Discovery of cationic domino reaction under the NMR experiment conditions: Diastereoselective dimerization of 2-arylmethylideneindolin-3-ones to pentacyclic 3-hydroxyindolenine system

Article abstract of DOI:10.1007/s11172-013-0116-z

NMR spectroscopy (1D and 2D) showed that the protonation of the capto-dative heterocyclic α-amino enones, viz., (Z)-2- arylmethylideneindolin-3-ones, with strong acids led to stable (aryl)(3-hydroxyindol-2-yl)methyl cations. These substrates in trifluoroacetic acid underwent cationic domino reaction, which resulted in polynuclear pyrido[1,2-a: 5,6-b′]-[1,2′]biindoles.

Full text of DOI:10.1007/s11172-013-0116-z

Russian Chemical Bulletin, International Edition, Vol. 62, No. 3, pp. 850—854, March, 2013
850
Discovery of cationic domino reaction under the NMR experiment conditions:
diastereoselective dimerization of 2ꢀarylmethylideneindolinꢀ3ꢀones
to pentacyclic 3ꢀhydroxyindolenine system*
A. S. Peregudov, I. A. Godovikov, I. N. Fedorova, O. V. Istomina, K. A. Lyssenko, and V. S. Velezheva
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 6549. Eꢀmail: asp@ineos.ac.ru
NMR spectroscopy (1D and 2D) showed that the protonation of the captoꢀdative heteroꢀ
cyclic ꢀamino enones, viz., (Z)ꢀ2ꢀarylmethylideneindolinꢀ3ꢀones, with strong acids led to
stable (aryl)(3ꢀhydroxyindolꢀ2ꢀyl)methyl cations. These substrates in trifluoroacetic acid unꢀ
derwent cationic domino reaction, which resulted in polynuclear pyrido[1,2ꢀa : 5,6ꢀb´]ꢀ
[1,2´]biindoles.
Key words: protonation, -amino enones, domino reaction, 3ꢀhydroxyindolenines, Wagꢀ
ner—Meerwein [1,2] sigmatropic rearrangement, pyrido[1,2ꢀa:5,6ꢀb´][1,2´]biindoles.
Studies of reactivity and selectivity of captoꢀdative
aminoalkenes (enamines having, besides the fragment
NR2, a geminal electronꢀwithdrawing group), including
ꢀamino enones, showed not only the prospects of this
approach for the solution of important theoretical probꢀ
lems, but also helped to find new synthetic potential of
this class of compounds.1—4 The unique chemical properꢀ
ties of captoꢀdative aminoalkenes are used in the conꢀ
struction of numerous carboꢀ and heterocyclic systems.5
Recently, several cyclic ꢀamino enones were successfully
used in the synthesis of polycyclic alkaloid hexahydroapoꢀ
erisopin and its analogs.6 An important place among amiꢀ
no enones of similar type is taken by methylideneꢀ and
arylmethylidenequinuclidinꢀ3ꢀones,7—9 as well as by meꢀ
thylideneꢀ and arylmethylideneinꢀ
dolinꢀ3ꢀones of the type 1. The latꢀ
ter exhibit various reactivity: give
the indolinone ring opening and
expansion reactions, the substituꢀ
tion reaction for the vinyl hydrogen
atom with electrophilic and nucleoꢀ
philic agents, the cyclocondensaꢀ
the CN and CF3 groups showed that these compounds
exist only in the Nꢀprotonated form, which upon standing
can convert to the Cꢀprotonated enammonium salt.3—5
gemꢀTrifluoromethylated enamines treated with strong
carboxylic or mineral acids are converted to the products
of both Nꢀ and Cꢀprotonation.16 The formation of the
Cꢀprotonated forms was explained by the prototropic
transformations characteristic of this type of enamines.17,18
The representatives of the heterocyclic series of ꢀamino
enones, viz., arylmethylideneꢀ and ferrocenylmethylideneꢀ
quinuclidinones, are protonated at the nitrogen atom,
and in this case, the latter can also convert to Nꢀ and
Oꢀprotonated dications.7,8,19 The data on the reaction of
indolinones 1 with electrophilic agents are very scarce, howꢀ
ever, the presence of three Cꢀ, Nꢀ, and Oꢀnucleophilic
centers in the structures of these compounds does not
allow one to predict a direction of the electrophilic attack.
Since the protonated forms of indolinones 1 principalꢀ
ly can be used in the synthesis of complex organic moleꢀ
cules, it seems of interest to study the dependence of the
regioselectivity of protonation of indolinones 1 on the naꢀ
ture of the protonating agent and the electron effects of
the aryl substituent. The following acids were chosen as
the protonating agents: AcOH, TFA, and TfOH. The aryl
substituents had either an electronꢀdonating (4ꢀMe) or an
electronꢀwithdrawing (4ꢀCF3) group. NMR spectroscopy
was the main method of study.
tion reactions, as well as the Diels—Alder reaction
with the normal and inverse electron demands.10—15
The various, but hardly predictable reactivity of this type
of heterocyclic ꢀamino enones to a greater extent is
due to their polydentate nucleophilic and electrophilic
character.5
Earlier, the studies of the protonation of acyclic amino
enones R1R2C=C(NR3R4)C(O)R5 and their analogs with
Results and Discussion
Initially, it was found that the dissolution of comꢀ
pounds 1a—c in TFA or TfOH (Scheme 1) resulted in the
* Dedicated to Academician of the Russian Academy of Sciences
I. P. Beletskaya on the occasion of her anniversary.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0849—0853, March, 2013.
1066ꢀ5285/13/6203ꢀ850 © 2013 Springer Science+Business Media, Inc.

Pentacyclic 3ꢀhydroxyindolenines
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
851
changes of chemical shifts of 1H and 13C nuclei (as well as
19F for 1a) in the NMR spectra as compared to chemical
shifts found for compounds 1a—c in solutions in DMSOꢀd6.
The chemical shift changes for atoms C(3) and C(10), as
well as for proton H(10), are the most important for the
analysis of the protonation character (Table 1). Under the
conditions used, the 13C NMR spectrum showed the disꢀ
appearance of the signal for the carbonyl carbon atom at
 187 and the appearance of the signal in the region
 174—176 instead, the signal for atom C(10) shifted
of carbenium cations 2a—c stable at room temperature.
The structure of these cations was confirmed by the data
of NMR experiments (1D and 2D). Also note that the
formation of cations 2a—c only occurred in strong acids,
whereas in weaker acetic acid indolinones 1a—c did not
undergo protonation, which was indicated by the absence
of considerable changes in chemical shifts of the indicaꢀ
tive nuclei in the NMR spectra on going from solutions in
DMSOꢀd6 to solutions in AcOH (see Table 1).
In contrast to orange color of indolinones, their soluꢀ
tions in strong acids are colored in dark violet, that is one
of the evidences of existence of these cations. It should be
noted that after addition of water, the dark violet color of
acidic solutions changes to the yellow immediately or withꢀ
in several hours of standing depending on the substituent,
and the starting indolinones are recovered virtually unꢀ
changed.
1
downfield by more than 20 ppm. In the H NMR specꢀ
trum, the signal for the vinyl proton H(10) also shifted
downfield by 2.0—2.5 ppm. An increase in the shielding of
19F nuclei of the CF3 group by 5 ppm was also indicative.
Scheme 1
Further, we found that the stability of the cations
strongly depends on the nature of protonating agent. The
NMR spectra of the solutions of compounds 1a—c in
TfOH remain virtually unchanged within several days.
Conversely, the storage of the solutions of 1a in TFA in an
NMR tube at room temperature already after 1 h resulted
in the appearance of an additional set of signals in the
1
region of aromatic protons in the H NMR spectrum, as
well as three multiplets for aliphatic protons at  3.37,
4.07, and 5.37. In the 19F NMR spectrum, two lowꢀfield
signal at  –65.46 and –65.86 appeared near the main
signal of the CF3 group at  –66.06. After 24 hours of
storage, these additional signals became predominant.
When the reaction was run on a preparative scale unꢀ
der the same conditions (~20 C, 24 h) with subsequent
treatment of the reaction mixture with water, a new comꢀ
pound was isolated in 67% yield, which appeared to be a
pentacyclic hydroxyindolenine 3a (Scheme 2). The NMR
spectra showed that this compound having four asymmetꢀ
ric centers existed in solution as a single stereoisomer. The
stereochemistry at atoms C(10), C(11), C(12), and C(13)
was determined as (S*), (R*), (R*), and (S*), respectively.
This result was concluded from the NOESY experimental
data: the proton of the OH group ( 7.07) gave crossꢀ
peaks not only with proton orthoꢀCH(8) ( 7.17), but also
with proton CH(11) ( 4.07); the proton CH(13) ( 5.37)
had crossꢀpeaks with orthoꢀprotons CH(24) and CH(28)
( 7.62); protons CH(11) ( 4.07) and CH(12) ( 3.37)
had crossꢀpeaks with orthoꢀprotons of both substituents
4ꢀCF3C6H4; there were no crossꢀpeaks between the orthoꢀ
1, 2: R = CF3(a), H(b), Me(c)
The fact that, as we found in an additional experiment,
in 100% aqueous D2SO4 the vinyl proton H(10) was not
exchanged for deuterium indicated the virtually complete
absence of Cꢀprotonated form. The results obtained allow
us to state that in acidic medium indolinones 1 are selecꢀ
tively protonated at the oxygen atom with the formation
Table 1. Comparative NMR spectral data of indolinones 1a—c
and carbocations 2a—c
Comꢀ
pound
Solvent



F
CF3
C
H
H(10)
C(3)
C(10)
1а
1а
2a
2a
1b
1b
2b
2b
1c
1c
2c
2c
DMSOꢀd6
AcOH
TFA
187.0
187.9
—*
174.9
186.8
188.0
176.4
107.7
109.8
—*
137.0
110.2
113.2
135.7
6.65
6.96
7.55
8.24
6.65
6.95
7.92
8.11
6.62
7.03
7.94
8.11
–61.0
–63.4
–66.1
–66.2
—
—
—
—
—
TfOH
DMSOꢀd6
AcOH
TFA
protons of these substituents (Fig. 1, a). The stereoꢀ
TfOH
174.45 141.88
3
DMSOꢀd6
AcOH
TFA
186.8
187.7
174.3
174.5
110.6
113.6
137.4
141.9
chemistry of indolenine 3a also agrees with the J
1H,1H
—
—
—
values: for the coupling H(11)—H(12) and H(12)—H(13),
3J
= 5.5 and 11.5 Hz, respectively. Thus, it may be
1H,1H
TfOH
concluded that the reaction is chemoꢀ, regioꢀ, and diaꢀ
stereoselective.
The confirmation of the structure of compound 3a was
finalized by the Xꢀray diffraction data. Hydroxyindolꢀ
* Recording of the 13C NMR spectrum of pure cation under the
experimental conditions failed because of its rapid transformaꢀ
tion into the dimeric product 3a (see text).

852
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
Peregudov et al.
Scheme 2
case the equilibrium between the unprotonated and the
protonated forms virtually completely is shifted to the latꢀ
ter. Taking into account the difference in the strength of
acids TFA and TfOH, we assume that both forms are in
the equilibrium in TFA and give the Michael adduct A
(Scheme 3). It can be also suggested that one of the steps
of the domino reaction is the Wagner—Meerwein [1,2]
sigmatropic rearrangement,20,21 which involves the interꢀ
mediate 2ꢀspiropseudoindoxyl B, the product of the intraꢀ
molecular cyclization of adduct A. The postulated mechaꢀ
nism agrees with the fact that for Nꢀmethylated analog 1
no similar reaction is observed.
3: Ar = 4ꢀCF3C6H4 (a), Ph (b), 4ꢀMeC6H4 (c)
enine 3a crystallizes as a solvate with benzene molecules
(Fig. 1, b). The crystal contain three crystallographically
independent molecules, whose geometry and conformaꢀ
tion are indistinguishable within the error limits. The cenꢀ
tral sixꢀmembered ring in the molecule has the distorted
boat conformation with the deviation of atoms C(10) and
C(12) by 0.49 and 0.63 Å, respectively. The hydrogen
atoms at atoms C(12) and C(13) have the antiperiplanar
arrangement, whereas those at atoms C(11) and C(12) the
anticlinal one (the corresponding torsional angles are equal
to 179 and 144). In the crystal, molecules 3a are comꢀ
bined in the centrosymmetric dimers due to the intermoꢀ
lecular hydrogen bonds (the distance N...O 2.764(3) is
2.856(3)Å, the angle NHO is 145—165).
We also observed that substituents in the aryl radical
influenced the readiness of the formation of the dimeric
adduct from carbocation. If for 1a with the electronꢀwithꢀ
drawing substituent 4ꢀCF3, the 1H NMR spectrum showed
the formation of 12% of dimer already within 1 h after the
dissolution in TFA, in the case of unsubstituted 1b the
presence of only 3% of the dimeric compound was obꢀ
served after 4.5 h, and in the case of 1c with the electronꢀ
donating substituent 4ꢀMe, the formation of only 1.5% of
the dimer was observed after 2 days. To sum up, we found
that the decrease in the reactivity of indolinones 1 in the
process of their dimerization is due to the increase in the
stability of cations 2 with the growth of donor properties
of the aryl radical. The NMR spectral data (1D and 2D) of
dimeric products 2b and 2c indicate that their stereochemꢀ
istry is similar to that of compound 1a.
A consideration of the structure of hydroxyindolenine
3a shows that it is formed from two molecules of the startꢀ
ing 1a. The fact that in TfOH indolinones undergo only
protonation, but do not dimerize, indicates that in this
In conclusion, the acidꢀcatalyzed dimerization of inꢀ
dolinones 1 is the first example of the domino reaction, in
F(39)
b
F(40)
C(35)
F(36)
C(26)
C(25)
C(24)
a
F(41)
C(27)
C(28)
C(23)
C(33)
C(31)
F(38)
C(32)
C(34)
C(29)
C(37)
F(42)
C(11)
O(21)
C(12)
C(13)
C(30)
O(22)
C(8)
C(14)
C(15)
C(10)
C(2)
C(9)
C(7)
C(6)
N(1)
C(20)
C(4)
C(16)
C(5)
N(12)
C(19)
C(17)
C(18)
Fig. 1. Stereochemistry of hydroxyindolenine 3a (a) and a general view of one of the independent molecules of compound 3a in
representation of atoms with thermal ellipsoids of vibrations (p = 50%) (b).

Pentacyclic 3ꢀhydroxyindolenines
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
853
Scheme 3
b´][1,2´]biindolꢀ14ꢀone (3a). A cream solid compound, m.p.
209—211 C (from MeOH), the yield was 67%. Found (%):
C, 65.97; H, 3.40; N, 4.65; F, 19.40. C32H22N2O2. Calculated (%):
C, 66.44; H, 3.48; N, 4.84; F, 19.70. 1H NMR, : 3.37 (dd, 1 H,
H(12), JH,H = 11.6 Hz, JH,H = 5.5 Hz); 4.07 (d, 1 H, H(11),
3JH,H = 5.5 Hz); 5.37 (d, H(13), 3JH,H = 11.5 Hz); 6.78 (td, 1 H,
the course of which a complex polycyclic system containꢀ
ing a highly reactive hydroxyindolenine fragment is built
in one step. The ease of the transformation of this fragꢀ
ment was demonstrated on the conversion of hydroxyꢀ
indolenines 3a—c to 2ꢀspiropseudoindoxyls, that will be
the subjects of our further publications. The results obꢀ
tained are of interest for modern organic and medicinal
chemistry, the compounds synthesized are also related to
some alkaloids with indolenine fragment.
3
3
3
4
H(7), JH,H = 7.2 Hz, JH,H = 0.9 Hz); 6.94 (d, 2 H, H(30),
3
3
H(34), JH,H= 7.4 Hz); 7.05 (td, 1 H, H(6), JH,H = 7.4 Hz,
4JH,H = 1.0 Hz); 7.07 (s, 1 H, OH); 7.10 (d, 1 H, H(5), JH,H
= 7.4 Hz); 7.17 (d, 1 H, H(8), JH,H = 7.2 Hz); 7.31 (d, H(2),
H(31), H(33), 3JH,H = 8.0 Hz); 7.35 (t, 1 H, H(17), 3JH,H = 7.4 Hz);
7.61 (d, 2 H, H(24), H(28), 3JH,H = 8.1 Hz); 7.74—7.77 (m, 3 H,
3
=
3
Experimental
3
H(16), H(25), H(27)); 7.96 (td, 1 H, H(18), JH,H = 7.5 Hz,
4JH,H = 1.4 Hz); 8.60 (d, 1 H, H(19), 3JH,H = 8.5 Hz). 13C NMR,
: 49.05, 58.94, 64.90, 82.99, 117.33, 118.05, 122.92, 123.55
(q, 1JC,F = 270.0 Hz), 124.00 (1JC3,F = 270.0 Hz), 124.20, 124.25,
124.33, 124.54, 125.25 (q, 2 C, JC,F = 3 Hz); 125.34, 125.80
(2 C), 127.64 (q, 2JC,F = 31 Hz), 128.01 (q, 2JC,F = 31 Hz), 129.07
(2 C), 130.59 (2 C), 136.22, 138.14, 145.11, 146.19, 151.39,
155.53, 167.28, 196.16. IR (КВr), /cm–1: 3422, 1730, 1623.
MS, m/z: 579 [M]+.
(10R*,11S*,12S*,13R*)ꢀ10ꢀHydroxyꢀ11,12ꢀdiphenylꢀ
11,12,13,14ꢀtetrahydroꢀ10Hꢀpyrido[1,2ꢀa:5,6ꢀb´][1,2´]biindolꢀ
14ꢀone (3b). A cream powder, m.p. 200—202 C (from MeOH).
The yield was 53%. Found (%): C, 81.46; H, 4.79; N, 6.31;
C32H22N2O2. Calculated (%): C, 81.42; H, 5.01; N, 6.33.
1
H and 13C NMR spectra were recorded on an Avance 600
spectrometer (600.22 and 150.92 MHz, respectively). Chemical
shifts in the spectra of compounds 1a—c and 3a—c in DMSOꢀd6
were determined relative to the signal of the solvent, an external
standard DMSOꢀd6 was used to record the spectra in TFA and
TfOH, where chemical shift values were recalculated with reꢀ
spect to Me4Si. The 19F NMR spectra were recorded on an
Avance 400 spectrometer (376.5 MHz); Chemical shifts were
determined with respect to the external standard CFCl3. Mass
spectra were obtained on a Kratos MSꢀ30 instrument (EI, 70 eV).
Thinꢀlayer chromatography was carried out on Silufol F254
plates (Merck); compounds were visualized under UV irradiaꢀ
tion (wavelengths 254 and 365 nm).
3
3
1H NMR, : 3.08 (dd, 1 H, H(12), JH,H = 11.6 Hz, JH,H
=
3
2ꢀArylmethylideneindolinꢀ3ꢀones 1 were synthesized from
1ꢀacetylindolinꢀ3ꢀone and the corresponding aromatic aldehyde
according to the known procedure.22
= 5.2 Hz); 3.90 (d, 1 H, H(11), JH,H = 5.5 Hz): 5.29 (d, 1 H,
H(13), JH,H = 11.6 Hz); 6.66 (d, 2 H, H(30), H(34), JH,H
3
3
=
= 6.7 Hz); 6.75 (td, 1 H, H(7), 3JH,H = 7.4 Hz, 4JH,H = 0.9 Hz);
6.90 (m, 4 H, H(31), H(32), H(33), OH); 7.01 (td, 1 H, H(6),
3JH,H = 7.4 Hz, 4JH,H = 1.2 Hz); 7.06 (d, 1 H, H(5), 3JH,H = 7.6 Hz);
7.16 (d, 1 H, H(8), 3JH,H = 7.1 Hz); 7,35 (m, 6 H, H(17), H(24),
H(25), H(26), H(27), H(28)); 7.73 (d, 1 H, H(16), 3JH,H = 7.6 Hz);
7.94 (td, 1 H, H(18), 3JH,H = 7.6 Hz, 4JH,H = 1.2 Hz); 8.61 (d, 1 H,
19 H). 13C NMR, : 50.34, 59.77, 65.28, 83.19, 117.29, 117.86,
122.70, 124.09, 124.18, 124.21, 124.46, 127.01, 127.25, 128.05
(2 C), 128.37 (2 C), 128.84 (2 C), 129.35, 129.66 (2 C),136.80,
138.06, 141.00, 141.56, 151.39, 155.61, 167.74, 196.27. IR (КВr),
/cm–1: 3639, 1718, 1705, 1626. MS, m/z: 443 [M]+.
Pyrido[1,2ꢀa:5,6ꢀb´][1,2´]biindoles 3 (general procedure).
A solution of indolinone 1a—c (1 mmol) in trifluoroacetic acid
(2—3 mL) was stirred for 45 h at 20—25 C (for 1a,b) or 10 days
(for 1c), then the reaction mixture was poured onto ice. A preꢀ
cipitate formed was filtered off, washed with water to рH 7, and
dried. The crude product obtained was purified from the unreꢀ
acted starting indolinone 1 by passing through a layer of silica gel
(3—5 cm, eluent hexane—ethyl acetate, 2 : 1). The solvent was
evaporated, the residue triturated with diethyl ether, filtered,
and washed with diethyl ether.
(10R*,11S*,12S*,13R*)ꢀ10ꢀHydroxyꢀ11,12ꢀbis(4ꢀtrifluoroꢀ
methylphenyl)ꢀ11,12,13,14ꢀtetrahydroꢀ10Hꢀpyrido[1,2ꢀa:5,6ꢀ
(10R*,11S*,12S*,13R*)ꢀ10ꢀHydroxyꢀ11,12ꢀbis(4ꢀmethꢀ
ylphenyl)ꢀ11,12,13,14ꢀtetrahydroꢀ10Hꢀpyrido[1,2ꢀa:5,6ꢀb´]ꢀ

854
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
Peregudov et al.
[1,2´]biindolꢀ14ꢀone (3c). White powder, m.p.. 205—206 C
(from MeOH), the yield was 32%. Found (%): C, 80.25; H, 5.48;
N, 5.81; C32H22N2O2. Calculated (%): C, 81.68; H, 5.57; N, 5.95.
1H NMR, : 2.01 (s, 3 H, C(37)H3); 2.32 (s, 3 H, C(35)H3); 2.97
(dd, 1 H, H(12), 3JH,H = 11.4 Hz, 3JH,H = 5.0 Hz); 3.82 (d, 1 H,
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Heterocycl. Compd. (Engl. Transl.), 1992, 28, 234].
13. V. S. Velezheva, V. Yu. Marshakov, Khim. Geterotsikl. Soeꢀ
din., 1992, 568 [Chem. Heterocycl. Compd. (Engl. Transl.),
1992, 28, 478].
3
3
H(11), JH,H = 5.0 Hz); 5.22 (d, H(13), JH,H = 11.6 Hz); 6.52
3
(d, 2 H, H(30), H(34), JH,H = 7.7 Hz); 6.70 (d, 2 H, H(31),
H(33), 3JH,H = 7.7 Hz); 6.76 (t, 1 H, H(7), 3JH,H = 7.3 Hz); 6.82
(s, 1 H, OH); 7.02 (t, 1 H, H(6), 3JH,H = 7.3 Hz); 7.07 (d, 1 H,
H(5), 3JH,H = 7.7 Hz); 7.14 (d, 1 H, H(8), 3JH,H= 7.7 Hz); 7.15
3
(d, 2 H, H(25); H(27), JH,H = 7.8 Hz); 7.21 (d, 2 H, H(24),
3
3
H(28), JH,H = 7.7 Hz); 7.32 (t, 1 H, H(17), JH,H = 7.4 Hz);
7.72 (d, 1 H, H(16), 3JH,H = 7.6 Hz); 7.93 (t, 1 H, H(18), 3JH,H
=
= 7.4 Hz); 8.59 (d, 1 H, H(19), JH,H = 8.2 Hz). 13C NMR, :
20.88, 21.20, 50.35, 59.50, 65.33, 83.17, 117.26, 117.89, 122.76,
124.05, 124.10, 124.16, 124,45, 127.90 (2 C), 129.02 (2 C),
129.34, 129.43 (2 C), 129.51 (2 C), 135.77, 136.28, 137.00,
138.04,138.18, 138.51, 151.36, 155.65, 167.87, 196.28. IR (КВr),
/cm–1: 3430, 1725, 1625, 1606. MS, m/z: 471 [M]+.
3
Xꢀray diffraction studies. At 100 K, crystals 3a (C35H23F6N2O2,
–
M = 617.55) triclinic, space group P1, Z = 6 (Z´ = 3);
a = 14.552(7), b = 15.509(8), c = 19.722(8)Å,  = 99.275(9),
 = 99.102(11) g, = 93.788(8), V = 4318(3) Å, Z = 3 (Z´ = 3),
dcalc = 1.425 g cm–3, F(000) = 1902. Intensities of 40223 reflecꢀ
tions were measured on a Bruker APEX IICCD diffractometer
((MoK) = 0.71072Å, ꢀscan technique, 2 < 52), 16982 inꢀ
dependent reflection were used in further refinement. The strucꢀ
ture was solved by direct method and refined by the fullꢀmatrix
least squares method on F2 in anisotropicꢀisotropic approximaꢀ
tion. The hydrogen atoms of the hydroxy groups were localized
from the differential Fourier syntheses, positions of all other
hydrogen atoms were calculated geometrically. All the hydrogen
atoms were refined in isotropic approximation using the riding
model. The final R factor values for compound 3a: wR2 = 0.2214
and GOF = 0.883 for 16980 independent reflections, R1 = 0.0631
calculated on F for 6183 reflections with I > 2(I).
14. J.ꢀY. Merour, L. Chichereau, E. Desarbre, P. Gadonneix,
Synthesis, 1996, 519.
15. A. Buzas, J.ꢀY. Merour, Synthesis, 1989, 458.
16. A. Yu. Rulev, I. A. Ushakov, J. Fluorine Chem., 2010, 131, 53.
17. P. Perez, A. ToroꢀLabbe, Theor. Chem. Acc., 2001, 105, 422.
18. K. Z. Tilyabaev, F. G. Kamaev, A. M. Yuldashev, B. T.
Ibragimov, Zh. Org. Khim., 2012, 48, 948 [Russ. J. Org. Chem.,
2012, 48, 943].
19. V. N. Postnov, A. V. Goncharov, I. Hocke, D. P. Krut´ko,
J. Organomet. Chem., 1993, 456, 235.
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Received December 26, 2012