 Í, Í(3));
3.20—3.62 (m, 6 Í, Í(5), H(6), H(8));
2.96 (s, 1 H, OH)
29.8 (Me); 208.7 (C=O);
40.2 (C(3)); 23.7 (C(4));
69.95 (C(5)); 69.1 (C(6));
32.1 (C(7)); 60.91 (C(8))
MeCOCH2CH2CH2OCH2CH2CH2OH
(9b)
eters in CDCl3 relative to Me4Si as the internal standard. The
reaction products were analyzed by GLC on a Tsvet-5 chro-
matograph equipped with a flame ionization detector and a
300½0.3-cm column (Inerton AW-DMCS, SE-30). Preparative
separation was carried out on a Carlo Erba instrument equipped
with a flame ionization detector and a 600½0.5-cm column
(Chromaton N-AW, SE-30) using helium as the carrier gas.
Acetylcyclopropane was synthesized according to a procedure
reported previously.11 Alcohols (MeOH, EtOH, PrOH, PriOH,
BuOH, C5H11OH, Et2CHOH, C6H11OH, C10H21OH, and
PhCH2OH) were commercially available compounds (all of
reagent grade); PhCH(Ìå)OH and CF2HCF2CH2OH (both of
analytical grade) were purchased from Aldrich. The catalysts
PdCl2 and (CF3SO3Cu)2•C6H6 (both of reagent grade)
175—180 °C. When the temperature was increased to
190 °C, the reactions afforded higher oligomers as the
major products, whereas the reactions sharply slowed
down at temperatures below 175 °C.
The compositions and the structures of compounds
3, 7a—l, and 9à,b were established based on the data
from elemental analysis (Table 2) and 1H and 13C NMR
spectroscopy (Table 3). The spectral characteristics of
compounds 2, 4, and 5 correspond to those published in
the literature.10
Thus, we demonstrated the possibility of catalytic
regioselective cyclopropane ring opening in acetyl-
cyclopropane under the action of water, monohydric
alcohols, or dihydric alcohols in the presence of copper
or palladium compounds, which allows the preparation
of 6-oxaundeca-2,10-dione, 5-alkoxypentan-2-ones, and
5-(ω-hydroxyalkoxy)pentan-2-ones in good yields.
were purchased from Aldrich. The complexes K2[PdCl4],12
14
PdCl2•2 PPh3,13 and Pd2(DBA)3•CHCl3
according to known procedures.
were prepared
6-Oxaundeca-2,10-dione (3). Acetylcyclopropane (1.35 g,
16 mmol), H2O (1.40 g, 80 mmol), CuBr2 (0.016 g, 0.07 mmol),
and diethyl ether (2.80 g, 38 mmol) were placed in a 17-mL
microautoclave and the reaction mixture was heated at 180 °C
for 6 h. Then the solvent was distilled off and the residue was
fractionated to give a fraction with b.p. 143—146 °C (100 Torr),
which corresponded (according to the NMR spectral data) to a
mixture of compounds 2, 4, and 5, and a fraction with
Experimental
The 1H and 13C NMR spectra were recorded on Tesla
BS-567 (100 MHz) and JEOL FX-90Q (22.5 MHz) spectrom-

Russ.Chem.Bull., Int.Ed., Vol. 50, No. 7, July, 2001
1247
Catalytic ring opening of acetylcyclopropane
b.p 120—122 °C (1.5 Torr). Ether 3 was obtained as a colorless
liquid in a yield of 0.96 g (64%). Found (%): C, 64.59; H, 9.80.
C10H18O3. Calculated (%): C, 64.50; H 9.76. The 1H and
13C NMR spectral data for compound 3 are given in Table 3.
Synthesis of 5-alkoxypentan-2-ones (7a—l) (general pro-
cedure). Acetylcyclopropane (16 mmol), alcohol (ROH)
(16 mmol), H2O (80 mmol), a catalyst (0.07—0.14 mmol), and
a solvent (35—38 mmol) were placed in a 17-mL microautoclave
or a glass tube (∼20 mL) and the reaction mixture was heated at
175—180 °C from 7 to 50 h depending on the alcohol and the
catalyst used. Compounds 7a—h, 7j, and 7k were isolated by
vacuum distillation. Compounds 7i, 7l, 9a, and 9b were iso-
lated by preparative GLC. The boiling points and the data from
elemental analysis of the compounds synthesized are given in
Table 2. The 1H and 13C NMR spectral data are listed in
Table 3.
4. F. J. McQuillin and K. G. Powell, J. Chem. Soc., Dalton
Trans., 1972, 2123.
5. J. Beyr and R. Madsen, J. Am. Chem. Soc., 1998, 120,
12137.
6. T. Fujimura, S. Aoki, and E. Nakamura, J. Org. Chem.,
1991, 56, 2809.
7. T. Ichiyanagi, S. Kuniyama, M. Shimizu, and T. Fujisawa,
Chem. Lett., 1997, 1149.
8. T. Nakai, E. Wada, and M. Okawara, Tetrahedron Lett.,
1975, 1531.
9. B. A. Cheskis, M. M. Ivanov, A. M. Moiseenkov, and
O. M. Nefedov, Usp. Khim., 1993, 62, 365 [Russ. Chem.
Rev., 1993, 62 (Engl. Transl.)].
10. O. M. Nefedov, V. M. Shostakovskii, I. E. Dolgii, I. K.
Anikeev, V. N. Pavlychev, and Yu. M. Luchko, Izv. Akad.
Nauk SSSR, Ser. Khim., 1978, 234 [Bull. Acad. Sci. USSR,
Div. Chem. Sci., 1978, 27, 207 (Engl. Transl.)].
11. A. P. Meshcheryakov and V. G. Glukhovtsev, Izv. Akad.
Nauk SSSR, Ser. Khim. [Bull. Acad. Sci. USSR, Div. Chem.
Sci.], 1959, 1490 (in Russian).
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[Manual on Inorganic Synthesis], Khimiya, Moscow, 1965,
347 (in Russian).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 00-15-
97312).
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Received September 14, 2000;
in revived form March 2, 2001