Reaction of trifluoromethanesulfonamide with alkenes and cycloocta-1,5-diene under oxidative conditions. Direct assembly of 9-heterobicyclo[4.2.1]nonanes

Article abstract of DOI:10.1134/S1070428011090016

Reactions of trifluoromethanesulfonamide with α-methylstyrene, 2-methylpent-1-ene, and cycloocta-1,5-diene in the system t-BuOCl-NaI were studied. In the reaction with α-methylstyrene 1-iodo-2-phenylpropan-2-ol was the only isolated product. The reaction

Full text of DOI:10.1134/S1070428011090016

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 9, pp. 1271–1277. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © M.Yu. Moskalik, B.A. Shainyan, U. Schilde, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 9, pp. 1255–1260.
Reaction of Trifluoromethanesulfonamide with Alkenes
and Cycloocta-1,5-diene under Oxidative Conditions.
Direct Assembly of 9-Heterobicyclo[4.2.1]nonanes
M. Yu. Moskalika, B. A. Shainyana, and U. Schildeb
a Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: bagrat@irioch.irk.ru
b Chemisches Institut der Universität Potsdam, P.O. Box 69 15 53, Potsdam, D-14415 Germany
Received May 5, 2011
Abstract—Reactions of trifluoromethanesulfonamide with α-methylstyrene, 2-methylpent-1-ene, and cyclo-
octa-1,5-diene in the system t-BuOCl–NaI were studied. In the reaction with α-methylstyrene 1-iodo-2-phenyl-
propan-2-ol was the only isolated product. The reaction with 2-methylpent-1-ene gave a mixture of
N,N′-(2-methylpentane-1,2-diyl)bis(trifluoromethanesulfonamide), trifluoro-N-(2-hydroxy-2-methylpentyl)-
methanesulfonamide, and N,N′-[oxybis(2-methylpentan-2,1-diyl)]bis(trifluoromethanesulfonamide). Trifluoro-
methanesulfonamide reacted with cycloocta-1,5-diene to produce a mixture of 2,5-diiodo-9-(trifluoromethyl-
sulfonyl)-9-azabicyclo[4.2.1]nonane and 2,5-diiodo-9-oxabicyclo[4.2.1]nonane; this reaction may be regarded
as the first example of direct assembly of bicyclononane skeleton.
DOI: 10.1134/S1070428011090016
We recently showed that aziridination of styrene
with trifluoromethanesulfonamide in the oxidative
system t-BuOCl–NaI·2H2O leads to formation of both
linear structures I and II and heterocyclization product,
2,5-diphenyl-1,4-bis(trifluoromethylsulfonyl)pipera-
zine (III) [1]. The structure of III was proved by X-ray
analysis, and a mechanism involving intermediate
formation of 2-phenyl-1-trifluoromethylaziridine was
proposed [1]. However, the formation of substituted
piperazine instead of expected aziridine contradicted
the data reported by Minakata et al. [2], according to
which aziridines were obtained in reactions of styrene
and other alkenes with sulfonamides under analogous
conditions due to strong electron-withdrawing effect of
the CF3 group [1]. We tried to reproduce the conditions
described in [2] more accurately and carried out the
reaction of styrene with trifluoromethanesulfonamide
in the presence of anhydrous sodium iodide. In this
case, we isolated compounds I and II and 2,6-di-
phenyl-1,4-bis(trifluoromethylsulfonyl)piperazine (IV)
which is isomeric to III [3].
In the present work we studied reactions of tri-
fluoromethanesulfonamide with α-methylstyrene,
2-methylpent-1-ene, and cycloocta-1,5-diene under
oxidative conditions (in the presence of t-BuOCl–NaI
or t-BuOCl– NaI·2H2O) and analyzed possible ways
of formation of the corresponding products.
Taking into account that α-methylstyrene reacted
with trifluoromethanesulfonamide in a way similar to
styrene [2], i.e., with formation of the corresponding
aziridine, and that the reaction direction strongly
depends on the composition of the oxidative system,
α-methylstyrene (V) was brought into reaction with tri-
fluoromethanesulfonamide in two systems containing
NaI·2H2O or anhydrous NaI (as in [2]). In both cases,
the only product was 1-iodo-2-phenylpropan-2-ol (VI)
(Scheme 1). Compound VI is likely to be formed
via iodination of α-methylstyrene with t-BuOI to
Ph
Ph
H
N
SO2CF3
I
F3CSO2
N
OH
H
I
II
Ph
Ph
SO2CF3
Ph
SO2CF3
N
N
N
N
F3CSO2
F3CSO2
Ph
III
IV
1271

MOSKALIK et al.
1272
[PhC(Me)CH2I]+ and subsequent fast reaction of the
latter with water. This was proved by the formation of
the same product in the absence of trifluoromethane-
sulfonamide.
pattern and afforded 9-(4-methylphenylsulfonyl)-
9-azabicyclo[4.2.1]non-7-ene [4]. Below are given the
results of our study on the reaction of an isolated
diene, cycloocta-1,5-diene (1,5-COD), with trifluoro-
methanesulfonamide in the oxidative system t-BuOCl–
NaI·2H2O.
Scheme 1.
CF3SO2NH2, t-BuOCl
NaI or NaI·2H2O, MeCN
Cycloocta-1,5-diene is known not only as ligand for
complexation with transition metals but also as impor-
tant synthon for design of various carbo- and hetero-
cycles. Electrophilic transannular addition to 1,5-COD
could give rise to bicyclic compounds of three types,
bicyclo[3.3.0]octanes [5], 9-heterobicyclo[3.3.1]-
nonanes [6–11], or mixtures of the latter with isomeric
2,5-disubstituted 9-heterobicyclo[4.2.1]nonanes
[12–25] (Scheme 3). We have found no published data
on the synthesis of fluorinated azabicyclononanes from
1,5-COD.
CH2
HO
Ph
CH2I
Me
Ph
Me
V
VI
With a view to elucidate the effect of the presence
of two geminal substituents in the initial alkene on the
reaction direction, analogous reaction was carried out
with 2-methylpent-1-ene as substrate. Under the above
conditions, we isolated three products VII–IX
(Scheme 2), each containing trifluoromethanesulfon-
amide residues. Unlike the data reported for other sul-
fonamides [2], no aziridines were isolated or identified
in the reaction mixture by spectral methods.
As a first attempt to assemble N-(trifluoromethyl-
sulfonyl)-substituted azabicyclononane skeleton from
1,5-COD we examined its reaction with trifluoro-
methanesulfonamide in the presence of t-BuOCl–
NaI·2H2O. In the reaction with equimolar amounts of
the reactants and 3 equiv of the oxidant we isolated
two compounds which were identified by X-ray anal-
ysis as endo-2,endo-5-diiodo-9-trifluoromethylsul-
fonyl-9-azabicyclo[4.2.1]nonane (X) and endo-2,endo-
5-diiodo-9-oxabicyclo[4.2.1]nonane (XI) (Scheme 4,
see figure).
Aziridination of dienes with sulfonylnitrenes gen-
erated by oxidation of sulfonamides was not reported
previously, though the behavior of a number of linear
and cyclic 1,3-dienes in the reaction with p-methyl-
phenylsulfonylnitrene generated from (4-methyl-
phenylsulfonylimino)phenyl-λ3-iodane (PhI=NTs) was
studied. As a rule, p-methylphenylsulfonylnitrene adds
at only one C=C bond of conjugated diene to give the
corresponding aziridine [4]. The only exception was
the reaction of p-methylphenylsulfonylnitrene with
cycloocta-1,3-diene, which followed the 1,4-addition
Compounds X and XI crystallized in centrosym-
metric point symmetry group, and both enantiomers
were present in crystal. Molecules X and XI have
Scheme 2.
t-BuOCl, NaI·2H2O
MeCN
CH2
Me
F3CSO2NH
Pr
HO
Pr
NHSO2CF3
NHSO2CF3
+
CF3SO2NH2
+
Pr
Me
Me
VIII
VII
F3CSO2
O
SO2CF3
N
N
+
H
H
Pr
Pr
MeMe
IX
Scheme 3.
X
Y
Y
X
Y
Y
Y
Y
Y
Y2
Electrophile
X
Y
X
Y
Y
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 9 2011

REACTION OF TRIFLUOROMETHANESULFONAMIDE WITH ALKENES
1273
Scheme 4.
SO2CF3
N
O
t-BuOCl, NaI·2H2O
MeCN
+
CF3SO2NH2
+
I
I
I
I
X
XI
similar conformations. The pyrrolidine ring in X and
tetrahydrofuran ring in XI adopt envelope conforma-
tion. The seven-membered azepane and oxepane rings,
as well as cyclooctane fragments, have distorted chair
conformation. The iodine atoms occupy quasiaxial and
quasiequatorial positions with respect to the seven-
membered rings. Compound XI resembles its bromo-
substituted analog [26]. By contrast, isomeric 2,6-di-
iodo-9-oxabicyclo[3.3.1]nonane exists in a boat con-
formation [27]. The geometric parameters of mole-
cules X and XI are listed in table.
methylsulfonyl-substituted azabicyclo[4.2.1]nonane-
skeleton.
Selective formation of 9-heterobicyclo[4.2.1]-
nonane skeleton is not consistent with the lower (ac-
cording to the molecular mechanics data [28]) stability
of bicyclo[4.2.1]nonane compared to bicyclo[3.3.1]-
nonane. We performed MP2/6-311G** calculations of
chloro-substituted analogs of compounds X and XI
and their bicyclo[3.3.1]nonane isomers with complete
optimization of geometric parameters [29]. The poten-
tial energy surface of the chloro analog of X contained
endo Orientation of both iodine atoms in molecules
X and XI allowed us to draw some conclusions on the
mechanism of their formation. Presumably, initial reac-
tion of trifluoromethanesulfonamide with t-BuOCl–
NaI · 2 H2O gives intermadiate trifluoro-N-iodo-
methanesulfonamide CF3SO2NHI which reacts with
1,5-COD according to the trans-addition pattern. The
formation of bicyclo[4.2.1]nonane rather than isomeric
bicyclo[3.3.1]nonane skeleton is determined by more
facile attack by the nitrogen atom in intermediate A on
the nearest double-bonded carbon atom (Scheme 5).
F1
C9
(a)
F3
O1
F2
O2
N1
C8
C5
C6
C7
C2
Scheme 5.
I2
H
H
NHSO2CF3
C4
C1
C3
H
I
CF3SO2NHI
H
H
H
I1
H
H
1,5-COD
A
O1
(b)
SO2CF3
H
C7
C1
N
C5
C6
C8
H
I
CF3SO2NHI
H
H
–CF3SO2NH2
C4
I2
C2
C3
I
X
I1
Compound XI is formed via replacement of the
trifluoromethylsulfonylamino group in intermediate A
by hydroxy group, followed by closure of tetrahydro-
furan ring. The formation of compounds X and XI is
the first example of direct assembly of N-trifluoro-
Structures of the molecules of (a) endo-2,endo-5-diiodo-9-
trifluoromethylsulfonyl-9-azabicyclo[4.2.1]nonane (X) and
(b) endo-2,endo-5-diiodo-9-oxabicyclo[4.2.1]nonane (XI)
according to the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 9 2011

MOSKALIK et al.
1274
Selected bond lengths (d) and bond angles (ω) in the mole-
cules of endo-2,endo-5-diiodo-9-trifluoromethylsulfonyl-9-
azabicyclo[4.2.1]nonane (X) and endo-2,endo-5-diiodo-9-
oxabicyclo[4.2.1]nonane (XI)
The reaction of trifluoromethanesulfonamide with
cycloocta-1,5-diene in the system t-BuOCl–NaI·2H2O
demonstrated for the first time direct assembly of
N-(trifluoromethylsulfonyl)-substituted bicyclononane
skeleton and afforded 2,5-diiodo-9-trifluoromethylsul-
fonyl-9-azabicyclo[4.2.1]nonane and 2,5-diiodo-9-oxa-
bicyclo[4.2.1]nonane.
X
XI
Bond
C1–I1
C4–I2
C5–N1
C8–N1
N1–S1
d, Å
Bond
C1–I1
C4–I2
C5–O1
C8–O1
d, Å
2.179(6)
2.179(6)
1.491(7)
1.490(7)
1.589(5)
2.194(5)
2.182(4)
1.444(5)
1.434(6)
EXPERIMENTAL
The IR spectra were recorded on a Bruker
1
Vertex 70 spectrometer. The H, 13C, and 19F NMR
spectra were measured from solutions in CD3CN on
a Bruker DPX 400 spectrometer operating at 400, 100,
and 376 MHz, respectively. The chemical shifts were
determined relative to tetramethylsilane (1H, 13C) or
trichlorofluoromethane (19F). The high-resolution mass
spectra (electrospray ionization, positive ion detection)
of compounds VII and XI were obtained on
a Micromass Q-TOFmicro instrument. X-Ray analysis of
single crystals of compounds X and XI was performed
at 210 K on an STOE Imaging Plate Diffraction
System IPDS-2 (graphite monochromator, MoKα ir-
radiation, λ = 0.71073 nm) with account taken of
Lorentz, polarization, and absorption effects. The
structures were solved by the direct method [30] and
were refined by the full-matrix least-squares procedure
in anisotropic approximation for non-hydrogen atoms
and isotropic approximation for hydrogen atoms [31].
Angle
ω, deg
Angle
ω, deg
C5 N1C8
C1C2C3
C2C3C4
C3C4C5
C4C5C6
C5C6C7
C6C7C8
C7C8C1
C1C2C3C4
C2C3C4C5
C3C4C5C6
C4C5C6C7
C5C6C7C8
C6C7C8C1
C7C8C1C2
C8C1C2C3
110.4(4)
119.2(5)
113.1(5)
116.0(5)
115.5(5)
107.0(4)
107.0(5)
117.1(5)
–75.5(7)
071.1(6)
049.5(7)
–86.5(6)
–16.0(7)
113.3(6)
–69.3(7)
027.8(8)
C5O1C8
C1C2C3
C2C3C4
C3C4C5
C4C5C6
C5C6C7
C6C7C8
C7C8C1
C1C2C3C4
C2C3C4C5
C3C4C5C6
C4C5C6C7
C5C6C7C8
C6C7C8C1
C7C8C1C2
C8C1C2C3
108.8(3)
118.2(4)
111.2(4)
117.0(4)
116.6(4)
104.5(3)
104.7(4)
118.2(4)
–76.7(6)
067.6(5)
055.3(5)
–86.6(5)
–18.0(6)
118.0(5)
–75.0(6)
032.6(7)
Reaction of trifluoromethanesulfonamide with
α-methylstyrene. tert-Butyl hypochlorite, 6.5 g
(0.06 mol), was added dropwise to a mixture of 3 g
(0.02 mol) of trifluoromethanesulfonamide, 2.36 g
(0.02 mol) of α-methylstyrene, and 0.06 mol of NaI or
NaI·2H2O in 100 ml of acetonitrile. The mixture was
stirred for 10 h at –6°C, the solvent was removed
under reduced pressure at room temperature, the resi-
due was dissolved in chloroform, and the solution was
treated with 120 ml of a 0.3 M solution of Na2S2O3,
dried over MgSO4, and evaporated. The liquid residue
(4.8 g) was subjected to column chromatography on
silica gel (0.063–0.200 μm) using hexane as eluent to
remove tarry products, and the residue (3.0 g) was
separated by column chromatography on silica gel
(0.015–0.040 μm) using diethyl ether–hexane (1:2) as
eluent to isolate 1.0 g of unreacted trifluoromethane-
sulfonamide, 0.5 g of alcohol VI, and 0.5 g of tarry
substances which were not analyzed.
two minima corresponding to rotamers with respect to
the N–S bond with different orientations of the tri-
fluoromethyl group. The rotamer with the CF3 group
oriented toward the five-membered ring was more
stable (by 0.7 kcal/mol) than the 180° rotamer but less
stable (by 3.9 kcal/mol) than the [3.3.1] isomer. The
energy difference between the chloro analog of XI and
its [3.3.1] isomer is even smaller, 3.5 kcal/mol. These
data confirm the previous conclusion [19] that more
sterically strained bicyclo[4.2.1]nonanes are kinetically
controlled products, for their formation is accompanied
by smaller distortions of the substrate geometry.
Thus, unlike other sulfonamides, reactions of tri-
fluoromethanesulfonamide with alkenes in the oxida-
tive system t-BuOCl–NaI do not produce aziridines.
1-Iodo-2-phenylpropan-2-ol (VI) [32]. Oily sub-
1
stance. H NMR spectrum, δ, ppm: 1.38 s (3H, CH3),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 9 2011

REACTION OF TRIFLUOROMETHANESULFONAMIDE WITH ALKENES
1275
3.49 s (1H, OH), 3.59 d and 3.64 d (1H each, CH2I, J =
10.4 Hz), 7.27 t (1H, p-H, J = 7.3 Hz), 7.36 t (2H, m-H,
J = 7.7 Hz), 7.47 d (2H, o-H, J = 8.1 Hz). 13C NMR
spectrum, δ, ppm: 23.7 (CH2I), 29.4 (CH3), 73.1
(PhCH), 125.8 (Co), 127.9 (Cp), 128.9 (Cm), 146.5 (Ci).
19F NMR spectrum: δF –77.65 ppm. Found, %:
C 34.18; H 5.69; F 22.29; N 6.05. C7H14F3NO3S. Cal-
culated, %: C 33.73; H 5.66; F 22.87; N 5.62.
N,N′-[Oxybis(2-methylpentane-2,1-diyl)]bis(tri-
fluoromethanesulfonamide) (IX). IR spectrum
(CCl4): ν 3383 cm–1 (NH). 1H NMR spectrum, δ, ppm:
0.95 t (3H, CH2CH3, J = 7.3 Hz), 1.49 m (2H,
CH2CH3), 1.54 s (3H, CCH3), 1.75 m (2H, CCH2),
3.47 m (2H, NCH2), 6.85 br.s (1H, NH). 13C NMR
spectrum, δC, ppm: 14.3 (CH2CH3), 18.3 (CH2CH3),
27.5 (CCH3), 44.0 (CCH2), 55.3 (NCH2), 72.9 (COC),
120.9 q (CF3, J = 320.7 Hz). 19F NMR spectrum:
δF –77.43 ppm.
Reaction of trifluoromethanesulfonamide with
2-methylpent-1-ene. tert-Butyl hypochlorite, 4.4 g
(0.04 mol), was added dropwise to a mixture of 2 g
(13.4 mmol) of trifluoromethanesulfonamide, 1.12 g
(13.4 mmol) of 2-methylpent-1-ene, and 7.4 g
(0.04 mol) of NaI·2H2O in 80 ml of acetonitrile. The
mixture was stirred for 5 h at –6°C, the solvent was
removed under reduced pressure at room temperature,
the residue was dissolved in chloroform, and the
solution was washed with a 0.3 M solution of Na2S2O3,
dried over MgSO4, and evaporated. The liquid residue
(3.8 g) was passed through a column charged with
silica gel (0.063–0.200 μm) using diethyl ether–hexane
(1:2) as eluent to remove tarry products. The colorless
residue (3.0 g) was separated by column chromatog-
raphy on silica gel (0.015–0.040 μm) using diethyl
ether–hexane (1:2) as eluent to isolate 1.8 g (71%) of
compound VII as solid substance and 0.8 g of a liquid
mixture of compounds VIII and IX, which was
separated by preparative thin-layer chromatography on
silica gel using the same eluent. We thus isolated 0.3 g
(9%) of compound VIII and 0.2 g (6%) of IX.
Reaction of trifluoromethanesulfonamide with
cycloocta-1,5-diene. tert-Butyl hypochlorite, 7 g
(65 mmol), was added dropwise to a mixture of 3.3 g
(22 mmol) of trifluoromethanesulfonamide, 2.38 g
(22 mmol) of cycloocta-1,5-diene, and 12 g (65 mmol)
of NaI·2H2O in 100 ml of acetonitrile. The mixture
was stirred for 1.5 h at –10°C, the solvent was
removed under reduced pressure, the residue was dis-
solved in chloroform, and the solution was treated with
a 0.3 M solution of Na2S2O3, dried over CaCl2, and
evaporated. The residue was 6.4 g of a tarry material
which was subjected to column chromatography on
silica gel (63–200 μm) using hexane as eluent to
isolate 3 g of a colorless liquid which was subjected to
repeated chromatography on a column charged with
silica gel (15–40 μm) using hexane as eluent to isolate
1.5 g (14%) of compound X and 0.6 g (7%) of XI as
colorless finely crystalline substances. Single crystals
of X and XI suitable for X-ray analysis were obtained
by crystallization from hexane.
N,N′-(2-Methylpentane-1,2-diyl)bis(trifluoro-
methanesulfonamide) (VII). mp 103–105°C. IR spec-
trum (CCl4), ν, cm–1: 3374, 3290 (NH). 1H NMR spec-
trum, δ, ppm: 0.94 t (3H, CH2CH3, J = 7.2 Hz), 1.36 s
(3H, CCH3), 1.38 m (2H, CH2CH3), 1.57 m (2H,
CCH2), 3.33 d and 3.41 d (1H each, NCH2, J =
13
14.1 Hz), 6.66 br.s (2H, NH). C NMR spectrum, δC,
endo-2,endo-5-Diiodo-9-trifluoromethylsulfonyl-
9-azabicyclo[4.2.1]nonane (X). mp 84–86°C. IR spec-
trum (KBr), ν, cm–1: 2966, 2890, 1640, 1435, 1394,
1363, 1231, 1189, 1159, 1073, 1038, 972, 894, 659,
ppm: 14.2 (CH3CH2), 17.1 (CH3CH2), 21.1 (NCCH3),
41.0 (C2H5CH2), 53.4 (NCH2), 63.0 (NCMe), 120.3 q
(2-CF3, J = 320.3 Hz), 120.9 q (1-CF3, J = 321.0 Hz).
19F NMR spectrum, δF, ppm: –77.23, –77.76. Found:
m/z 380.0299 [M]+. C8H14F6N2O4S2. Calculated:
M 380.0294.
1
605. H NMR spectrum, δ, ppm: 2.29 d.d (2H,
2
2
NCHCH2, J = 14.5 Hz), 2.30 d.d (2H, ICHCH2, J =
8.1 Hz), 2.38 d.d (2H, NCHCH2), 2.56 d.d (2H,
ICHCH2), 4.60 m (4H, NCH, CHI). 13C NMR spec-
Trifluoro-N-(2-hydroxy-2-methylpentyl)-
methanesulfonamide (VIII). IR spectrum (CCl4), ν,
1
trum, δC, ppm: 31.2 (NCHCH2, JCH = 134 Hz), 32.8
(CHI, JCH = 144.5 Hz), 36.4 (ICHCH2, JCH =
1
1
1
cm–1: 3622 (OH), 3390 (NH). H NMR spectrum, δ,
1
134 Hz), 66.9 (CHN, JCH = 153.7 Hz), 120.5 q (CF3,
JCF = 323.1 Hz). 19F NMR spectrum: δF –76.63 ppm.
Found, %: C 21.99; H 2.36; N 2.79; S 6.21.
C9H12F3I2NO2S. Calculated, %: C 21.23; H 2.38;
N 2.75; S 6.30. X-Ray diffraction data: MR = 509.06;
1.00×0.75×0.65-mm single crystal, orthorhombic
ppm: 0.92 t (3H, CH2CH3, J = 7.0 Hz), 1.14 s (3H,
CCH3), 1.36 m (2H, CH2CH3), 1.44 m (2H, CCH2),
2.80 br.s (1H, OH), 3.15 m (2H, NCH2), 6.60 br.s (1H,
NH). 13C NMR spectrum, δC, ppm: 14.9 (CH2CH3),
17.5 (CH2CH3), 24.5 (CCH3), 42.5 (CCH2), 54.1
(NCH2), 72.1 (COH), 121.0 q (CF3, J = 320.1 Hz).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 9 2011

MOSKALIK et al.
1276
10. Stetter, H. and Heckel, K., Chem. Ber., 1973, vol. 106,
crystal system, space group Pbca; a = 9.3600(4), b =
15.1754(5), c = 20.0671(7) Å; V = 2850.37(18) Å3; Z =
p. 339.
8; dcalc = 2.372 g/cm3; μ(MoKα) = 4.59 mm–1; 2Θmax
=
11. Converso, A., Burow, K., Marzinzik, A., Sharp-
less, K.B., and Finn, M.G., J. Org. Chem., 2001, vol. 66,
p. 4386.
49.99°; 16951 reflections, 2496 independent reflections
(Rint = 0.099); R = 0.0384, wR = 0.0859 [I > 2σ(I)].
12. Cope, A.C., McKervey, M.A., and Weinshenker, N.M.,
endo-2,endo-5-Diiodo-9-oxabicyclo[4.2.1]nonane
(XI). mp 76–78°C; published data [6]: mp 81–82°C.
IR spectrum (KBr), ν, cm–1: 2923, 1629, 1472, 1393,
1352, 1284, 1233, 1165, 1125, 1036, 896, 784, 682,
J. Org. Chem., 1969, vol. 34, p. 2229.
13. Ganter, C., Wicker, K., Zwahlen, W., and Schaffner-
Sabba, K., Helv. Chim. Acta, 1970, vol. 53, p. 1618.
14. Toshimitsu, A., Aoai, T., Uemura, S., and Okano, M.,
1
609, 567. H NMR spectrum, δ, ppm: 2.11 d.d (2H,
J. Org. Chem., 1981, vol. 46, p. 3021.
2
2
NCHCH2, J = 5.7 Hz), 2.21 d.d (2H, ICHCH2, J =
7.4 Hz), 2.28 d.d (2H, NCHCH2), 2.41 d.d (2H,
15. Haufe, G. and Kleinpeter, E., Tetrahedron Lett., 1982,
vol. 23, p. 3555.
ICHCH2), 4.64 m (2H, OCH), 4.52 m (4H, ICH).
1
16. Haufe, G., Tetrahedron Lett., 1984, vol. 25, p. 4365.
13C NMR spectrum, δC, ppm: 31.5 (NCHCH2, JCH
=
1
17. Haufe, G., Rolle, U., Kleinpeter, E., Kivikoski, J., and
131.6 Hz), 36.1 (CHI, JCH = 151.9 Hz), 36.5
1
1
Rissanen, K., J. Org. Chem., 1993, vol. 58, p. 7084.
(ICHCH2, JCH = 132.1 Hz), 84.0 (CHO, JCH
=
154.4 Hz). Found: m/z 377.8972 [M]+. C8H12I2O. Cal-
culated: M 377.8967. X-Ray diffraction data: MR =
18. Barluenga, J., Jiménez, C., Nájera, C., and Yus, M.,
J. Chem. Soc., Perkin Trans. 1, 1984, p. 721.
19. Barluenga, J., Jiménez, C., Nájera, C., and Yus, M.,
377.98; 0.45×0.40×0.35-mm single crystal, triclinic
–
J. Heterocycl. Chem., 1984, vol. 21, p. 1733.
crystal system, space group P1; a = 5.1059(8), b =
20. Barluenga, J., Pérez-Prieto, J., Bayón, A.M., and
9.9078(15), c = 10.4345(16) Å; α = 86.063(13), β =
83.479(13), γ = 78.883(12)°; V = 514.01(14) Å3; Z = 2;
Asensio, G., Tetrahedron, 1984, vol. 40, p. 1199.
dcalc. = 2.442 g/cm3; μ(MoKα) = 6.07 mm–1; 2Θmax
=
21. Barluenga, J., Pérez-Prieto, J., Asensio, G., Garcia-
Granda, S., and Salvado, M.A., Tetrahedron, 1992,
vol. 48, p. 3813.
50.00°; 3261 reflections, 1696 independent reflections
(Rint = 0.055); R = 0.0244, wR = 0.0577 [I > 2σ(I)].
22. Davies, S.G., Polywka, M.E.C., and Thomas, S.E.,
This study was performed under financial support
by the Russian Foundation for Basic Research and by
the German Research Society (project nos. 10-03-
00110, 08-03-91954).
Tetrahedron Lett., 1985, vol. 26, p. 1461.
23. Davies, S.G., Polywka, M.E.C., and Thomas, S.E.,
J. Chem. Soc., Perkin Trans. 1, 1986, p. 1277.
24. Chiappe, C. and Ruasse, M.-F., The Chemistry of Dienes
and Polyenes, Rappoport, Z., Ed., Chichester: Wiley,
2000, vol. 2, p. 566.
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