Synthesis of 3-oxatricyclo[4.4.0.02,7]decene derivatives

Article abstract of DOI:10.1134/S1070428006110078

Unsaturated haloethers of norpinane structure were prepared by reaction of N-iodo-and N-bromosuccinimides with 1-phenyltricyclo[4.1.0.0^2,7]- heptane in the presence of unsaturated propargyl or allyl alcohol. The iodopropargyloxy derivative unde

Full text of DOI:10.1134/S1070428006110078

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 11, pp. 1636−1642.  Pleiades Publishing, Inc. 2006.
Original Russian Text  R.N. Zolotarev, M.E. Yakovlev, V.V. Razin, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42, No. 11,
pp. 1649−1654.
Synthesis of 3-Oxatricyclo[4.4.0.02,7]decene Derivatives
R. N. Zolotarev, M. E. Yakovlev, and V. V. Razin
St. Petersburg State University, St. Petersburg, 198504 Russia
Received December 8, 2005
Abstract—Unsaturated haloethers of norpinane structure were prepared by reaction of N-iodo- and N-bromo-
succinimides with 1-phenyltricyclo[4.1.0.02,7]-heptane in the presence of unsaturated propargyl or allyl alcohol.
The iodopropargyloxy derivative underwent reductive 6-exo-cyclization when treated with tributyltin hydride
resulting in 5-methylene-3-oxa-2-phenyltricyclo[4.4.0.02,7]decane, and the iodoallyloxy derivative on heating in
the presence of benzoyl peroxide suffered isomerization into 5-iodomethyl-3-oxa-2-phenyltricyclo[4.4.0.02,7]decene.
Bromopropargyloxy and bromoallyloxy derivatives failed to undergo the reductive cyclization under the treatment
with a system cobaloxime(III)–sodium borohydride, but suffered hydrogenetion at the multiple carbon–carbon
bond.
DOI: 10.1134/S1070428006110078
In extension of our research directed at application of
tricyclo[4.1.0.02,7]heptane for building up the bridging
system of tricyclo[4.n.0.0]alkane [1] we report on the
present study of a two-stage synthesis of 3-oxa-2-
phenyltricyclo-[4.4.0.02,7]-decene derivatives based on an
available 1-phenyltricyclo[4.1.0.02,7]heptane (I). In the
first stage we planned to perform a conjugate halogenation
of initial hydrocarbon I at the central bicyclobutane C1–
C7 bond by treating with N-bromo(iodo)succinimide in
the presence of unsaturated (propargyl or allyl) alcohol
expecting that the addition would occur regio- and
stereoselective providing the corresponding adducts IIa–
Va, since according to the previously obtained results [2]
hydrocarbon I reacts in the cold with N-bromosuccinimide
in methanol giving in high yields diastereomeric adducts
VIa and VIb in a ratio 15:1.
IIa–Va where the multiple bond and carbon atom attached
to the halogen are spatially close favoring the formation
of a system of 3-oxa-2-phenyltricyclo[4.4.0.02,7]decene.
The reactions of bromo(iodo)propargyloxy(allyloxy)-
lation were carried out in dichloromethane using the
corresponding N-halosuccinimide (NXS) in a slight excess
and the unsaturated alcohol ROH in a large excess with
respect to the initial hydrocarbon I.All reactions took the
expected route and resulted in formation of two-
component mixtures of stereoisomeric products of the
conjugate halogenation IIa, IIb–Va, Vb with a high
degree of anti-stereoselectivity.
The composition of the reaction mixture was analyzed
by 1H NMR spectroscopy, yields and isomers ratio are
presented in the table. The main reaction products
obtained with propargyl alcohol, compounds IIa and IVa,
were isolated by crystallization from methanol, but the
isolation of the main products of reaction with allyl alcohol,
compounds IIIa and Va, required chromatographic
separation on silica gel.As seen from the table, the yields
obtained with propargyl alcohol are higher than with allyl
alcohol*, and the iodination is less stereoselective than
bromination.
In the second stage it was necessary by any method
to carry out a cyclization of the unsaturated haloderivative
R
NXS
ROH
X
O
Ph
X
Ph
1H and 13C NMR spectra were registered from all
compounds IIa, IIb–Va, Vb. The spectral characteristics
Ph
O
R
I
IIa_VIIa
IIb_VIIb
*
Bromoallyloxylation of alkenes using NBS practically failed for
R = CH2Ca”CH (II, IV), CH2CH=CH2 (III, V), CH3 (VI),
CH2CH2CH3 (VII); X = Br (II, III, VI, VII), I (IV, V).
under these conditions the allyl alcohol was converted into
epibromohydrin [6].
1636

SYNTHESIS OF 3-OXATRICYCLO[4.4.0.02,7]DECENE DERIVATIVES
1637
of each of the four stereoisoneris pairs as expected
Yield and stereoselectivity (anti:syn) of conjugate
halogenation of hydrocarbon I
resemble the corresponding spectra of the known
bromides VIa and VIb [2]. The norpinane structure of
the carbon skeleton is reliably confirmed by the 13C NMR
spectra, and the spatial arrangement, by the data of
1H NMR spectra. In particular, the syn-orientation of
the halogen atom in all compounds IIa, IIb–Va, Vb
corresponds to the appearance of a triplet signal (J 6 Hz)
of H7 atom [3], and the assumed configuration at the C6
atom in compounds IIa–VIa is consistent with the high
value of the chemical shift of H7 (~ 5.5 ppm) and with
the upfield shift of the signals of endo-H3 (~ 0.6 ppm)
[2]. The indication of a changed configuration at C6 in
epimers IIb–VIb is a strong upfield shift of the triplet
signal from H7 (~ by 1.2 ppm) and downfield shift of H3
signals to 1.5–2 ppm [2] as compared with epimers IIa–
VIa.
Reaction product
Yield, %
anti:syn (a:b)
58
28
63
32
59
20:1
5:1
7:1
3:1
7:1
IIa, IIb
IIIa, IIIb
IVa, IVb
Va, Vb
VIIa, VIIb
proved to be stable with respect to a system cobal-
oxime(III)–sodium borohydride, and the multiple bonds
underwent hydrogenation. Taking into account that
alkyliodiodides are prone to generation of hydrocarbon
radicals we used for cyclization iodides IVa and Va. To
perform the reductive cyclization of iodide IVa we applied
the widely known method with the use of tributyltin hydride
[7] and obtained a single reduction product, ether VIII.
Apparently in an intermediate stage forms radical A that
further undergoes 6-exo-cyclization resulting in
compound VIII. The structure of compound VIII was
reliably confirmed by 1H and 13C NMR spectra. In the
1H NMR spectrum alongside the multiplet of aromatic
protons appeared two broadened singlets from non-
equivalent olefin protons (5.33 and 5.45 ppm), and
a singlet of protons of OCH2 group (4.18 ppm), and also
signals from the protons of norpinane fragment analogous
to the corresponding signals in the spectra of norpinanes
IIa–VIIa.
To achieve the cyclization of haloderivatives IIa–Va
it was necessary first to perform the homolytic rupture
of the carbon–halogen bond in the initial compound. The
examples of radical cyclization of bromo- and iodo-
derivatives of unsaturated organic compounds are well
known [4]. First we attempted to carry out a cyclization
catalyzed by cobaloxime [5] of the most available for us
bromide IIa and followed the procedure recommended
in [6] for the use with unsaturated vicinal bromoethers.
However the only reaction product was bromide IIIa,
namely, occurred the reduction of a triple bond C≡C into
a double bond. When we carried out the same procedure
with bromide IIIa, the double bond C=C suffered
reduction to give bromide VIIa, identical to the product
of an independent sysnthesis by reaction of hydrocarbon
I with NBS in the presence of propanol. Thus contrary
to expectations the C–Br bond in bromides IIa and IIIa
The other route to building up the system of 3-oxatri-
cyclo[4.4.0.02,7]decene that we succeeded to find was
a radical isomerization of iodide Va initiated by benzoyl
peroxide [8].Apparently first formed radical B that further
Bu3SnH
IVa
Ph
Ph
Ph
(PhCOO)2, PhH, ∆
O
O
O
A
VIII
DBU
(PhCOO)2
PhH, ∆
Ph
Ph
Ph
Va
O
O
O
I
B
IX
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 11 2006

ZOLOTAREV et al.
1638
suffered 6-exo-cyclization. The structure of iodide IX
unambiguously follows from its 1H and 13C NMR spectra.
The 1H NMR spectrum confirms magnetic nonequival-
ence of protons in each methylene group OCH2 and CH2I,
and also of protons H1 and H7 and and methylene groups
C8 and C10 originating from the chirality of C5 atom.
Nonequivalence of C1 and C7 atoms is observed also in
the 13C NMR spectrum, but C8 and C10 more remote
from the chiral center appear as a unique signal.
syn-7-Bromo-exo-6-propargyloxy-6-phenyl-
bicyclo[3.1.1]heptane (IIa). Yield 2.61 g (55%), mp
114–116°C (methanol), Rf 0.47 (eluent hexane–dichloro-
methane, 8:1). IR spectrum, cm–1: 3320 s, 3040 m, 2950 s,
2875 m, 2120 w, 1950 w, 1870 w, 1810 w, 1760 w, 1070 s,
1
1050 s. H NMR spectrum, δ, ppm: 0.45–0.90 m (1H)
and 0.95–1.34 m (1H) – H3; 1.70–2.40 m (4H, H2,4),
2.95 d.t (2H, H1,5, J 6.0 and 1.5 Hz), 2.14 t (1H, J 2.5 Hz)
and 3.61 d (2H, J 2.5 Hz) – OCH2Ca”CH; 5.22 t (1H,
H7, J 6.0 Hz), 7.24 br.s (5H, C6H5). 13C NMR spectrum,
δ, ppm: 12.3 (C3), 25.2 (2C, C2,4), 47.1 (2C, C1,5), 55.3
(C7), 51.6, 73.8 and 80.7 (OCH2Ca”CH), 85.8 (C6), 127.3
(2C), 128.3 (2C), 128.5 and 137.8 (C6H5). Found, %:
C 62.87; H 5.63; Br 25.85. C16H17BrO. Calculated, %:
C 62.96; H 5.62; Br 26.18.
The relation of framework structures VIII and IX as
derivatives of 3-oxatricyclo-[4.4.0.02,7]decene was
proved by conversion of iodide IX into methylene
derivative VIII by dehydroiodination effected with
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
syn-7-Bromo-endo-6-propargyloxy-6-phenyl-
bicyclo[3.1.1]heptane (IIb). Yield 0.14 g (3%), mp 98–
99°C (methanol), Rf 0.57 (eluent – hexane–dichloro-
methane, 8:1). IR spectrum, cm–1: 3320 s, 3040 m, 2950 s,
2875 m, 2120 s, 1950 w, 1870 w, 1810 w, 1760 w, 1125 s,
EXPERIMENTAL
1H and 13C NMR spectra were registered on a spec-
trometer Bruker AM-300 (300 MHz) from solutions in
CDCl3. IR spectra were recorded on a spectrophotom-
eter UR-20 from solutions in CCl4. Elemental analysis
was carried out on a CHN-analyzer HP 185B. TLC was
performed on Silufol UV-254 plates. Preparative column
chromatography was done on silica gel L 40/100
(Chemapol). 1-Phenyltricyclo[4.1.0.02,7]heptane (I) was
prepared by method [2]. Chloro(pyridin)bis-(di-
methylglyoximato)cobalt(III) [cobaloxime(III)] was
obtained by a known procedure [9]. Tributyltin hydride,
diazabicyclo[5.4.0]undec-5-ene, and benzoyl peroxide
were commercial reagents.
1
1070 s, 1050 s. H NMR spectrum, δ, ppm: 1.50–1.85 m
(2H, H3), 1.90–2.40 m (4H, H2,4), 2.98 d.t (2H, H1,5
,
J 6.0 and 1.4 Hz), 2.12 t (1H, J 2.5 Hz) and 3.55 d (2H,
J 2.5 Hz) – OCH2Ca”CH; 4.07 t (1H, H7, J 6.0 Hz),
7.10–7.50 m (5H, C6H5). 13C NMR spectrum, δ, ppm:
13.4 (C3), 24.3 (2C, C2,4), 48.3 (C7), 48.8 (2C, C1,5), 52.7,
73.7 and 79.9 (OCH2C≡CH), 80.2 (C6), 127.6 (2C), 128.2
(2C), 128.8 and 140.2 (C6H5). Found, %: C 62.89; H 5.68;
Br 25.97. C16H17BrO. Calculated, %: C 62.96; H 5.62;
Br 26.18.
By analogous procedure applying allyl alcohol and
propanol we obtained the corresponding bromides IIIa,
IIIb and VIIa, VIIb. The isolation of individual
stereoisomers was performed by column chromatography
on silica gel.
Bromides IIa, IIb, IIIa, IIIb, VIIa, and VIIb. To
a suspension of 3.56 g (20 mmol) of N-bromosuccinimide
in 10 ml of propargyl alcohol and 10 ml of dichloro-
methane was added dropwise within 45 min a solution
of 2.55 g (15 mmol) of hydrocarbon I in 10 ml of dichloro-
methane. The mixture was stirred at room temperature
for 12 h, then 20 ml of 1 N water solution of NaOH was
added, and the products were extracted into
dichloromethane (3×20 ml). The extract was washed with
1 N water solution of NaOH and dried with magnesium
sulfate. The ratio of reaction products IIa and IIb in the
reaction mixture was determined by means of 1H NMR
spectroscopy. The main amount of the major component
of the mixture IIa was isolated by crystallization from
methanol of the residue obtained on removing the solvent.
The mother liquor was subjected to chromatography on
a column charged with silica gel (eluent hexane–
dichloromethane) to isolate the minor component IIb and
additional portion of bromide IIa.
exo-6-Allyloxy-syn-7-bromo-6-phenylbicyclo-
[3.1.1]heptane (IIIa). Yield 23%, mp 38–39°C, Rf 0.65
(eluent hexane–dichloromethane, 8:1). IR spectrum,
cm–1: 3090 m, 3070 m, 3035 m, 2950 s, 2875 s, 1950 w,
1880 w, 1850 w, 1820 w, 1760 w, 1650 m, 1540 m, 1450 s,
1
1205 s, 1070 s, 1050 s. H NMR spectrum, δ, ppm: 0.40–
0.85 m (1H) and 1.05–1.25 m (1H) – H3, 1.70–2.40 m
(4H, H2,4), 3.01 d.t (2H, H1,5, J 6.0 and 1.5 Hz), 3.52 d
(1H, OCH2, J 6.5 Hz), 4.82–5.12 m (2H) and 5.40–
5.90 m (1H) – CH=CH2; 5.16 t (1H, H7, J 6.0 Hz),
7.25 br.s (5H, C6H5). 13C NMR spectrum, δ, ppm: 12.3
(C3), 25.0 (2C, C2,4), 46.8 (2C, C1,5), 55.6 (C7), 64.2
(OCH2), 84.5 (C6), 115.9 and 135.0 (CH=CH2), 127.1
(2C), 127.8 (2C), 128.1 and 138.5 (C6H5). Found, %:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 11 2006

SYNTHESIS OF 3-OXATRICYCLO[4.4.0.02,7]DECENE DERIVATIVES
1639
C 62.63; H 6.27. C16H19BrO. Calculated, %: C 62.55;
H 6.23.
propargyl alcohol and 10 ml of dichloromethane was
added within 25 min a solution of 1.70 g (10 mmol) of
hydrocarbon I in 10 ml of dichloromethane. The mixture
was stirred for 8 h at room temperature, then 20 ml of
10% solution of sodium carbonate was added, and the
reaction products were extracted into dichloromethane
(3×20 ml). The extract was washed in succession by
10% solution of sodium thiosulfate (2×10 ml), with water,
and with saturated NaCl solution, and dried with sodium
sulfate. The ratio of reaction products IVa and IVb in
the reaction mixture was determined by means of
1H NMR spectroscopy. The main amount of the major
component of the mixture IVa was isolated by
crystallization from methanol, and iodide IVb and
additional portion of iodide IVa were obtained by subjecting
the mother liquor to column chromatography on silica gel.
endo-6-Allyloxy-syn-7-bromo-6-phenylbicyclo-
[3.1.1]heptane (IIIb). Yield 4.5%, oily fluid, Rf 0.72
(eluent hexane–dichloromethane, 8:1). IR spectrum,
cm–1: 3070 m, 3050 m, 3015 m, 2920 s, 2875 s, 1950 w,
1880 w, 1850 w, 1820 w, 1760 w, 1650 m, 1540 m, 1450 s,
1
1205 s 1050 s, 950 s. H NMR spectrum, δ, ppm: 1.45–
1.75 m (2H, H3), 1.80–2.35 m (4H, H2,4), 2.96 d.t (2H,
H1,5, J 6.0 and 1.5 Hz), 3.47 d (1H, OCH2, J 6.5 Hz),
4.08 t (1H, H7, J 6.0 Hz), 4.78–5.06 m (2H) and 5.45–
5.82 m (1H) – CH=CH2; 7.05–7.40 m (5H, C6H5).
13C NMR spectrum, δ, ppm: 13.2 (C3), 24.5 (2C, C2,4),
48.3 (2C, C1,5), 48.4 (C7), 65.1 (OCH2), 80.0 (C6), 115.7
and 134.2 (CH=CH2), 126.3 (2C), 127.6 (2C), 128.5 and
141.6 (C6H5). Found, %: C 62.47; H 6.19. C16H19BrO.
Calculated, %: C 62.55; H 6.23.
syn-7-Iodo-exo-6-propargyloxy-6-phenylbicyclo-
[3.1.1]heptane (IVa). Yield 1.97 g (56%), mp 123°C
(methanol), Rf 0.57 (eluent hexane– dichloromethane, 2:1).
1H NMR spectrum, δ, ppm: 0.42–0.78 m (1H) and 0.96–
1.35 m (1H) – H3; 1.81–2.25 m (4H, H2,4), 3.10 d.t (2H,
H1,5, J 6.0 and 1.5 Hz), 2.32 t (1H, J 2.5 Hz) and 3.76 d
(2H, J 2.5 Hz) – OCH2C≡CH; 5.49 t (1H, H7, J 6.0 Hz),
7.15–7.60 m (5H, C6H5). 13C NMR spectrum, δ, ppm:
11.6 (C3), 28.2 (2C, C2,4), 38.9 (C7), 46.5 (2C, C1,5), 51.4,
73.5 and 80.3 (OCH2C≡CH), 85.0 (C6), 126.7 (2C), 128.0
(2C), 128.1 and 137.7 (C6H5). Found, %: C 54.52; H
4.85; I 35.97. C16H17IO. Calculated, %: C 54.56; H 4.86;
I 36.03.
syn-7-Bromo-exo-6-propyloxy-6-phenylbicyclo-
[3.1.1]heptane (VIIa). Yield 51%, oily yellowish fluid,
Rf 0.76 (eluent hexane–dichloromethane, 8:1). IR
spectrum, cm–1: 3070 m, 3040 m, 2950 s, 2880 s, 1950 w,
1880 w, 1810 w, 1760 w, 1600 s, 1450 s, 1290 s, 1200 m,
1
1070 s, 1020 m. H NMR spectrum, δ, ppm: 0.45–0.90
m (1H) and 0.95–1.35 m (1H) – H3; 1.60–2.30 m (4H,
H2,4), 0.72 t (3H, J 7.5 Hz), 1.28 m (2H) and 2.91 t (2H,
J 6.3 Hz) – OCH2CH2CH3; 2.90 d.t (2H, H1,5, J 6.0 and
1.5 Hz), 4.07 t (1H, H7, J 6.0 Hz), 7.0–7.35 m (5H, C6H5).
13C NMR spectrum, δ, ppm: 11.9 (C3), 25.0 (2C, C2,4),
14.5, 31.3 and 49.6 (OCH2CH2CH3), 46.1 (2C, C 1,5),
55.9 (C7), 84.1 (C6), 126.1 (2C), 127.4 (2C), 127.4 and
137.1 (C6H5). Found, %: C 62.15; H 6.84. C16H21BrO.
Calculated, %: C 62.13; H 6.84.
syn-7-Iodo-endo-6-propargyloxy-6-phenyl-
bicyclo[3.1.1]heptane (IVb). Yield 0.25 g (7%),
mp 102°C (methanol), Rf 0.65 (eluent hexane– dichloro-
syn-7-Bromo-endo-6-propyloxy-6-phenylbicyclo-
[3.1.1]heptane (VIIb). Yield 7%, oily yellowish fluid,
Rf 0.82 (eluent hexane–dichloromethane, 8:1). IR
spectrum, cm–1: 3085 m, 3030 m, 2950 s, 2860 s, 1950 w,
1860 w, 1810 w, 1720 w, 1600 s, 1440 s, 1290 s, 1210 m,
1105 s, 1010 m. 1H NMR spectrum, δ, ppm: 1.45–1.70 m
(2H, H3), 1.70–2.30 m (4H, H2,4), 0.77 t (3H, J 7.5 Hz),
1.30 m (2H) and 2.80 t (2H, J 6.2 Hz) – OCH2CH2CH3;
2.95 d.t (2H, H1,5, J 6.0 and 1.5 Hz), 5.11 t (1H, H7,
J 6.0 Hz), 7.20 br.s (5H, C6H5). 13C NMR spectrum, δ,
ppm: 13.1 (C3), 23.7 (2C, C2,4), 15.1, 31.7 and 51.2
(OCH2CH2CH3), 47.7 (2C, C 1,5), 48.7 (C7), 78.9 (C6),
127.2 (2C), 127.3 (2C), 128.2 and 140.5 (C6H5). Found,
%: C 62.22; H 6.90. C16H21BrO. Calculated, %: C 62.13;
H 6.84.
1
methane, 2:1). H NMR spectrum, δ, ppm: 1.55–1.85 m
(2H, H3), 1.90–2.40 m (4H, H2,4), 3.03 d.t (2H, H1,5
,
J 5.8 and 1.4 Hz), 2.33 t (1H, J 2.5 Hz) and 3.68 d (2H,
J 2.5 Hz) – OCH2C≡CH; 4.25 t (1H, H7, J 5.5 Hz),
7.14–7.65 m (5H, C6H5). 13C NMR spectrum, δ, ppm:
12.5 (C3), 26.8 (2C, C2,4), 28.8 (C7), 48.5 (2C, C1,5), 52.3,
73.5 and 79.9 (OCH2C≡CH), 85.0 (C6), 127.3 (2C), 128.0
(2C), 128.5 and 139.7 (C6H5). Found, %: C 54.51;
H 4.84; I 35.94. C16H17IO. Calculated, %: C 54.56;
H 4.86; I 36.03.
By analogous procedure using allyl alcohol we
obtained iodides Va and Vb, and the separation of the
mixture required application of column chromatography
on silica gel.
Iodides IVa, IVb and Va, Vb. To a suspension of
4.50 g (20 mmol) of N-iodosuccinimide in 10 ml of
exo-6-Allyloxy-syn-7-iodo-6-phenylbicyclo-
[3.1.1]heptane (Va). Yield 24%, mp 41°C, Rf 0.68
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 11 2006

ZOLOTAREV et al.
1640
1
(eluent hexane–ether, 10:1). H NMR spectrum, δ, ppm:
0.49–0.72 m (1H) and 1.13–1.34 m (1H) – H3; 2.0–
2.24 m (4H, H2,4), 3.07 d.t (2H, H1,5, J 6.1 and 1.5 Hz),
3.66 d (2H, OCH2, J 6.6 Hz), 5.02–5.23 m (2H) and
5.69–5.84 m (1H) – CH=CH2; 5.47 t (1H, H7, J 6.1 Hz),
7.21–7.45 m (5H, C6H5). 13C NMR spectrum, δ, ppm:
11.7 (C3), 28.1 (2C, C2,4), 38.7 (C7), 46.2 (2C, C1,5), 64.1
(OCH2), 84.1 (C6), 116.2 and 135.5 (CH=CH2), 126.8
(2C), 127.5 (2C), 127.9 and 138.1 (C6H5). Found, %:
C 54.33; H 5.42. C16H19IO. Calculated, %: C 54.25;
H 5.41.
bromoether VIIa was isolated (yield 34%), whose
1H NMR spectrum was identical to the spectrum of the
previously obtained sample of compound VIIa.
Reductive cyclization of iodide IVa. 5-Methylene-
3-oxa-2-phenyltricyclo[4.4.0.02,7]decene (VIII). To
a solution of 0.352 g (1 mmol) of iodide IVa and 0.350 g
(1.2 mmol) of tributyltin hydride in 50 ml of toluene under
an argon atmosphere while stirring and heating (114°C)
was added by portions 0.024 g (0.1 mmol) of benzoyl
peroxide. The reaction progress was monitored by TLC
(reaction time ~2 h). The solvent was evaporated in
a vacuum, the residue was subjected to column chromato-
graphy on silica gel (eluent hexane–ether, 20:1). Yield of
ether VIII 82 mg (36%). Colorless oily fluid, Rf 0.69
endo-6-Allyloxy-syn-7-iodo-6-phenylbicyclo-
[3.1.1]heptane (Vb). Yield 8%, mp 32°C, Rf 0.75 (eluent
– hexane–ether, 10:1). H NMR spectrum, δ, ppm: 1.41–
1
1
(eluent hexane– ether, 10:1). H NMR spectrum, δ, ppm:
1.71 m (2H, H3), 1.86–2.34 m (4H, H2,4), 3.02 d.t (2H,
H1,5, J 6.0 and 1.5 Hz), 3.51 d (1H, OCH2, J 6.5 Hz),
4.87–5.14 m (2H) and 5.73–5.89 m (1H) – CH=CH2;
4.29 t (1H, H7, J 6.0 Hz), 7.01–7.36 m (5H, C6H5).
13C NMR spectrum, δ, ppm: 12.5 (C3), 26.9 (2C, C2,4),
29.0 (C7), 48.1 (2C, C1,5), 65.2 (OCH2), 79.3 (C6), 115.8
and 134.3 (CH=CH2), 126.2 (2C), 127.5 (2C), 128.3 and
141.0 (C6H5). Found, %: C 54.31; H 5.43. C16H19IO.
Calculated, %: C 54.25; H 5.41.
0.51–0.69 m (1H) and 1.04–1.21 m (1H) – H9; 1.91–
2.10 m (4H, H8,10), 2.96 s (1H, H6), 3.12 s (2H, H1,7),
4.18 s (2H, OCH2), 5.34 br.s (1H) and 5.46 br.s (1H) –
C=CH2; 7.24–7.43 m (5H, C6H5). 13C NMR spectrum,
δ, ppm: 11.6 (C9), 29.2 (2C, C8,10), 50.4 (2C, C1,7), 57.6
(C6), 70.2 (C4), 83.9 (C2), 124.1 (CH2=), 133.3 (C5),
125.8 (2C), 127.4 (2C), 128.6 and 138.7 (C6H5). Found,
%: C 84.81; H 8.07. C16H18O. Calculated, %: C 84.91;
H 8.02.
Treatment of bromides IIa and IIIa with the
reagent cobaloxime(III)–sodium borohydride. To
a solution of 31 mg (1 mmol) of bromide IIa in 15 ml of
95% ethanol was added 0.5 g (13 mmol) of sodium
borohydride and 1 ml of 0.1 N alcoholic solution of sodium
hydroxide. Then under an argon atmosphere while stirring
at 50°C was added within 3 h by small portions 90 mg
(0.22 mmol) of cobaloxime(III). On adding to the reaction
mixture of each new portion of catalyst a gas evolution
was observed, and the solvent got darker, but some time
later it turned again colorless.Additionally 0.5 g of sodium
borohydride and 40 mg of cobaloxime(III) was introduced,
and stirring was continued for 2 h. Then the mixture was
diluted with 10 ml of ether and 10 ml of water, the organic
layer was separated, and the reaction products were
extracted from the water layer into ether (3×10 ml). The
extract was dried with magnesium sulfate. The residue
after removal of ether was separated by column
chromatography (eluent hexane–ether, 20:1). Yield of
Izomerization of iodide Va. 5-Iodomethyl-3-oxa-
2-phenyltricyclo[4.4.0.02,7]-decene (IX). To a solution
of 0.354 g (1 mmol) of iodide Va in 50 ml of benzene
under an argon atmosphere was added at heating (80°C)
by portions 0.048 g (0.2 mmol) of benzoyl peroxide within
4 h, and the mixture was stirred till complete conversion
of initial iodide Va (~ 4 h, TLC monitoring). The cooled
reaction mixture was washed with 5% solution of sodium
hydrogen carbonate (3×10 ml) and with water, and dried
with sodium sulfate. On subjecting the product to column
chromatography (eluent hexane– ether, 20:1) we obtained
113 mg (32%) of iodide IX. Colorless oily substance,
1
Rf 0.79 (eluent hexane– ether, 10:1). H NMR spectrum,
δ, ppm: 0.51–0.69 m (1H) and 1.07–1.22 m (1H) – H9;
2.02–2.20 m (2H) and 2.30–2.46 m (2H) – H8,10; 2.55–
2.66 m (1H, H5), 2.92 br.s (1H, H6), 3.04 d.d (1H, J 16
and 4.5 Hz) and 3.14 d.d (1H, J 16 and 6 Hz) – CH2I;
3.22 br.s (1H) and 3.24 br.s (1H) – H1,7; 4.01 d.d (1H,
J 16.5 and 4.5 Hz) and 4.18 d.d (1H, J 16.5 and 10 Hz)
– OCH2; 7.28–7.43 m (5H, C6H5). 13C NMR spectrum,
δ, ppm: 6.6 (CH2I), 11.8 (C9), 28.5 (2C, C8,10), 43.5 (C5),
49.8 and 50.2 (2C, C1,7), 55.7 (C6), 64.8 (C4), 86.8 (C2),
125.0 (2C), 128.1, 128.3 (2C) and 141.2 (C6H5). Found,
%: C 54.35; H 5.46. C16H19IO. Calculated, %: C 54.25;
H 5.41.
1
bromoether IIIa 86 mg (28%). Its H and 13C NMR
spectra were identical to the spectra of the previously
obtained sample of compound IIIa.
By similar procedure bromoether IIIa was treated
with the reagent cobaloxime(III)–sodium borohydride
(reaction time ~ 20 h). By chromatography on silica
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 11 2006

SYNTHESIS OF 3-OXATRICYCLO[4.4.0.02,7]DECENE DERIVATIVES
1641
and Razin, V.V., Mendeleev Commun., 1998, p. 122; Zolota-
rev, R.N. and Razin, V.V., Zh. Org. Khim., 1998, vol. 34,
p. 1863; Razin, V.V. and Zolotarev, R.N., Zh. Org. Khim., 2003,
vol. 39, p. 1782; Zolotarev, R.N. and Razin,V.V., Zh. Org. Khim.,
2003, vol. 39, p. 1788.
2. Razin, V.V., Zadonskaya, N.Yu. and Shamurzaev, Kh.T., Zh.
Org. Khim., 1991, vol. 27, p. 1253.
3. Razin, V.V., Vasyn, V.A., and Blinkov, I.E., Zh. Org. Khim.,
1993, vol. 29, p. 916.
4. Surran, D.P., Synthesis, 1988, p. 417; Jasperse, C.P., Cur-
ran, D.P. and Fevig, T.L., Chem. Rev., 1991, vol. 91, p. 1237.
5. Scheffold, R., Rytz, G., and Walder, L., Modern Synthetic
Methods, vol. 3, Scheffold, R., Ed., Frankfurt: Diesterweg/
Salle, Sauer-lander, 1983, 355 p.; Tada, M. and Okabe, M.,
Chem. Lett., 1980, p. 201; Okabe, M.,Abe, M., and Tada, M.,
J. Org. Chem., 1982, vol. 47, p. 1775; Torii, S., Inokuchi, T.,
and Yukawa, T., J. Org. Chem., 1985, vol. 50, p. 5875; Beg-
ley, M.J., Landlow, M., and Pattenden, G., J. Chem. Soc.,
Perkin Trans. 1, 1988, p. 1095.
Dehydrohalogenation of iodide IX. A mixture of
106 mg (0.3 mmol) of iodide IX and 76 mg (0.5 mmol) of
diazabicyclo[5.4.0]undec-7-ene in 5 ml of 1,2-di-
methoxyethane was heated for 1 h at 80°C. The reaction
mixture was poured into 20 ml of 1 N hydrochloric acid
cooled to 0°C, and it was stirred. From the solution
obtained the reaction product was extracted into hexane
(4×10 ml). The extract was washed in succession with
10 ml of 0.5 N hydrochloric acid, with water (3×5 ml),
and with saturated NaCl solution, and dried with
magnesium sulfate. On subjecting the product to column
chromatography (eluent hexane–ether, 20:1) we obtained
1
52 mg (76%) of ether VIII, whose H and 13C NMR
spectra were identical to the spectra of the sample
previously prepared.
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1. Razin, V.V., Zadonskaya, N.Yu., and Makarychev, Yu.A., Zh.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 11 2006