Fragmentation of tertiary cyclopropanol compounds catalyzed by vanadyl acetylacetonate

Article abstract of DOI:10.1016/j.tet.2005.03.033

Tertiary cyclopropanol compounds react with a catalytic amount of vanadyl acetylacetonate in the presence of oxygen affording β-hydroxyketones and β-diketones. For 3-substituted-bicyclo[4.1.0]alkanols, peroxides are obtained, as are the β-hydroxyketones. Conversely, 2- ethoxycarbonylcyclopropyl silyl ethers produce ethyl γ-oxocarboxylate derivatives given the same reaction conditions.

Full text of DOI:10.1016/j.tet.2005.03.033

Tetrahedron 61 (2005) 4831–4839
Fragmentation of tertiary cyclopropanol compounds catalyzed
by vanadyl acetylacetonate
b
c
c
c
Masayuki Kirihara,a, Hiroko Kakuda, Motohiro Ichinose, Yuta Ochiai, Shinobu Takizawa,
*
Asuka Mokuya,a Kumiko Okubo,a Akihiko Hatanoa and Motoo Shirod
aDepartment of Materials Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan
bLaboratory of Chemistry, Toyama Medical and Pharmaceutical University, Sugitani 2630, Toyama 930-0194, Japan
cFaculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, Sugitani 2630, Toyama 930-0194, Japan
dRigaku Corporation, 3-9-12 Matsubara-cho, Akishima-shi, Tokyo 196-8666, Japan
Received 30 August 2004; accepted 4 March 2005
Available online 11 April 2005
Abstract—Tertiary cyclopropanol compounds react with a catalytic amount of vanadyl acetylacetonate in the presence of oxygen affording
b-hydroxyketones and b-diketones. For 3-substituted-bicyclo[4.1.0]alkanols, peroxides are obtained, as are the b-hydroxyketones.
Conversely, 2-ethoxycarbonylcyclopropyl silyl ethers produce ethyl g-oxocarboxylate derivatives given the same reaction conditions.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
of a catalytic amount of VO(acac)2 (0.1 equiv; Scheme 3).
b-Diketone (3a) was the major product when a stoichio-
metric amount of VO(acac)2 was present. However,
b-hydroxyketone (2a) predominated when a catalytic
amount of VO(acac)2 was used.
Tertiary cyclopropanol compounds (1) are important
synthetic intermediates owing to their great reactivity.
Many different reactions have been developed using
derivatives of 1 as reagents,1 including those whose
purpose is to specifically cleave at bonds ‘a’ and/or ‘b’2–4
(Scheme 1).
Generally, reactions involving derivatives of 1 and
0.1 equiv of VO(acac)2 under oxygen and in ethanol caused
the cyclopropane ring to fragment and produced b-hydroxy
ketones and b-diketones (Table 1). For 1-(trimethyl-
siloxy)bicyclo[n.1.0]alkanes or bicyclo[n.1.0]alkanols
(entries 1–6), the ‘b’ bond was specifically cleaved
yielding ring-enlarged b-hydroxyketones and b-diketones.
With VO(acac)2 present, silyl ethers hydrolyzed immedi-
ately upon dissolution into ethanol and the corresponding
alcohols were formed. Here, the reactive species are the
tertiary cyclopropanols rather than the starting materials.
When the cyclopropane ring lacked an oxygen functionality,
the reaction did not occur (entry 6, Table 1).
We found that when tertiary cyclopropyl silyl ethers or
tertiary cyclopropanols (1) are treated with a catalytic
amount of vanadyl acetylacetonate under oxygen and in
ethanol, the cyclopropyl ring fragments and b-hydroxy-
ketones (2) and b-diketones (3) are produced (Scheme 2).
We described these findings in a preliminary communi-
cation.5 We have further investigated the properties of the
reactions and report full experimental details herein.
2. Results and discussion
Although vanadyl acetylacetonate did not react with 1a
or 1b in an aprotic solvent (e.g., dichloromethane), it did
To begin, we aerobically reacted ethanolic 1a with 1.0 equiv
of vanadyl acetylacetonate [VO(acac)2]6 at room tempera-
ture and obtained as products, b-hydroxyketone (2a) and
b-diketone (3a). The reaction also occurred in the presence
Keywords: Fragmentation reactions; Cyclopropanes; Peroxides; Vanadium
compounds.
*
Corresponding author. Tel: C81 538 45 0166; fax: C81 538 45 0110;
e-mail: kirihara@ms.sist.ac.jp
Scheme 1.
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.03.033

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M. Kirihara et al. / Tetrahedron 61 (2005) 4831–4839
react with those compounds in trifluoroethanol with the
b-diketones (3a and 3b) as the main products (Scheme 4).
Interestingly, reaction of 5-but-3-enylbicyclo[4.1.0]hep-
tane-1-ol (1i) did not result in a tandem ring expansion
and cyclization, but instead a simple ring expansion
Scheme 2.
Scheme 3.
Table 1.
Entry
1
Starting material
Products
1a
2a 41%
3a 24%
2
3
1b (RZTMS)
1b0 (RZH)
2b RZTMS (40%)
RZH (36%)
3b RZTMS (25%)
RZH (39%)
2c RZTMS (25%)
RZH (21%)
3c RZTMS (30%)
RZH (35%)
1c (RZTMS)
1c0 (RZH)
4
5
6
1d
1e
2d 31%
2e 75%
2f 29%
3d 33%
3e 10%
3f 31%
1f
7
8
1g
1h
2g 47%
2h 80%

M. Kirihara et al. / Tetrahedron 61 (2005) 4831–4839
4833
Recently, Blanco and co-workers reported that ether
solutions of 3-alkylbicyclo[n.1.0]alkanols when treated
with ferric acetylacetonate and light in the presence of
oxygen and silica gel produced peroxidated compounds
(Scheme 8).7
Scheme 4.
occurred giving 2i and 3i. This result contrasts sharply with
the reaction of 1i with an equimolar or excess amount of
iron(III) chloride3c,d or manganese(III) picolinate3g under an
inert atmosphere. For the latter, a radical tandem reaction
occurs (Scheme 5).
Scheme 8.
We also found that both peroxidated compounds (4) and
b-hydroxyketones (2) were produced when 3-substituted
bicyclo[4.1.0]alkanols (1j, 1k, and 1l) were treated with a
catalytic amount of VO(acac)2 under oxygen. Peroxides 4
were the principal products when trifluoroethanol was the
solvent (Table 2).
We assumed that the reaction of VO(acac)2 is a radical
reaction and molecular oxygen reacted with the radical
faster than the radical reacted with the alkene. Actually, in
the presence of oxygen, the cyclopropanol (1i0)† reacted
with Fe(III) or Mn(II) producing 2i and 3i (Scheme 6).
Scheme 5.
Scheme 6.
The b-diketone (3a) was not obtained by reaction of the
b-hydroxyketone (2a) with VO(acac)2 (Scheme 7).
Therefore, most likely, b-diketones are directly produced
from cyclopropanol derivatives.
The structure of 4j was determined by X-ray crystal-
lography. The ORTEP plot shows the X-ray structure of 4j
(Scheme 9).
Treatment of 4j with a catalytic amount of VO(acac)2 in
ethanol and oxygen afforded b-hydroxyketone 2j at 75%
yield (Scheme 10). Therefore, peroxide derivatives are
probably reaction intermediates formed during production
of b-hydroxyketones and b-diketones from cyclopropyl
compounds. For 3-unsubstituted bicyclo[4.1.0]alkanols (1),
peroxidated species might be unstable reaction inter-
mediates and immediately form b-hydroxyketones and
b-diketones.
Scheme 7.
A plausible reaction mechanism is depicted in Scheme 11.
Tertiary cyclopropyl silyl ethers are immediately
† The tertiary cyclopropyl silyl ether (1i) did not react under the same
reaction condition.

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M. Kirihara et al. / Tetrahedron 61 (2005) 4831–4839
Table 2.
Entry
1
Starting material
Solvent
Products
EtOH
1j
4j 45%
2j 53%
2j 10%
2k trace
2l 26%
2
3
4
CF3CH2OH
1j
4j 86%
CF3CH2OH
1k
4k 43%
CF3CH2OH
1l
4l 43%
Scheme 10.
hydrolyzed into the corresponding alcohols by V(IV) in
ethanol. The resulting cyclopropanols react with V(IV)
resulting in the ring expansion and free radical formation.
The radical then reacts with molecular oxygen to provide b-
perhydroxyketones which are, in turn, transformed into
endoperoxide compounds.‡ The peroxy compounds
then react with ethanol to provide b-hydroxyketones.
b-Diketones might be obtained by reaction of the peroxy
compounds with V(IV) and molecular oxygen, because a
b-diketone was the main product a stoichiometric amount
of VO(acac)2.
We also examined the reaction of 1-(trimethylsiloxy)bi-
cyclo[n.1.0]alkanes bearing an ethoxycarbonyl group (5) at
the 2-position and found that the ‘a’ bond was specifically
cleaved to provide non-oxygenated compounds (6; Table 3).
The same result was obtained when 5b reacted in the
absence of oxygen (Scheme 12). In these cases, VO(acac)2
might act as a simple Lewis Acid.
‡ Although we reported previously that a stoichiometric amount of
VO(acac)2 reacted with 1-(trimethylsiloxy)bicyclo[4.1.0]heptane in the
absence of oxygen,5 it is possible that a trace amount of oxygen
that was dissolved in the solvent might have reacted with
1-(trimethylsiloxy)bicyclo[4.1.0]heptane.
Scheme 9.

M. Kirihara et al. / Tetrahedron 61 (2005) 4831–4839
4835
Scheme 11.
Table 3.
Entry
1
Starting material
Products
Yield (%)
84
6a
6b
5a
5b
5c
2
3
82
86
6c
5d
6d
4
5
6
90
90
88
6e
5e
5f
6f
peroxide intermediates. Conversely, 2-ethoxycarbonyl-
cyclopropyl silyl ethers afford ethyl g-oxocarboxylate
given the same conditions. In these cases, VO(acac)2
probably acts as a Lewis acid.
Scheme 12.
4. Experimental
4.1. General
3. Conclusions
Tertiary cyclopropyl silyl ethers react with a catalytic
amount of VO(acac)2 to provide b-hydroxyketones and
b-diketones. For 3-substituted-bicyclo[n.1.0]alkanol deriva-
tives, peroxides and with b-hydroxyketones are produced.
The b-hydroxyketones and b-diketones obtained from the
tertiary cyclopropyl silyl ethers must be derived from
IR spectra were recorded using a Perkin–Elmer 1600 FT-IR
or a Jasco IR-8300 FT-IR spectrophotometer. NMR spectra
acquired using a Varian Gemini 300, a JEOL JNM-400, or a
Varian UNITY plus 500 spectrometer. All NMR samples

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M. Kirihara et al. / Tetrahedron 61 (2005) 4831–4839
were dissolved in CDCl3 containing tetramethylsilane as an
internal standard. Coupling constants (J) are given in hertz
(Hz). Low-resolution and high-resolution mass spectra
(electron impact) were recorded on using a JEOL D-200,
a JEOL JMS D-200 or a JEOL AX505 spectrometer.
Melting points were determined using a Yanagimoto micro-
melting point apparatus and are reported as uncorrected
values. For column chromatography, silica gel (Merck
Kieselger 60) was the support.
HRMS calcd for C11H20O2 (MC): 184.1444, found
184.1468.
4.2.6. 5-t-Butylcyclohepta-1,3-dione (3c). IR (neat) cmK1
:
1699; 1H NMR (CDCl3) d: 0.91 (9H, s), 1.59–1.71 (2H, m),
2.08–2.16 (1H, m), 2.38–2.51 (2H, m), 2.60–2.67 (2H, m),
3.56 (2H, s); MS (m/z) 182 (MC); HRMS calcd for
C11H18O2 (MC): 182.1326, found 182.1303.
4.2.7. 3-Hydroxycyclooctanone (2d). IR (neat) cmK1
:
3420, 1696; 1H NMR (CDCl3) d: 1.23–1.29 (1H, m),
1.46–1.67 (4H, m), 1.80–1.82 (1H, m), 1.84–2.03 (2H, m),
2.33–2.42 (2H, m), 2.66–2.70 (1H, m), 2.78–2.81 (1H, m),
4.05–4.10 (1H, m); MS (m/z) 142 (MC); HRMS calcd for
C8H14O2 (MC): 142.0994, found 142.1001.
Tertiary cyclopropyl silyl ethers and tertiary cyclopropanols
were prepared according to reported methods.1b,8
4.2. General procedure for the syntheses of b-hydroxy
ketones and b-diketones from tertiary cyclopropyl silyl
ethers using vanadyl acetylacetonate
4.2.8. Cycloocta-1,3-dione (3d). IR (neat) cmK1: 1700; 1H
NMR (CDCl3) d: 1.62–1.70 (2H, m), 1.80–1.84 (4H, m),
2.50 (4H, t, JZ6.5 Hz), 3.52 (2H, s); MS (m/z) 140 (MC);
HRMS calcd for C8H12O2 (MC): 140.0837, found
140.0812.
A mixture of a tertiary cyclopropyl silyl ether (or a tertiary
cyclopropanol) (1) (0.50 mmol), vanadyl acetylacetonate
(0.50 mmol or 0.05 mmol) and ethanol (5 ml) was stirred at
room temperature under an oxygen atmosphere for 20 h.
Saturated aqueous sodium bicarbonate (3 ml) was added to
the mixture, and that was then extracted with ethyl acetate
(20 ml !3). The combined organic extracts were washed
with brine, dried over magnesium sulfate, and evaporated
to give a crude mixture of a b-hydroxy ketone (2) and a
b-diketone (3). Separation and purification by column
chromatography (hexane-ethyl acetate) gave pure samples.
4.2.9. 3-Hydroxycyclohexanone (2e). IR (neat) cmK1
:
3420, 1696; 1H NMR (CDCl3) d: 1.66–1.82 (2H, m),
1.99–2.16 (2H, m), 2.31 (2H, t, JZ6.7 Hz), 2.40 (1H, dd,
JZ14.1, 7.5 Hz), 2.65 (1H, dd, JZ14.1, 3.2 Hz), 4.19 (1H,
heptet, JZ3.7 Hz); MS (m/z) 114 (MC); HRMS calcd for
C6H10O2 (MC): 114.0681, found 114.0622.
4.2.1. 3-Hydroxycycloheptanone (2a). IR (neat) cmK1
:
4.2.10. 4-Hydroxybicyclo[5.1.0]octan-2-one (2:1 mixture
3420, 1696; 1H NMR (CDCl3) d: 1.67–1.93 (4H, m), 1.94–
2.03 (2H, m), 2.46–2.56 (2H, m), 2.75–2.83 (2H, m) 4.08–
4.14 (1H, m); MS (m/z) 128 (MC); HRMS calcd for
C7H12O2 (MC): 128.0837, found 128.0840.
1
of stereoisomers) (2f). IR (neat) cmK1: 3405, 1665; H
NMR (CDCl3) d: 1.04–1.19 (1H, m), 1.24–1.38 (1H, m),
1.41–1.54 (1H, m), 1.66–2.37 (5H, m), 2.52–2.71 (2H, m),
3.70–3.78 (2/3H, m), 3.94–3.98 (1/3H, m); MS (m/z) 140
(MC); HRMS calcd for C8H12O2 (MC): 140.0837, found
140.0852.
4.2.2. Cyclohepta-1,3-dione (3a). IR (neat) cmK1: 1670;
1H NMR (CDCl3) d: 1.97–2.04 (4H, m), 2.57–2.60 (4H, m),
3.60 (2H, s); MS (m/z) 126 (MC); HRMS calcd for C7H10O2
(MC): 126.0681, found 126.0685.
4.2.11. Bicyclo[5.1.0]octane-2,4-dione(3f). IR(neat) cmK1
:
1698, 1676; 1H NMR (CDCl3) d: 1.19–1.28 (5H, m), 2.40–
2.52 (3H, m), 3.79 (2H, s); MS (m/z) 138 (MC); HRMS
calcd for C8H10O2 (MC): 138.0681, found 138.0686.
4.2.3. 6-Hydroxy-2-methylcycloheptanone (3:1 mixture
of stereoisomers) (2b). IR (neat) cmK1: 3427, 1694;
1H NMR (CDCl3) d: 1.03 (3H, d, JZ6.8 Hz), 1.36–1.47
(2H, m), 1.56–1.70 (2H, m), 1.89–2.02 (1H, m), 2.39–2.44
(1H, m), 2.60–2.80 (3H, m), 3.96–4.06 (3/4H, m), 4.08–4.16
(1/3H, m); MS (m/z) 142 (MC); HRMS calcd for C8H14O2
(MC): 142.0995, found 142.0994.
4.2.12. 3-Hydroxy-1-phenylpropan-1-one (2g). IR
1
(neat) cmK1: 3422, 1680; H NMR (CDCl3) d: 2.78 (1H,
s), 3.15 (2H, t, JZ5.4 Hz), 3.95 (2H, t, JZ5.4 Hz), 7.36–
7.53 (3H, m), 7.86–7.90 (2H, m); MS (m/z) 150 (MC);
HRMS calcd for C9H10O2 (MC): 150.0681, found
150.0622.
4.2.4. 4-Methylcyclohepta-1,3-dione (3b). IR (neat) cmK1
:
1
4.2.13. 1-Hydroxydodecan-3-one (2h). IR (neat) cmK1
:
1698; H NMR (CDCl3) d: 1.08 (3H, d, JZ6.6 Hz), 1.57–
1.63 (1H, m), 1.89–1.97 (1H, m), 1.98–2.03 (2H, m), 2.44–
2.50 (1H, m), 2.52–2.58 (1H, m), 2.69–2.73 (1H, m), 3.53
(1H, d, JZ15.0 Hz), 3.60 (1H, d, JZ15.0 Hz); MS (m/z)
140 (MC); HRMS calcd for C8H12O2 (MC): 140.0995,
found 140.0994.
1
3381, 1703; H NMR (CDCl3) d: 0.81 (3H, t, JZ6.4 Hz),
1.19–1.28 (14H, m), 2.37 (2H, t, JZ5.3 Hz), 2.60 (2H, t,
JZ5.5 Hz), 3.81 (2H, t, JZ5.5 Hz); MS (m/z) 200 (MC);
HRMS calcd for C12H24O2 (MC): 200.1776, found
200.1781.
4.2.5. 5-t-Butyl-3-hydroxycycloheptanone (2.7:1 mixture
4.2.14. 4-(3-Butenyl)-3-hydroxycycloheptanone (2i). IR
1
1
of stereoisomers) (2c). IR (neat) cmK1: 3420, 1698; H
(neat) cmK1: 3417, 1694; H NMR (CDCl3) d: 1.17–2.36
NMR (CDCl3) d: 0.98 (9H, s), 1.08–1.11 (1H, m), 1.38–1.48
(2H, m), 1.95–2.01 (1H, m), 2.28–2.32 (2H, m), 2.51–2.60
(1H, m), 2.65–2.74 (1H, m), 2.80–2.92 (1H, m), 3.90–3.95
(2.7/3.7H, m), 4.30–4.35 (1/3.7H; MS (m/z) 184 (MC);
(7H, m), 2.83–2.88 (1H, m), 3.36–3.39 (2H, m), 3.43–3.49
(2H, m), 4.23–4.26 (2H, m), 4.92–5.03 (2H, m), 5.72–5.79
(1H, m); MS (m/z) 182 (MC); HRMS calcd for C11H18O2
(MC): 182.1307, found 182.1320.

M. Kirihara et al. / Tetrahedron 61 (2005) 4831–4839
4837
4.2.15. 4-(3-Butenyl)-3-hydroxycycloheptane-1,3-dione
(3i). IR (neat) cmK1: 1697; 1H NMR (CDCl3) d: 1.20–
1.35 (2H, m), 1.58–1.70 (2H, m), 1.75–1.99 (2H, m), 2.00–
2.04 (2H, m), 2.49–2.59 (2H, m), 2.60–2.70 (1H, m), 3.53
(2H, s), 4.94–5.06 (2H, m), 5.65–5.80 (1H, m); MS (m/z)
180 (MC); HRMS calcd for C11H16O2 (MC): 180.1158,
found 180.1150.
(CDCl3) d: 1.26 (3H, s), 1.56–1.74 (6H, m), 2.32–2.52
(3H, br), 2.60 (1H, dd, JZ14.0, 1.7 Hz), 2.83 (1H, d, JZ
13.0 Hz); MS (m/z) 142 (MC); HRMS calcd for C8H14O2
(MC): 142.0994, found 142.1003.
4.4.3. 6-Benzyl-7,8-dioxabicyclo[4.2.1]nonan-1-ol (4k)
Colorless crystals, Mp 89–91 8C (n-hexane–CHCl3); IR
1
4.3. General procedure for the syntheses of 2i and 3i
from 1i using Fe(III) or Mn(II)
(KBr) cmK1: 3346, 2924; H NMR (CDCl3) d: 1.35–1.64
(3H, m), 1.77–2.04 (5H, m), 2.45 (1H, d, JZ13.0 Hz), 2.64–
2.72 (2H, m), 2.88 (2H, d, JZ4.0 Hz), 7.16–7.30 (5H, m);
MS (m/z) 234 (MC); HRMS calcd for C14H18O3 (MC):
234.1256, found 234.1212.
A mixture of the tertiary cyclopropanol (1i) (83.1 mg,
0.50 mmol), iron(III) chloride, iron(III) acetylacetonate or
manganese(II) acetylacetonate (0.05 mmol) and ethanol
(5 ml) was stirred at room temperature under an oxygen
atmosphere for 48 h. Next, saturated aqueous sodium
bicarbonate (3 ml) was added to the mixture, that was
then extracted with ethyl acetate (20 ml !3). The combined
organic extracts were washed with brine, dried over
magnesium sulfate, and evaporated to provide a crude
mixture of 2i and 3i. Separation and purification by column
chromatography (hexane–ethyl acetate) gave pure samples.
4.4.4. 2,6-Dimethyl-7,8-dioxabicyclo[4.2.1]nonan-1-ol
(2:1 mixture of stereoisomers) (4l)
A colorless oil, IR (neat) cmK1: 3447, 2919; 1H NMR
(CDCl3) d: 0.97 (3H!1/3, d, JZ6.6 Hz), 1.04 (3H!2/3, d,
JZ7.1 Hz), 1.30 (3H!2/3, s), 1.32–2.13 (8H, m), 2.22
(1H!1/3, brd, JZ13.0 Hz), 2.43 (1H!2/3, brd, JZ
13.0 Hz), 2.71 (1H!1/3, d, JZ13.0 Hz), 2.86 (1H!2/3,
d, JZ13.0 Hz); MS (m/z) 172 (MC); HRMS calcd for
C9H16O3 (MC): 172.1099, found 172.1052.
4.4. General procedure for the syntheses of b-hydroxy-
ketones and peroxidated compounds from a tertiary
cyclopropyl silyl ethers
4.4.5. 6-Hydroxy-2,6-dimethylcycloheptanone
(4:1 mixture of stereoisomers) (2l)
A mixture of a tertiary cyclopropyl silyl ether (1j, 1k or 1l)
(0.50 mmol), vanadyl acetylacetonate (0.05 mmol), and
either ethanol or 2,2,2-trifluoroethanol (5 ml) was stirred
at room temperature under an oxygen atmosphere for 20 h.
Saturated aqueous sodium bicarbonate (3 ml) was added to
the mixture, that was then extracted with ethyl acetate
(20 ml!3). The combined organic extracts were washed
with brine, dried over magnesium sulfate, and evaporated
to afford a crude mixture of a b-hydroxy ketone and a
peroxidated compound. Separation and purification by
column chromatography (hexane-ethyl acetate) gave pure
samples.
A colorless oil, IR (neat) cmK1: 3853, 2929, 1699; 1H NMR
(CDCl3) d: 1.08 (3H!1/5, d, JZ6.3 Hz), 1.09 (3H!4/5, d,
JZ7.1 Hz), 1.30 (3H!4/5, s), 1.31 (3H!1/5, s), 1.36–2.57
(8H, m), 2.48 (1H!1/5, d, JZ12.0 Hz), 2.62 (1H!4/5, d,
JZ12.0 Hz), 2.85 (1H!4/5, d, JZ12.0 Hz), 2.93 (1H!
1/5, d, JZ13.0 Hz); MS (m/z) 156 (MC); HRMS calcd for
C9H16O2 (MC): 156.1150, found 156.1175.
4.5. General procedure for the syntheses of an ethyl
g-oxocarboxylates from atertiary cyclopropyl silylethers
A mixture containing a tertiary cyclopropyl silyl ether (5)
(0.50 mmol), vanadyl acetylacetonate (0.05 mmol) and
ethanol (5 ml) was refluxed under an oxygen or a nitrogen
atmosphere for 3 h. Next, saturated aqueous sodium
bicarbonate (3 ml) was added to the mixture, that was
then extracted with ethyl acetate (20 ml!3). The combined
organic extracts were washed with brine, dried over
magnesium sulfate, and evaporated to afford the crude
product. Separation and purification by column chromato-
graphy (hexane-ethyl acetate) gave pure samples.
4.4.1. 6-Methyl-7,8-dioxabicyclo[4.2.1]nonan-1-ol (4j).
Colorless crystals, Mp 85–86 8C (n-hexane–CHCl3); IR
(KBr) cmK1: 3354, 2915; 1H NMR (CDCl3) d: 1.30 (3H, s),
1.41–1.49 (1H, m), 1.51–1.74 (2H, m), 1.83–1.93 (4H, m),
1.99–2.03 (1H, m), 2.41 (1H, d, JZ12.0 Hz), 2.79 (1H, d,
JZ12.0 Hz), 3.00–3.34 (1H, br); MS (m/z) 158 (MC);
HRMS calcd for C8H14O3 (MC): 158.0943, found
158.0923. Anal. Calcd for C8H14O3: C, 60.74; H, 8.92.
Found: C, 60.70; H, 8.88.
X-ray crystallographic data for 4j. Colorless prisms,
˚
C8H14O3, MZ158.20, monoclinic, aZ5.665(1) A,
4.5.1. Ethyl 4-oxophenylbutanoate (6a)
˚
˚
bZ23.297(7) A, cZ14.969(5) A, bZ121.71(2)8, VZ
3
1680.8(8) A , space group P21/c (#14), ZZ8, DcZ
A colorless oil, IR (neat) cmK1: 1732, 1687; 1H NMR
(CDCl3) d: 1.20 (3H, t, JZ7.1 Hz), 2.69 (2H, t, JZ7.2 Hz),
3.25 (2H, t, JZ7.2 Hz), 4.11 (2H, q, JZ7.2 Hz), 7.37–7.42
(1H, m), 7.47–7.53 (2H, m), 7.90–7.94 (2H, m); MS (m/z)
206 (MC); HRMS calcd for C12H14O3 (MC): 206.0943,
found 206.0988.
˚
1.25 g cmK3, F(000)Z688.00, m(Mo Ka)Z0.94 cmK1
RZ0.046, RwZ0.064.
,
There are two independent molecules in the asymmetric unit
of 4j.
4.4.2. 3-Hydroxy-3-methylcycloheptanone (2j)
4.5.2. Ethyl 4-oxotridecanoate (6b)
A colorless oil; IR (neat) cmK1: 3854, 2932, 1696; 1H NMR
A colorless oil, IR (neat) cmK1: 1736, 1717; 1H NMR

4838
M. Kirihara et al. / Tetrahedron 61 (2005) 4831–4839
Soc. 1993, 115, 12330–12339. (h) Ryu, I.; Murai, S.; Sonoda, N.
J. Org. Chem. 1986, 51, 2389–2391. (i) Aoki, S.; Fujimura, T.;
Nakamura, E.; Kuwajima, I. J. Am. Chem. Soc. 1988, 110,
3296–3298. (j) Ikura, K.; Ryu, I.; Kambe, N.; Sonoda, N. J. Am.
Chem. Soc. 1992, 114, 1520–1521. (k) Nakahira, H.; Ryu, I.;
Han, L.; Kambe, N.; Sonoda, N. Tetrahedron Lett. 1991, 32,
229–232. (l) Nakahira, H.; Ryu, I.; Ikebe, M.; Oku, Y.; Ogawa,
A.; Kambe, N.; Sonoda, N.; Murai, S. J. Org. Chem. 1992, 57,
17–28.
(CDCl3) d: 0.86 (3H, t, JZ6.6 Hz), 1.19–1.26 (17H, m),
2.42 (2H, t, JZ7.3 Hz), 2.55 (2H, t, JZ6.3 Hz), 2.70 (2H, t,
JZ6.3 Hz), 4.10 (2H, q, JZ6.6 Hz); MS (m/z) 256 (MC);
HRMS calcd for C15H28O3 (MC): 256.2038, found
256.2035.
4.5.3. Ethyl 2-(2-oxocyclohexyl)acetate (6c)
A colorless oil, IR (neat) cmK1: 1734, 1713; 1H NMR
(CDCl3) d: 1.23 (3H, t, JZ7.3 Hz), 1.36–1.83 (4H, m),
2.07–2.15 (2H, m), 2.33–2.40 (2H, m), 2.70–2.88 (3H, m),
4.11 (2H, q, JZ7.3 Hz); MS (m/z) 184 (MC); HRMS calcd
for C10H16O3 (MC): 184.1099, found 184.2033.
3. Specific ‘b’-bond cleavage (a) Ito, Y.; Fujii, S.; Saegusa, T.
J. Org. Chem. 1976, 41, 2073–2074. (b) Lewicka-Piekut, S.;
Okamura, W. H. Synth. Commun. 1980, 10, 415–420.
(c) Blanco, L.; Mansouri, A. Tetrahedron Lett. 1988, 29,
3239–3242. (d) Booker-Milburn, K. I. Synlett 1992, 809–810.
(e) Booker-Milburn, K. I.; Thompson, D. F. Synlett 1993,
592–594. (f) Torii, S.; Okamoto, T.; Ueno, N. J. Chem. Soc.,
Chem. Commun. 1978, 293–294. (g) Iwasawa, N.; Hayakawa,
S.; Isobe, K.; Narasaka, K. Chem. Lett. 1991, 1193–1196.
(h) Iwasawa, N.; Funahashi, M.; Hayakawa, S.; Narasaka, K.
Chem. Lett. 1993, 545–548. (i) Iwasawa, N.; Hayakawa, S.;
Funahashi, M.; Isobe, K.; Narasaka, K. Bull. Chem. Soc. Jpn
1993, 66, 819–827.
4.5.4. Ethyl 2-(2-oxocycloheptyl)acetate (6d)
A colorless oil, IR (neat) cmK1: 1732, 1704; 1H NMR
(CDCl3) d: 1.23 (3H, t, JZ7.0 Hz), 1.28–1.85 (8H, m),
2.23–2.31 (1H, m), 2.37–2.48 (1H, m), 2.57–2.67 (1H, m),
2.74–2.84 (1H, m), 3.03–3.13 (1H, m), 4.80 (2H, q, JZ
7.0 Hz); MS (m/z) 198 (MC); HRMS calcd for C11H18O3
(MC): 198.1256, found 198.1277.
4. Cleavage at both ‘a’ and ‘b’ (a) Rubottom, G. M.; Marrero, R.;
Krueger, D. S.; Schreiner, J. L. Tetrahedron Lett. 1977,
4013–4016. (b) Rubottom, G. M.; Beedle, E. C.; Kim, C.-W.;
Mott, R. C. J. Am. Chem. Soc. 1985, 107, 4230–4233.
(c) Kirihara, M.; Yokoyama, S.; Kakuda, H.; Momose, T.
Tetrahedron Lett. 1995, 36, 6907–6910. (d) Kirihara, M.;
Yokoyama, S.; Momose, T. Synth. Commun. 1998, 28,
1947–1956. (e) Kirihara, M.; Yokoyama, S.; Kakuda, H.;
Momose, T. Tetrahedron 1998, 54, 13943–13954. (f) Momose,
T.; Nishio, T.; Kirihara, M. Tetrahedron Lett. 1996, 37,
4987–4990. (g) Kirihara, M.; Nishio, T.; Yokoyama, S.;
Kakuda, H.; Momose, T. Tetrahedron 1999, 55, 2911–2926.
(h) Kirihara, M.; Shimizu, M.; Yokoyama, S.; Kakuda, H. ITE
Lett. 2003, 3, 215–219.
4.5.5. Ethyl 2-(2-oxocyclooctyl)acetate (6e)
A colorless oil, IR (neat) cmK1: 1732, 1704; 1H NMR
(CDCl3) d: 1.21 (3H, t, JZ7.2 Hz), 1.36–1.87 (10H, m),
2.21–2.33 (2H, m), 2.64–2.73 (1H, m), 2.79–2.89 (1H, m),
3.17–3.28 (1H, m), 4.05 (2H, q, JZ7.2 Hz); MS (m/z) 212
(MC); HRMS calcd for C12H20O3 (MC): 212.1412, found
212.1444.
4.5.6. Ethyl 2-(3-methyl-2-oxocyclohexyl)acetate (6f)
A colorless oil, IR (neat) cmK1: 1737, 1711; 1H NMR
(CDCl3) d: 1.00 (3H, d, JZ6.7 Hz), 1.38–1.91 (6H, m),
1.17–1.26 (3H, m), 2.06–2.23 (2H, m), 2.66–2.79 (1H, m),
2.98–3.04 (1H, m), 4.11 (2H, q, JZ6.7 Hz); MS (m/z) 198
(MC); HRMS calcd for C11H18O3 (MC): 198.1256, found
198.1257.
5. Kirihara, M.; Ichinose, M.; Takizawa, S.; Momose, T. Chem.
Commun. 1998, 1691–1692.
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Rev. 1997, 97, 2707–2724. (b) Takada, T.; Sakurai, H.; Hirao,
T. J. Org. Chem. 2001, 66, 300–302. (c) Hirao, T.; Morimoto,
C.; Takada, T.; Sakurai, H. Tetrahedron Lett. 2001, 42,
1961–1963. (d) Hirao, T.; Morimoto, C.; Takada, T.; Sakurai,
H. Tetrahedron 2001, 57, 5073–5079. (e) Hirao, T.; Takada, T.;
Sakurai, H. Org. Lett. 2000, 2, 3659–3661. (f) Ishikawa, T.;
Nonaka, S.; Ogawa, A.; Hirao, T. Chem. Commun. 1998,
1209–1210. (g) Ishikawa, T.; Ogawa, A.; Hirao, T. J. Am.
Chem. Soc. 1998, 120, 5124–5125. (h) Ishikawa, T.; Ogawa, A.;
Hirao, T. Organometallics 1998, 17, 5713–5716. (i) Hirao, T.;
Asahara, M.; Muguruma, Y.; Ogawa, A. J. Org. Chem. 1998,
63, 2812–2813. (j) Hirao, T. J. Inorg. Biochem. 2000, 80,
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122, 10452–10453. (l) Bolm, C.; Ku¨ehn, T. Synlett 2000,
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N. B.; Hon, S.-W.; Li, T.-W.; Chao, S.-D.; Liu, C.-C.; Li, Y.-C.;
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