Stereochemistry of dihydroxylation of N-arylbicyclo[2.2.1]-hept-5-ene-endo- and -exo-2,3-dicarboximides

Article abstract of DOI:10.1134/S1070428007110097

Stereochemistry of the oxidation of N-arylbicyclo[2.2.1]hept-5-ene-endo- and-exo-2,3-dicarboximides at the double bond with peroxyacetic acid generated in situ in the presence of sulfuric acid and with an anhydrous dioxane solution of peroxyacetic acid was studied. In both cases, the reaction was stereospecific, regardless of the substituent in the N-aryl group and configuration of the imide ring, but the reaction direction depended on the presence of water in the system. In the first case, the corresponding trans-5,6-dihydroxy derivatives were formed, while in the second, exo-5,6-epoxy derivatives. The oxidation of N-arylbicyclo[2.2.1]-hept-5-ene-endo-and-exo-2,3- dicarboximides with a solution of potassium permanganate in aqueous acetone gave the corresponding N-aryl-cis-5,6-dihydroxybicyclo[2.2.1]heptane-endo-and-exo-2, 3-dicarboximides. The exo,cis,exo and exo,cis,endo configurations of the synthesized compounds were determined by ¹H NMR spectroscopy.

Full text of DOI:10.1134/S1070428007110097

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 11, pp. 1635–1641. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © B.T. Bagmanov, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 11, pp. 1640–1645.
Stereochemistry of Dihydroxylation of N-Arylbicyclo[2.2.1]-
hept-5-ene-endo- and -exo-2,3-dicarboximides
B. T. Bagmanov
Institute of Polymeric Materials, National Academy of Sciences of Azerbaidjan,
ul. S. Vurguna 124, Sumgait, 5004 Azerbaidjan
Received November 18, 2006; revised July 24, 2007
Abstract—Stereochemistry of the oxidation of N-arylbicyclo[2.2.1]hept-5-ene-endo- and -exo-2,3-dicarbox-
imides at the double bond with peroxyacetic acid generated in situ in the presence of sulfuric acid and with
an anhydrous dioxane solution of peroxyacetic acid was studied. In both cases, the reaction was stereospecific,
regardless of the substituent in the N-aryl group and configuration of the imide ring, but the reaction direction
depended on the presence of water in the system. In the first case, the corresponding trans-5,6-dihydroxy
derivatives were formed, while in the second, exo-5,6-epoxy derivatives. The oxidation of N-arylbicyclo[2.2.1]-
hept-5-ene-endo- and -exo-2,3-dicarboximides with a solution of potassium permanganate in aqueous acetone
gave the corresponding N-aryl-cis-5,6-dihydroxybicyclo[2.2.1]heptane-endo- and -exo-2,3-dicarboximides. The
1
exo,cis,exo and exo,cis,endo configurations of the synthesized compounds were determined by H NMR
spectroscopy.
DOI: 10.1134/S1070428007110097
It is known [1−3] that the rate and stereochemistry
of addition reactions at the double bond of norbornene
derivatives strongly depend on the nature of endo and
exo substituents in positions 2 and 3. We previously
showed [4] that oxidation of bicyclo[2.2.1]hept-5-ene-
endo- and -exo-2,3-dicarboxylic anhydrides at the
endocyclic double bond with an anhydrous solution of
peroxyacetic acid in dioxane is strictly stereoselective.
The observed exo-stereoselectivity is determined [5]
by strong steric shielding of the double bond by the
cyclohexene ring having a boat-like conformation, as
compared to the effect of the exo-methylene bridge. If
hydrogen atoms in the methylene bridge of the nor-
bornene fragment are replaced by methyl groups, steric
effect of the syn-CH3 groups forces the oxidation with
peroxy acids to occur at the opposite side to produce
the corresponding endo-epoxy derivatives [6]. How-
ever, the available data are insufficient to rationalize
Scheme 1.
HO
R
R
CH3CO3H, H+/H2O
O
O
N
N
OH
O
O
I–X
XXI–XXX
R
R
O
O
HO
CH3CO3H, H+/H2O
N
N
O
O
OH
XI–XX
XXXI–XL
I, XI, XXI, XXXI, R = H; II, XII, XXII, XXXII, R = o-MeO; III, XIII, XXIII, XXXIII, R = m-MeO; R = IV, XIV, XXIV,
XXXIV, p-MeO; V, XV, XXV, XXXV, R = o-Cl; VI, XVI, XXVI, XXXVI, R = m-Cl; VII, XVII, XXVII, XXXVII, R = p-Cl;
VIII, XVIII, XXVIII, XXXVIII, R = o-HOCO; IX, XIX, XXIX, XXXIX, R = m-HOCO; X, XX, XXX, XL, R = p-HOCO.
1635

BAGMANOV
1636
the effect of substituent configuration in positions 2
and 3 on the reactivity of N-arylbicyclo[2.2.1]hept-
5-ene-endo- and -exo-2,3-dicarboximides I−XX.
Epoxidation of N-arylimides I−XX is stereoselec-
tive. Electrophilic oxygen atom approaches the double
bond from the side of the endo-methylene bridge,
regardless of endo or exo configuration of the imide
fragment. Negative inductive effect of the imide frag-
ment is sufficient to stabilize both epoxide ring and
norbornane skeleton, for the process is not accom-
panied by Wagner−Meerwein rearrangement [11].
In the present work we studied stereochemical
relations holding in the oxidation of N-arylbicyclo-
[2.2.1]hept-5-ene-endo- and -exo-2,3-dicarboximides
I−XX at the double bond with peroxyacetic acid
generated in situ from acetic acid and 30% hydrogen
peroxide in the presence of a catalytic amount of
sulfuric acid. We anticipated formation of stable epoxy
derivatives, taking into account that negative inductive
effect (–I) of the imide carbonyl groups should favor
stabilization of the epoxide ring [7]. However, regard-
less of the substituent in the N-aryl group and imide
ring configuration, the oxidation of imides I−XX at
room temperature led to the formation of the corre-
sponding trans-dihydroxy imides XXI−XL [8]
(Scheme 1). This means that, in contrast to the data of
[9, 10], the initially formed epoxide ring undergoes
fast opening.
The presence of a proton-donor carboxy group in
the N-aryl substituent of compounds VIII and XVIII
does not affect the stability of the oxirane ring and
stereochemistry of epoxidation. A probable reason is
formation of intramolecular hydrogen bond between
strongly electronegative imide carbonyl oxygen atom
and hydroxy proton of the carboxy group in ortho
isomers XLVIII and LVIII. The carboxy group in
para isomers X and XX is unlikely to be involved in
such intramolecular hydrogen bond.
H
O
O
O
O
O
On the other hand, the oxidation of compounds
I−XX with anhydrous peroxyacetic acid in dioxane
gave exo-epoxy derivatives XLI−LX as the only prod-
ucts (Scheme 2). Their acid hydrolysis in aqueous me-
dium leads to trans-dihydroxy compounds XXI−XL,
regardless of the configuration of the imide ring and
the nature and position of substituent in the aromatic
ring. Thus the main factors determining the direction
of oxidation of endo- and exo-imides I−XX with
peroxy acids are the reaction medium and substrate
structure.
O
N
N
O
H
O
O
O
XLVIII
LVIII
The oxidation of imides I−X with a dilute solution
of potassium permanganate in aqueous acetone (neu-
tral medium) at 10°C was strictly stereoselective, and
the products were exclusively the corresponding cis-
dihydroxy derivatives LXI−LXX with exo-oriented
hydroxy groups (Scheme 3). Thus, either cis- or trans-
dihydroxy imides can be obtained, depending on the
conditions.
Scheme 2.
O
The trans configuration of the hydroxy groups in
diols XXI−XL was proved by the presence in their IR
spectra of an absorption band at 3620 cm−1, which is
typical of stretching vibrations of free hydroxy groups
[12]. cis-Diols LXI−LXX displayed bands at 3465,
3480, and 3405 cm−1, which characterize hydroxy
groups involved in intramolecular hydrogen bond.
R
O
CH3CO3H, dioxane
I–X
N
O
XLI–L
R
O
O
The steric structure of the obtained compounds was
CH3CO3H, dioxane
1
XI–XX
confirmed by analysis of their H NMR spectra [13].
N
O
Protons in the bridging methylene group (syn-7-H
and anti-7-H) resonate as a doublet of doublets at
δ 1.25−1.75 ppm (AB spin system, 2J = 10 Hz). The syn-
7-H proton in endo-dihydroxy derivatives XXI−XXX
shows additional long-range W-coupling [14, 15] with
LI–LX
XLI, LI, R = H; XLII, LII, R = o-MeO; XLIII, LIII, R =
m-MeO; R = XLIV, LIV, p-MeO; XLV, LV, R = o-Cl;
XLVI, LVI, R = m-Cl; XLVII, LVII, R = p-Cl; XLVIII,
LVIII, R = o-HOCO; XLIX, LIX, R = m-HOCO; L, LX,
R = p-HOCO.
2-H and 3-H. Its signal is a broadened doublet (W1/2
=
5 Hz) located in a weaker field relative to the anti-7-H
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

STEREOCHEMISTRY OF DIHYDROXYLATION OF N-ARYLBICYCLO[2.2.1]-...
1637
Scheme 3.
O
O
HO
Mn
O
K+
O
R
R
KMnO4, H2O, Me2CO
O
O
HO
I–X
N
N
O
O
A
LXI–LXX
LXI, R = H; LXII, R = o-MeO; LXIII, R = m-MeO; R = LXIV, p-MeO; LXV, R = o-Cl; LXVI, R = m-Cl; LXVII, R = p-Cl;
LXVIII, R = o-HOCO; LXIX, R = m-HOCO; LXX, R = p-HOCO.
molecular ion was present (m/z 255); no ion peaks
with m/z 227 or 198 were observed. These findings
confirm trans and cis configurations of the diols.
signal (W1/2 = 3.5 Hz). These data suggest exo orienta-
tion of 2-H and 3-H and hence endo orientation of the
imide ring. No analogous broadening of the syn-7-H
1
signal is observed in the H NMR spectra of exo-
The presence of hydroxy groups in trans-5,6-di-
hydroxy derivatives XXI−XL was confirmed by their
transformation into the corresponding diacetates
LXXI−XC by treatment with excess acetic anhydride.
Compounds LXXI−XC were also obtained by opening
of the oxirane ring in XLI−LX under similar condi-
tions (Scheme 4).
imides XXXI−XL, which is consistent with the ab-
sence of exo-oriented protons in positions 2 and 3. The
2-H and 3-H signals of exo isomers XXXI−XL are
displaced upfield relative to the corresponding signals
of endo isomers XXI−XXX, in keeping with published
data [15, 16] on the chemical shifts of endo- and exo-
1
protons in norbornane derivatives. In the H NMR
EXPERIMENTAL
spectra of trans-diols XXI−XL, the 5-H and 6-H
signals appear in a stronger field (δ 3.20−3.25 ppm
against δ 6.10−6.55 ppm for initial norbornenes).
The 1H NMR spectra were recorded on a Tesla BS-
487 spectrometer at 80 MHz using CDCl3 as solvent
and hexamethyldisiloxane as internal reference [17].
The IR spectra (400−3800 cm−1) were measured on
a UR-20 instrument from samples dispersed in mineral
oil [12, 18]. The UV spectra were obtained on
a Specord M-40 spectrophotometer. The purity of
the products was checked by TLC on silica gel L (5–
40 μm) [19]; detection under UV light.
The mass spectra of trans-diols XXI−XL contain
strong molecular ion peaks, fragment ion peaks corre-
sponding to loss of one and two water molecules, as
well as strong ion peaks with m/z 227, 198, 173, and
155. Their cis isomers showed in the mass spectra
weak molecular ion peak, but a strong peak resulting
from elimination of one water molecule from the
Scheme 4.
AcO
R
O
Ac2O
Ac2O
XXI–XXX
XLI–L
N
OAc
O
LXXI–LXXX
R
O
AcO
Ac2O
Ac2O
XXXI–XL
LI–LX
N
O
OAc
LXXXI–XC
LXXI, LXXXI, R = H; LXXII, LXXXII, R = o-MeO; LXXIII, LXXXIII, R = m-MeO; R = LXXIV, LXXXIV, p-MeO; LXXV,
LXXXV, R = o-Cl; LXXVI, LXXXVI, R = m-Cl; LXXVII, LXXXVII, R = p-Cl; LXXVIII, LXXXVIII, R = o-HOCO; LXXIX,
LXXXIX, R = m-HOCO; LXXX, XC, R = p-HOCO.
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BAGMANOV
1638
Table 1. Yields, melting points, Rf values, and elemental analyses of N-aryl-trans-5,6-dihydroxybicyclo[2.2.1]heptane-endo-
and -exo-2,3-dicarboximides XXI−XL
Found, %
Calculated, %
Compound Yield,
mp, °C
Rf
Formula
no.
%
C
H
Cl
N
C
H
Cl
N
91
83
85
91
93
95
90
83
91
94
93
92
86
94
97
82
91
81
79
83
199−200 0.69 66.31 5.05
169−170 0.79 64.22 5.91
163−164 0.72 63.67 5.07
184−185 0.60 63.92 5.78
–
–
–
–
6.05
4.83
5.10
4.69
C15H15NO4
C16H17NO5
C16H17NO5
C16H17NO5
66.42 4.79
63.66 5.61
63.66 5.61
63.66 5.61
–
–
–
–
5.17
4.60
4.60
4.60
XXI
XXII
XXIII
XXIV
201−202 0.75 59.01 4.61 12.01 4.72
227−228 0.76 59.42 4.47 11.17 4.92
202−203 0.70 59.13 5.11 12.03 4.52
C15H14ClNO4 58.53 4.55 11.54 4.55
C15H14ClNO4 58.53 4.55 11.54 4.55
C15H14ClNO4 58.53 4.55 11.54 4.55
XXV
XXVI
XXVII
XXVIII
XXIX
225−226 0.86 60.47 4.57
285−287 0.83 60.60 5.19
260−261 0.81 60.79 4.82
202−203 0.60 66.00 4.86
177−178 0.51 62.71 4.79
159−160 0.66 63.44 5.04
206−207 0.59 63.41 5.09
–
–
–
–
–
–
–
4.77
4.76
4.53
4.61
3.99
4.42
4.32
C16H15NO6
C16H15NO6
C16H15NO6
C15H15NO4
C16H17NO5
C16H17NO5
C16H17NO5
60.56 4.73
60.56 4.73
60.56 4.73
66.42 4.79
63.66 5.61
63.66 5.61
63.66 5.61
–
–
–
–
–
–
–
4.41
4.41
4.41
5.17
4.60
4.60
4.60
XXX
XXXI
XXXII
XXXIII
XXXIV
XXXV
XXXVI
XXXVII
XXXVIII
XXXIX
XL
180−181 0.73 57.98 4.43 11.50 4.22
208−210 0.69 57.81 4.47 11.10 3.97
160−161 0.68 57.43 4.50 11.41 4.51
C15H14ClNO4 58.53 4.55 11.54 4.55
C15H14ClNO4 58.53 4.55 11.54 4.55
C15H14ClNO4 58.53 4.55 11.54 4.55
220−222 0.87 60.93 4.81
284−286 0.85 61.11 4.99
261−262 0.79 60.19 4.93
–
–
–
4.72
5.03
4.63
C16H15NO6
C16H15NO6
C16H15NO6
60.56 4.73
60.56 4.73
60.56 4.73
–
–
–
4.41
4.41
4.41
N-Arylbicyclo[2.2.1]hept-5-ene-endo- and exo-2,3-
dicarboximides I−XX were synthesized by the proce-
dure described in [20].
with distilled water, and dried. Yield of trans-diols
XXI−XL 78−90%.
Anhydrous peroxyacetic acid. A flask was
charged with 72 g (1.2 mol) of acetic acid, 22.6 g of
a 30% solution of hydrogen peroxide in dioxane, and
9.5 g (10 wt %) of KU-2 cation exchanger. The mix-
ture was stirred for 3 h at 30°C until complete con-
sumption of hydrogen peroxide and filtered from KU-2
through a Schott filter. The filtrate, 89.7 g, contained
58.8 g of acetic acid, 15.1 g of peroxyacetic acid, and
15.8 g of dioxane. The yield of peroxyacetic acid,
calculated on the hydrogen peroxide taken, was 99.3%;
concentration 16.8%.
N-Aryl-trans-5,6-dihydroxybicyclo[2.2.1]hep-
tane-endo- and -exo-2,3-dicarboximides XXI−XL
(general procedure). a. One or two drops of concen-
trated sulfuric acid was added to a solution of 0.01 mol
of N-aryl imide I−XX in 30 ml of acetic acid, and
a mixture of 10 ml of 30% hydrogen peroxide and
10 ml of acetic acid was added under continuous
stirring. The mixture was heated for 2 h at 70°C, 15 ml
of water was added, and the mixture was heated for
an additional 1 h. When the reaction was complete, the
precipitate was filtered off, washed with water, and
recrystallized from ethanol. The yields, melting points,
Rf values, and elemental analyses of trans-diols
XXI−XL are given in Table 1.
N-Aryl-exo-5,6-epoxybicyclo[2.2.1]heptane-
endo- and -exo-2,3-dicarboximides XLI−LX. A solu-
tion of 0.01 mol of imide I−XX in 15 ml of dioxane
was cooled to 8−10°C, and 10 ml of an anhydrous
solution of peroxyacetic acid in dioxane was added,
maintaining the temperature at 10°C. When peroxy-
acetic acid was consumed completely (3.5−4 h), the
solvent and acetic acid were distilled off under reduced
b. A mixture of 0.01 mol of N-aryl 5,6-exo-epoxy-
bicyclo[2.2.1]heptane-endo- or -exo-2,3-dicarboximide
XLI−LX and 30 ml of 5% sulfuric acid was heated for
4 h at 60°C. The precipitate was filtered off, washed
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STEREOCHEMISTRY OF DIHYDROXYLATION OF N-ARYLBICYCLO[2.2.1]-...
1639
Table 2. Yields, melting points, Rf values, and elemental analyses of N-aryl-exo-5,6-epoxybicyclo[2.2.1]heptane-endo- and
-exo-2,3-dicarboximides XLI−LX
Found, %
Calculated, %
Compound Yield,
mp, °C
Rf
Formula
no.
%
C
H
Cl
–
N
C
H
Cl
–
N
80
87
90
87
90
91
89
87
90
86
89
88
93
88
86
90
94
80
83
87
185−187 0.59 75.01 5.00
4.79
4.80
5.19
5.10
C15H13NO3
C16H15NO4
C16H15NO4
C16H15NO4
74.90 5.09
67.37 5.26
67.37 5.26
67.37 5.26
5.49
4.91
4.91
4.91
XLI
160
154
0.60 67.17 5.16
0.60 67.07 5.30
–
–
XLII
XLIII
XLIV
XLV
XLVI
XLVII
XLVIII
XLIX
L
–
–
164−165 0.54 66.81 5.19
–
–
190−192 0.56 62.43 4.10 12.53 4.67
174−175 0.66 62.12 3.76 12.12 4.19
190−191 0.69 61.12 4.11 12.30 4.89
C15H12ClNO3 62.18 4.14 12.26 4.84
C15H12ClNO3 62.18 4.14 12.26 4.84
C15H12ClNO3 62.18 4.14 12.26 4.84
207−208 00.825 63.62 4.17
241−242 0.78 64.60 3.75
219−220 0.80 64.13 4.33
196−197 0.58 75.12 4.87
170−171 0.50 68.11 4.91
154−155 0.62 68.01 5.35
157−158 0.58 67.40 5.33
–
–
–
–
–
–
–
5.02
4.92
4.19
5.39
5.10
5.19
4.14
C16H13NO5
C16H13NO5
C16H13NO5
C15H13NO3
C16H15NO4
C16H15NO4
C16H15NO4
64.21 4.34
64.21 4.34
64.21 4.34
74.90 5.09
67.37 5.26
67.37 5.26
67.37 5.26
–
–
–
–
–
–
–
4.68
4.68
4.68
5.49
4.91
4.91
4.91
LI
LII
LIII
LIV
172−173 0.63 61.93 3.76 12.13 5.13
190−191 0.67 62.08 4.21 11.78 5.06
162−263 0.66 61.71 4.00 12.10 5.13
C15H12ClNO3 62.18 4.14 12.26 4.84
C15H12ClNO3 62.18 4.14 12.26 4.84
C15H12ClNO3 62.18 4.14 12.26 4.84
LV
LVI
LVII
LVIII
LIX
201−203 0.76 64.10 4.59
235−236 0.80 64.92 4.73
241−243 0.67 63.93 3.89
–
–
–
3.92
4.53
4.99
C16H13NO5
C16H13NO5
C16H13NO5
64.21 4.34
64.21 4.34
64.21 4.34
–
–
–
4.68
4.68
4.68
LX
Table 3. Yields, melting points, Rf values, and elemental analyses of N-aryl-cis-5,6-dihydroxybicyclo[2.2.1]heptane-endo-
and -exo-2,3-dicarboximides LXI−LXX
Found, %
Calculated, %
Compound Yield,
mp, °C
Rf
Formula
no.
%
C
H
Cl
–
N
C
H
Cl
–
N
70.0
60.4
67.5
62.8
75.2
75.0
72.5
60.6
64.5
60.5
207
239
252
255
196
237
218
236
255
265
0.71 66.00 5.42
0.73 63.14 5.25
0.70 63.50 5.37
0.68 63.16 5.39
5.07
4.21
4.12
4.20
C15H15NO4
C16H17NO5
C16H17NO5
C16H17NO5
65.93 5.49
63.37 5.61
63.37 5.61
63.37 5.61
5.13
4.62
4.62
4.62
LXI
–
–
LXII
–
–
LXIII
LXIV
LXV
–
–
0.75 58.40 4.25 11.14 4.31
0.71 58.13 4.09 11.06 4.15
0.74 58.11 4.15 11.12 4.18
C15H14ClNO4 58.53 4.55 11.54 4.55
C15H14ClNO4 58.53 4.55 11.54 4.55
C15H14ClNO4 58.53 4.55 11.54 4.55
LXVI
LXVII
LXVIII
LXIX
LXX
0.68 60.12 4.51
0.70 68.18 4.29
0.80 60.10 4.24
–
–
–
4.37
4.27
4.18
C16H15NO6
C16H15NO6
C16H15NO6
60.56 4.73
60.56 4.73
60.56 4.73
–
–
–
4.41
4.41
4.41
pressure (water-jet pump), and the residue was recrys-
tallized from anhydrous benzene. The yields, melting
points, Rf values, and elemental analyses of com-
pounds XLI−LX are given in Table 2.
N-Aryl-cis-5,6-dihydroxybicyclo[2.2.1]heptane-
endo-2,3-dicarboximides LXI−LXX (general proce-
dure). A solution of 1.6 g of potassium permanganate
in 250 ml of distilled water was added dropwise to
a solution of 0.01 mol of imide I−X in 100 ml of
acetone under vigorous stirring at room temperature.
When potassium permanganate was consumed com-
pletely (the initial pink color disappeared), a dark
brown solid separated (it turned colorless on treatment
with dilute hydrochloric acid). The mixture was left to
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BAGMANOV
1640
Table 4. Yields, melting points, Rf values, and elemental analyses of N-aryl-trans-5,6-diacetoxybicyclo[2.2.1]heptane-endo-
and -exo-2,3-dicarboximides LXXI−XC
Found, %
Calculated, %
Compound Yield,
mp, °C
Rf
Formula
no.
%
C
H
Cl
N
C
H
Cl
N
72
78
80
85
74
70
76
81
71
73
70
69
70
71
77
70
66
72
73
69
174−175 0.66 63.02 4.12
162−164 0.65 63.01 3.99
159−160 0.61 62.16 5.59
132−134 0.58 61.06 5.27
–
–
–
–
4.13 C19H19NO6
3.60 C20H21NO7
4.21 C20H21NO7
4.23 C20H21NO7
63.86 5.32
62.02 5.69
62.02 5.69
62.02 5.69
–
–
–
–
3.92
3.62
3.62
3.62
LXXI
LXXII
LXXIII
LXXIV
LXXV
175−176 0.57 58.19 5.08 1.09 3.58 C19H18ClNO6
146−148 0.65 57.98 5.05 9.72 3.52 C19H18ClNO6
130−132 0.67 57.99 5.67 9.95 3.45 C19H18ClNO6
58.23 4.59 9.06 3.57
58.23 4.59 9.06 3.57
58.23 4.59 9.06 3.57
LXXVI
LXXVII
LXXVIII
LXXIX
LXXX
185−186 0.77 59.02 4.81
194−195 0.71 59.66 4.65
186−188 0.74 60.11 4.95
175−176 0.53 63.19 4.93
163−164 0.48 61.75 5.33
140−141 0.60 61.90 4.97
163−164 0.51 62.10 5.81
–
–
–
–
–
–
–
3.12 C20H19NO8
3.37 C20H19NO8
3.14 C20H19NO8
3.42 C19H19NO6
3.47 C20H21NO7
3.59 C20H21NO7
3.17 C20H21NO7
59.99 4.74
59.99 4.74
59.99 4.74
63.86 5.32
62.02 5.69
62.02 5.69
62.02 5.69
–
–
–
–
–
–
–
3.49
3.49
3.49
3.90
3.62
3.62
3.62
LXXXI
LXXXII
LXXXIII
LXXXIV
LXXXV
LXXXVI
LXXXVII
LXXXVIII
LXXXIX
XC
146−147 0.65 58.41 4.60 8.81 3.41 C19H18ClNO6
170−172 0.66 58.22 4.19 9.23 3.43 C19H18ClNO6
136−137 0.57 57.47 4.37 8.95 3.32 C19H18ClNO6
58.23 5.69 9.06 3.57
58.23 4.59 9.06 3.57
58.23 4.59 9.06 3.57
171−173 0.74 59.60 4.63
210−211 0.71 60.01 4.68
200−202 0.64 59.57 5.08
–
–
–
3.31 C20H19NO8
3.47 C20H19NO8
3.57 C20H19NO8
59.99 4.74
59.99 4.74
59.99 4.74
–
–
–
3.49
3.49
3.49
3. Kas’yan, L.I., Okovityi, S.I., Bombushkar’, M.F., and
Dryuk, V.G., Russ. J. Org. Chem., 2000, vol. 36, p. 195;
Kas’yan, L.I., Krishchik, O.V., Tarabara, I.N., Kas’-
yan, A.O., and Pal’chikov, V.A., Russ. J. Org. Chem.,
2006, vol. 42, 501.
4. Bagmanova, M.I., Bagmanov, B.T., and Umaeva, V.S.,
Abstracts of Papers, Konferentsiya “Tonkii organiche-
skii sintez i kataliz” (Conf. “Fine Organic Synthesis and
Catalysis”), Baku, 1999, p. 47.
stand for 12 h, and the precipitate was filtered off and
recrystallized from methanol. The yields, melting
points, Rf values, and elemental analyses of cis-diols
LXI−LXX are given in Table 3.
N-Aryl-trans-5,6-diacetoxybicyclo[2.2.1]heptane-
endo- and -exo-2,3-dicarboximides LXXI−XC (gen-
eral procedure). A mixture of 0.1 mol of trans-5,6-diol
XXI−XL or 5,6-epoxy derivative XLI−LX, KU-2
cation exchanger (H-form, 40% of initial reactant mix-
ture), and 35 ml of acetic anhydride was heated for 6 h.
When the reaction was complete, the mixture was
filtered from KU-2, and crystals precipitated from the
filtrate were were filtered off, washed with distilled
water, and dried. The yields, melting points, Rf values,
and elemental analyses of diacetates LXXI−XC are
given in Table 4.
5. Malinovskii, M.S., Khim. Geterotsikl. Soedin., 1974,
p. 29.
6. Vereshchagin, A.N., Anastas’eva, A.P., and Arbu-
zov, B.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1970,
p. 995.
7. Salakhov, M.S. and Bagmanova, M.I., Russ. J. Org.
Chem., 2002, vol. 38, p. 244.
8. Bagmanov, B.T., Abstracts of Papers, Konferentsiya
molodykh uchenykh po probleme “Monomery
i
polimery” (Conf. of Young Scientists on the Problem
“Monomers and Polymers”), Sumgait, 1985, p. 5.
9. Meinwald, J., Nozaki, H., and Wiley, G.A, J. Am. Chem.
Soc., 1957, vol. 79, p. 5579.
REFERENCES
1. Nazarov, I.N., Kucherov, V.F., and Bukharov, V.G., Izv.
Akad. Nauk SSSR, Otd. Khim. Nauk, 1959, p. 328.
2. Yur’ev, Yu.K. and Zefirov, N.S., Zh. Obshch. Khim.,
10. Organic Reactions, Adams, R., Ed., New York: Wiley,
1961, vol. 31, p. 840.
1954, vol. 8.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

STEREOCHEMISTRY OF DIHYDROXYLATION OF N-ARYLBICYCLO[2.2.1]-...
1641
11. Sapunov, V.N. and Lebedev, N.N., Zh. Obshch. Khim.,
16. Henbest, H. and Nickels, B., J. Chem. Soc., 1959,
1966, vol. 36, p. 273.
vol. 86, p. 221.
12. Kazitsyna, L.A. and Kupletskaya, N.B., Primenenie
UF-, IK-, YaMR- i mass-spektroskopii v organicheskoi
khimii (Application of UV, IR, NMR, and Mass
Spectroscopy in Organic Chemistry), Moscow: Mosk.
Gos. Univ., 1978.
17. Bhacca, N.S. and Williams, D.H., Applications of NMR
Spectroscopy in Organic Chemistry. Illustrations from
the Steroid Field, San Francisco: Holden-Day, 1964.
Translated under the title Primenenie YaMR v organi-
cheskoi khimii, Moscow: Mir, 1966, pp. 151, 207.
13. Samitov, Yu.Yu., Atlas spektrov yadernogo magnitnogo
rezonansa prostranstvennykh izomerov (Atlas of
Nuclear Magnetic Resonance Spectra of Stereoisomers),
Kazan: Kazan. Gos. Univ., 1978, vol. 1, p. 120.
18. Gordon, A.J. and Ford, R.A., The Chemist’s Com-
panion, New York: Wiley, 1972. Translated under the
title Sputnik khimika, Moscow: Mir, 1976, p. 285.
19. Akhrem, A.A. and Kuznetsova, A.I., Tonkosloinaya khro-
matografiya (Thin-Layer Chromatography), Moscow:
Nauka, 1965.
14. Walborsky, H. and Loucrini, G., J. Am. Chem. Soc.,
1954, vol. 76, p. 5396.
15. Kwart, H. and Loucrini, G., J. Am. Chem. Soc., 1954,
20. Salakhov, M.S., Musaeva, N.F., Suleimanov, S.N., and
vol. 76, p. 5400.
Bairamov, A.A., Zh. Org. Khim., 1979, vol. 15, p. 2326.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007