Efficient synthesis and structure peculiarity of macrocycles with bi-indolizinylquinoxalinone moieties

Article abstract of DOI:10.1016/j.tet.2013.09.014

Monoindolizinylquinoxalinepodands, easily available from indolizinylquinoxalines and various dihalides, undergo smooth oxidative dimerization in the presence of molecular iodine to afford corresponding macrocycles in good yields in a short reaction time.

Full text of DOI:10.1016/j.tet.2013.09.014

Tetrahedron 69 (2013) 10675e10687
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Tetrahedron
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Efficient synthesis and structure peculiarity of macrocycles with
bi-indolizinylquinoxalinone moieties
*
Vakhid A. Mamedov , Aleksey A. Kalinin, Aidar T. Gubaidullin, Sergey A. Katsuba,
Victor V. Syakaev, Il’dar K. Rizvanov, Shamil K. Latypov
A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center of the Russian Academy of Sciences, Arbuzov Str. 8, 420088 Kazan,
Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 2 July 2013
Received in revised form 19 August 2013
Accepted 3 September 2013
Available online 11 September 2013
Monoindolizinylquinoxalinepodands, easily available from indolizinylquinoxalines and various dihalides,
undergo smooth oxidative dimerization in the presence of molecular iodine to afford corresponding
macrocycles in good yields in a short reaction time. The use of inexpensive and readily available mo-
lecular iodine makes this method quite simple, more convenient, and practical. In solution the title
macrocycles exist in an equilibrium of several conformations arising from restricted rotation around the
IndeQx bonds (ca. C2 symmetrical and nonsymmetrical forms). The population of the forms and ex-
change rate between them depends strongly on the spacer type (length).
Keywords:
Oxidative dehydrogenation
Monoindolizinylquinoxalinepodands
Molecular iodine
Ó 2013 Elsevier Ltd. All rights reserved.
Ring closure
Biindolizinacyclophanes
X-ray diffraction analysis
IR data
NMR data
1. Introduction
have been developed only with electron donating groups in good
yields, despite the use of various dehydrating agents, such as
Recently, in connection with the creation of various electro-
switched (electrochemically switched, redox-switched) nano-
dimensional molecular devices, special attention has been paid to
supramolecular systems based on macrocyclic compounds con-
taining electrochemically active building blocks. A biindolizine
fragment that can impart the ability to react to the external in-
fluences of heterocyclophanes has so far been little used,16e18 as an
active site, unlike ferrocenes,1 tetratiofulvalens,2e7 and quater-
nized-4,40 dipyridyl,6e9 hydroquinone,9,10 anilines,11,12 phenazine,13
thiophenes.13e15 This is probably due to the difficulty of introducing
the indolizine fragment into macrocyclic systems of different sizes
synthetically. It is also difficulty to perform the indolizi-
ne/biindolizine transformation in the presence of a common ac-
ceptor or heteroaryl substituents in the composition of
indolizines.16,19,20 3,30-Biindolizines are reversible two-step redox
systems of theoretical and practical interest, which have attracted
attention as a structural unit of cyclophanes16e18 and as chiral
ligands.21e23 So far the methods used to synthesize biindolizines
K3[Fe(CN)6],24 Pd/C,19,25e28 Pt/C19 Fe (III)/O2,20 and electrochemi-
cally as well.20,29 Indolizines with acceptor substituents are either
unable to oxidize at all,19 or the yields were very low16,20 as in the
cases of the heteroaryl substitutes of biindolizines. Recently, a new
method for the oxidative dimerization of indolizines when exposed
18
to Pd(OAc)2 has been developed to produce high yields of biin-
dolizines including acceptor substituents. At present, molecular
iodine has received considerable attention in organic synthesis
because of its low cost and ready availability. The mild Lewis acidity
associated with iodine has enhanced its use in organic synthesis to
perform several organic transformations with stoichiometric levels
to catalytic amounts.18,30e34 However, so far no examples are
known in which molecular iodine was used as a mild oxidant for
the transformation of the indolizine/biindolizine. Nevertheless, it
should be noted that recently molecular iodine has been used as an
excellent reagent-catalyst in the synthesis of the indolizine de-
rivatives by 5-endo-dig cyclization.35,36 In our previous paper37 the
molecular iodine and the binary system of the molecular iodine and
the NaOAc (I2eNaOAc) mediated one-pot process for the oxidative
dimerization of indolizines under mild conditions have been de-
scribed. The reaction afforded a variety of products from indolizines
* Corresponding author. Tel.: þ7 843 2727304; fax: þ7 843 2732253; e-mail
address: mamedov@iopc.ru (V.A. Mamedov).
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.09.014

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V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
with acceptor groups in good to excellent yields. Macrocyclic sys-
tems with the biindolizine fragment(s) connected with 3-
oxapentane, 3,6,9-trioxaundecane, 3,6,9,12-tetraoxatetradecane
macrocyclic systems with various crown ether residues, as well as
the study of structural peculiarities of some obtained compounds.
Initially, we attempted the oxidative dimerization of readily
available indolizinylquinoxalines 1a,b with the use of molecular
iodine as a dehydrogenating reagent and the products, 2a and 2b
were isolated in 92 and 70% yields, respectively (Table 1).
This result provided the incentive for further study of the me-
diated dehydrogenation with monoindolizinylquinoxalinepodands
4aej, which are easily available by the interaction of indolizi-
nylquinoxaline 1a with various dihalides 3. These mono-
indolizinylquinoxalinepodands 4aej can be distinguished by the
nature and length of the spacers (Table 2).
spacers
have
also
been
synthesized
from
mono-
indolizinylquinoxalinepodands under the same conditions. In our
view, the application of molecular iodine for the dehydrogenation
of indolizines, will allow us on the one hand to avoid the use of
catalysts or toxic reagents, while on the other hand make it possible
to carry out the reaction under mild conditionsdat room temper-
ature and with easily removable solvents, such as methylene
chloride.
2. Results and discussion
2.2. Synthesis of a,u-bis-[3-(1-phenylindolizin-2-yl)quinox-
alin-2-on-1-yl]oxaalkanes 4aej
2.1. Iodine mediated dehydrogenation of 3-(indolizin-2-yl)
quinoxalin-2-ones 1
The interaction of 3-(1-phenylindolizin-2-yl)quinoxalin-2(1H)-
one (1) with
a,u-dibromo- or ditosylatealkanes 3aej in boiling
It is known that the complexing ability of macrocycles depend
both on the size of the cavity and the number of atoms involved in
the complex formation. In this connection the synthesis of biin-
dolizine macrocycles with various lengthwise and number of oxy-
gen atoms in the crown ether residues remains are of particular
interest in designing new macrocyclic systems. As modified crown
ethers and due to the biindolizine fragment they prove promising
redox switchable ligands for different supramolecular
systems.16,17,19e21,38e43
Table 1
A facile iodine mediated synthesis of biindolizines 1
In continuation of our work on developing the indolizine
chemistry and the macrocyclization of quinoxalinemonopodands,
herein we report the use of the previously discovered new
method.37 The latter involves CeC bond creation (molecular iodine
and the binary system (I2eNaOAc) mediated oxidative coupling of
indolizines) for the synthesis of new bi-indolizinylquinoxalinone
Entry
R
Yield (%) of biindolizine 2
1 (a)
H
Me
92
70
2 (b)a
a
The compound has been described in a previous paper37 without detailed
characteristics.
Table 2
The synthesis of
a
,
u
-bis-[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]oxaalkanes 4aej
Entry
3
Product (yield, %)
4a (51)
1
2
4b (38)
3
4
5
6
4c (34)
4d (45)
4e (51)
4f (33)
7
4g (49)

V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
10677
Table 2 (continued )
Entry
3
Product (yield, %)
8
9
4h (36)
4i (31)
10
4j$H2O (48)
Table 3
A facile iodine mediated synthesis of diquinoxalinadiindolizinacyclophanes 5aej
dioxane in the presence of KOH for 24 h results in the formation of
quinoxalinepodands 4aej with 28e51% yields. In this way com-
pound 4a is precipitated from the reaction mixture in an analyti-
cally pure form. Other a,u-bis[(3-phenylindolizin-2-yl)quinoxalin-
2-on-1-yl]alkanes 4bej were purified by column chromatography
on silica gel.
The MALDI mass spectra of the compounds 4aei displayed
ion peaks at appropriate MHþ values.
a,u-Bis[(3-phenyl-
indolizin-2-yl)quinoxalin-2-on-1-yl]alkane 4j with longer
spacers separated from the reaction mixture as hydrates. This
was confirmed by its MALDI mass spectra, which displayed ion
peaks at appropriate [MþH3O]þ, and also by their elemental
analysis data.
Entry
Product
Yield, %a (%b)
1H NMR spectra of compounds 4bej contain the signals of the
protons of phenylindolizin-2-ylquinoxalin-2-on-1-yle aromatic
ring fragments resonating in the region of 6.5e8.5 ppm and the
signals of the protons of spacers in the areas of 4.4 ppm, (NCH2),
3.4e3.8 ppm, (OCH2), and 1.2e1.8 ppm, (the remaining of CH2
groups).
1
30 (50)
The symmetric structure of compounds 4bej indicates the
relation of intensities of the signals of the NCH2 and CH2
groups, which is 1:4 for compounds 4b; the signals of NCH2
and OCH2 groups are 1:1, 1:2, 1:3, and 1:4 for the compounds
of 4cee,h,i, and h correspondingly; the signals of NCH2, OCH2,
and CH2 (the remaining) groups are 1:3:4 and 1:5:2 for the
compounds of 4f and 4j correspondingly. These data, as well
2
49 (59)
as the frequencies of the
n(C]O) group in IR spectra at
1654e1647 cmꢀ1 indicates N-alkylation at the both quinoxalin-
2(1H)-one fragments of the molecule and the formation of
compounds 4bej.
2.3. Iodine mediated oxidative cyclization of
phenylindolizin-2-yl)-quinoxaline-2-one-1-yl]oxaalkanes 4aej
a,u-bis-[3-(1-
3
4
35 (60)
The interaction of
a,u-bis-[3-(1-phenylindolizin-2-yl)-qui-
noxaline-2-one-1-yl]oxaalkanes 4aej with molecular iodine at
room temperature for 20 h in a solution of methylene chloride
provides the formation of cyclophanes 5aej as the result of ox-
idative cyclization. The yields of the cyclophanes 5aej depending
on the length of the spacer were in the range of 30e75%
(Table 3).
68 (74)
It should be pointed out that an appreciable increase in yields
(7e25%) occurs when the binary system (I2eNaOAc) was used in-
stead of molecular iodine.37
All the synthesized compounds were characterized by NMR, MS
and IR spectra, and elemental analyses. Furthermore, the confor-
mational behavior of the macrocycle 5e in solid state and solutions
by IR spectroscopic method and B3LYP/6-31G* optimization ap-
proach (see SD) and the structure of the macrocycle 5f was further
determined by X-ray crystallographic analysis of its complex with
Pb(ClO4)2 as 5fꢁ Pb(ClO4)2 (see SD).
5
69 (92)
(continued on next page)

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V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
Table 3 (continued )
the spacer type and their length in particular. Firstly, while in
their precursors 4 the geminal protons of methylene groups of
spacers in the 1H NMR spectra are equivalent and resonate at
‘normal’ frequencies, these protons in macrocycles become
nonequivalent in pairs. This is a clear indication that there is no
mutual exchange between two conjugated conformations of the
macrocycle 5 because of very a high barrier to rotation around
the bond linking two indolizine fragments.37 Secondly, the con-
version of podands in macrocycles inevitably restricts the flux-
ionarity around other single bonds (e.g., IndeQ), which leads to
specific conformations in which the spacer protons fall within
the shielding/deshielding zones of strongly anisotropic hetero-
aromatic groups. Therefore, some nuclei resonate at a higher
Entry
Product
Yield, %a (%b)
6
7
8
79 (86)
field than in the source
a,u-bis-[3-(1-phenylindolizin-2-yl)-qui-
noxaline-2-one-1-yl]oxaalkanes 4aej.
If experimental data are considered in greater detail one can see
that the compounds with a relative short spacer undergo a slow
exchange (5a, 5c), with well resolved lines for all the protons
(Fig. 1a, b) that correspond to 5a rigid (in the NMR time scale)
structure. As soon as the spacers become longer there are charac-
teristic broadenings in the 1H NMR spectra for heteroaromatic and
spacers moieties as well (Fig. 1c, d). Further elongation of the
linkers (5g) produces a narrowing of the lines in the 1H NMR
spectra due to the exchange rate being higher in these cases, al-
though the fast exchange regime in the NMR time scale has not
been reached. The latter fact indicates that intramolecular dy-
namics depends not only on the spacer flexibility but on the re-
stricted rotation around the heterocyclic IndeQ units. In addition, it
is also worth mentioning that from the point of view of hetero-
aromatic protons this influence of spacer’s on the conformational
characteristics is reflected on the H5 Ind and H5 Qx signals to
a greater extent. It is assumed that these protons (in their envi-
ronment) undergo changes more during conformational
transformations.
75 (86)
58 (67)
The above spectral peculiarities for a variety of macrocycles
can be well explained in the framework of the conformational
exchange scheme outlined before for 5e (Fig. 2).44 These mac-
rocycles can exist in several basic conformations due to their
rotation around IndeQx bonds. There are ca. two C2 symmetrical
forms with both quinoxaline C]O bonds in-(SYM)y and out-
(SYM*)y wardly directed in respect to the macrocycle annule
(Fig. 2). In addition there are two nonsymmetrical and equiva-
lent (in terms of the NMR) conformations in which the Qx C]O
bonds directed only to one side (NSYM and NSYM*)y and
therefore the two halves of the macrocycle have are non-
equivalent.
9
60 (69)
10
60 (80)
2.5. Molecular structure of the complex 5f with Pb(ClO4)2
The molecular structure of compound 5f$Pb(ClO4)2 was un-
ambiguously established by a single-crystal X-ray analysis (Fig. 3).
The crystals of 5f$Pb(ClO4)2 were obtained by slow evaporation of
the compound from chloroform solution. The single-crystal X-ray
analysis reveled that, the molecule, possesses its own symmetry Cs,
but loses it in the crystal and is located in a general positions of the
monoclinic unit cell. The compound crystallizes with one cation
complex, two ClOꢀ4 anions and two solvate chloroform molecules in
the asymmetric part of the unit cell. Both solvate molecules are
disordered in the crystal over two positions with relative occu-
pancies 0.69:0.31 and 0.62:0.38. One of the two alkyl fragments
(C6eC9) of the macrocycle is disordered over two positions with
the relative occupancies 0.5:0.5.
a
Yields of isolated products when molecular iodine was used as oxidative
reagent.
b
Yields of isolated products when the binary system (I2eNaOAc) has been used
instead of molecular iodine.
c
The compounds have been described in previous paper37 without character-
ization data.
d
The compound has been described in previous paper37 with characterization
data.
2.4. Conformational peculiarities of the title macrocycles
In general, the 1H NMR spectra of the title macrocycles reflect
y
It means that there are set of conformations in fast exchange with characteristic
dependence of their conformational diversity and dynamics on
orientation of C]O bonds.

V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
10679
Fig. 1. 1H NMR spectra of macrocycles 5a, cee, g in DMSO-d6 at T¼303 K.
Fig. 2. Schematically presentation of the main conformer’s geometries of 5.
Fig. 3. Two projection of the molecular complex in the crystal 5f$Pb(ClO4)2 and partial numbering scheme. (a) All heteroatoms are represented by sphere of arbitrary radii. The
solvent CHCl3 molecules and hydrogen atoms were omitted for clarity; (b) carbon, oxygen, and nitrogen atoms are represented by sticks.
The loss of symmetry of the macrocycle cation is connected,
probably, with the realization of more favorable asymmetrical ar-
rangement of its heterocyclic and alkyl fragments in the crystal. The
dihedral angle between the planes of the two connected indolizine
fragments is 125.7ꢂ, angles between the planes of bounded indo-
lizine and quinoxaline fragments are 48.8ꢂ and 64.1ꢂ and between
the planes of two pairs of bounded indolizine and phenyl fragments
are 39.4ꢂ and 42.1ꢂ.
Within the complex 5f$Pb(ClO4)2 the coordination number of
lead cation is equal to 8 and two carboxyl groups, three ether ox-
ygen atoms and oxygen atoms of two ClOꢀ4 anions are involved in its
coordination. Two perchlorate anions are also located in the first
coordination sphere of the cation, one of which take part in the
direct interaction with the Pb2þ cation by one oxygen atom and
anotherdby two oxygen atoms. Thus, the lead cation is completely
encapsulated in the pseudocavity formed by the crown’s basket,

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V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
heterocycles, and anions. The guest is, in this instance, not a cation,
but a neutral C60H58Cl2N6O13Pb molecule. The space fill represen-
tation of the lead and oxygen atoms (Fig. 4) is noteworthy. Minimal
distance between the centers of the nearest lead cations in the
angle between aromatic planes is equal to 0ꢂ, and the shortest
distance between these Ar/Ar planes is equal to 3.29 A. At the
same time the opposite side of this aromatic fragment takes part in
ꢀ
the one else CH/
p
contact with the H70400 hydrogen atom
belonged to the nearest molecule (H70400/Cg distance is equal to
ꢀ
crystal is equal to 9.39 A.
ꢀ
ꢀ
3.43 A, shortest distance 2.84 A, symmetry operation 3/2ꢀx,1/
2þy,1/2ꢀz). This type of supramolecular synthon links the mole-
cules into a two-dimensional supramolecular structuredthe gof-
fered (wave-like) layers arranged parallel to the crystallographic
planes (110) in the crystal (Fig. 5).
The second type of supramolecular homosynthon formed by the
hydrogen bonds CeH/O type and brings together six molecules,
four of which belong to the same coffered layer and two others are
placed in the adjacent layers. Parameters of intermolecular CeH/O
hydrogen bonds are summarized in Table 4. The first four CeH/O
hydrogen bonds act in the same directions as
p/p contacts.
Thanks to central symmetry, these H-bonds are dual and stabilize
the goffered layers. These layers are further linked into a 3D-
structure by the other two dual hydrogen bonds.
Table 4
Parameters of the intermolecular H-bonds for complex 5f$Pb(ClO4)2 in crystals
ꢂ
ꢀ
ꢀ
ꢀ
DeH/A
DeH, A H/A, A D/A, A :DHA,
Symmetry
operation
C46eH46/O2
C13eH131/O4
C15eH152/O3
C68eH68/O8
0.93
0.97
2.52
2.48
2.64
2.63
3.35(1)
3.35(2)
149
149
170
131
1ꢀx,2ꢀy,1ꢀz
1ꢀx,1ꢀy,1ꢀz
1ꢀx,1ꢀy,1ꢀz
3/2ꢀx,1/2þy,
1/2ꢀz
Fig. 4. Top view of the molecular complex in the crystal 5f$Pb(ClO4)2. Pb atom and
coordinated oxygen atoms are represented in ‘space-fill’ style. All other atoms are
represented by ‘ball-and-stick’. The solvent CHCl3 molecules are omitted for clarity.
C56eH56/O6
C37eH37/O3
0.93
2.41
2.69
3.28(1)
155
131
1ꢀx,1ꢀy,ꢀz
ꢀ1/2þx,3/2ꢀy,
ꢀ1/2þz
In the absence of classical hydrogen bonding supramolecular
structure in the crystals of this compound is primarily determined
by the intermolecular hydrogen bonds of CeH/O type and
The mutual action of two type homosynthonsdCeH/O H-
bonds and CeH/ and binding contactsdleads to formation
CeH/p and p/p contacts with a participation of electronic sys-
p
p/p
tems of the aromatic fragments. It should be mentioned that the
CeH/Cl type interactions, as a whole interaction with the solvate
chloroform molecules, apparently, are irrelevant for the formation
of the supramolecular structure in the crystal, as evidenced by the
disordered arrangement of chloroform molecules in the crystal.
Probably, the role of the solvate molecules is more similar to ‘void
filling’ aggregates in clathrate systems.45
of 3D supramolecular structure characterized by parallel arrange-
ment of corrugated layers, two of which are shown in Fig. 5b.
Disordered chloroform solvate molecules are distributed between
the goffered layers and form cluster, consisting of four perchlorate
moieties, with the shortest Cl/Cl distances into the cluster in the
ꢀ
range 3.23e4.26 A and Cl/Cl distances between cluster in the
range 9.75e11.53 A (Fig. 5c).
ꢀ
CHe
p and pep type contacts are concentrated in one place of
the unit cell (Fig. 5adred circle) and form a supramolecular
homosynthonsdtetramers of the molecules. Relative position of
two quinoxaline moieties belonged to adjacent molecules related
3. Conclusions
by center of symmetry is favorable for dual p/p contacts between
To summarize, we have described a new simple and efficient
electron 0systems of its benzofragments. For this interaction
protocol for the intramolecular oxidative cyclization of mono-
ꢀ
d(Cg/Cg ) (centers of gravity of the aromatics)¼3.90 A, dihedral
indolizinylquinoxalinepodands
with
molecular
iodine
as
Fig. 5. Top (a) and bottom (b) view on the goffered layers of the complex in the crystal of 5f$Pb(ClO4)2. (a) Two different supramolecular homosynthons are represented by red and
blue circles. CeH/O intermolecular hydrogen bonds (blue) and CeH/ contacts (red) are shown by dashed lines. The solvent molecule in (a, b) was omitted for clarity; (c)
‘space-fill’ representation of the disordered solvent chloroform molecules arrangement .in the crystal, view along the 110 direction.
p, p/p

V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
10681
a dehydrogenating reagent. The remarkable features of this pro-
cedure are its efficiency, high conversion, operational simplicity, and
the availability of reagents, all at low cost. In solution these macro-
cycles are in an equilibrium of several conformations due to restricted
rotation around IndeQx bonds (ca. C2 symmetrical and non-
symmetrical forms), and their population and exchange rates de-
pends on the spacer. It is anticipated that this methodology will have
versatile applications in the practical syntheses of structural blockers
for the various electroswitched nanodimensional molecular devices
and machines with redox-active biindolizine and crown ethers
moieties. Further expansion of the reaction scope and synthetic ap-
plications of this methodology are in progress in our laboratory.
residue was washed with aqueous 5% NaHCO3 (10 mL) and 5%
Na2S2O3 (10 mL), then filtered, and dried.
When synthesizing 2b,c the reaction mixture was stirred for
20 h at this temperature and then was washed with aqueous 5%
NaHCO3 (10 mL) and 5% Na2S2O3 (10 mL). The organic layer was
dried over Na2SO4, then filtered, and evaporated under reduced
pressure. The residue was purified by flash column chromatogra-
phy on silica gel (hexane/CH2Cl2, 1:1/CH2Cl2).
4. Experimental section
4.1. General
The melting points were determined on a Boetius hot-stage ap-
paratus and are uncorrected. Infrared (IR) spectra were recorded on
a Bruker Vector-22 spectrometer. NMR experiments were carried
out with Bruker spectrometers AVANCE-400 (400.1 MHz (1H),
100.6 MHz (13C)) and AVANCE-600 (600.1 MHz (1H), 150.9 MHz
4.2.1. 1,10-Diphenyl-2,20-di[quinoxalin-2(1H)-on-3-yl]-3,30-biindoli-
zine (2a). Yellow powder, mp >360 ꢂC. Found: C, 78.43; H, 4.28; N,
(
13C)), equipped with a pulsed gradient unit capable of producing
magnetic field pulse gradients in the z-direction of 53.5 G cmꢀ1. All
12.42. C44H28N6O2 requires: C, 78.56; H, 4.20; N, 12.49%. IR (nmax
,
cmꢀ1, KBr): 3220e2500, 1670, 1611, 1563, 1520, 1418, 1344, 1272,
1247, 1236, 1211, 1152, 1098, 1029, 961, 762, 729, 700, 602, 547, 473,
430. dH NMR (600.1 MHz, DMSO-d6): 6.79 (2H, ddd, J 7.2, 6.9, 1.0 Hz,
H6 Ind), 6.85 (2H, dd, J 9.3, 1.3 Hz, H5 Qx), 6.98 (2H, ddd, J 9.3, 6.7,
1.1 Hz, H6 Qx), 7.00 (2H, ddd, J 9.1, 6.9, 1.0 Hz, H7 Ind), 7.11 (2H, m,
H4 Ph), 7.14 (2H, dd, J 7.6, 1.1 Hz, H8 Qx), 7.26 (4H, dd, J 8.0, 7.6 Hz,
H3 Ph), 7.31 (4H, dd, J 7.6, 1.5 Hz, H2 Ph), 7.38 (2H, ddd, J 7.6, 6.7,
1.3 Hz, H7 Qx), 7.53 (2H, dd, J 7.2, 1.0 Hz, H5 Ind), 7.70 (2H, dd, J 9.1,
1.0 Hz, H8 Ind), 12.01 (2H, s, H1 Qx); dC (151 MHz, DMSO-d6): 111.9
(C6 Ind), 113.6 (C1 Ind), 113.8 (C3 Ind), 114.7 (C8 Qx), 117.6 (C8 Ind),
119.7 (C7 Ind),122.6 (C6 Qx),124.4 (C5 Ind),125.1 (C2 Ind),125.4 (C4
Ph), 128.2 (C3 Ph, C5 Qx), 129.0 (C2 Ph), 129.7 (C7 Qx), 130.2 (C8a
Ind), 131.7 (C4a Qx), 131.8 (C8a Qx), 134.5 (C1 Ph), 153.9 (C3 Qx),
154.7 (C2 Qx). MS (EI, 70 eV): m/z (%) 673.3 (Mþþ1, 55.4), 672.3
(Mþ, 100), 671.3 (2.7), 540.3 (1.5), 539.3 (3.35), 538.3 (1.30), 527.3
(1.32), 449.2 (0.4), 337.2 (4.6), 336.7 (7.8), 336.2 (16.8), 335.2 (3.3).
spectra were acquired in a 5-mm gradient inverse broad band probe
head. Chemical shifts are reported on the d (parts per million) scale
and are relative to the residual 1H and 13C signal of DMSO-d6 and
CDCl3. The MALDI mass spectra were obtained on a Bruker UltraFlex
III MALDI TOF/TOF instrument with 2,5-dihydroxybenzoic acid (2,5-
DHB) as a matrix. Mass spectra Electronic ionization (EI) was mea-
sured on a TRACE MS spectrometer. The elemental analyses were
carried out at the microanalysis laboratory of the Arbuzov Institute
of Organic and Physical Chemistry, Russian Academy of Sciences.
The 3-(1-phenylindolizin-2-yl)quinoxalin-2(1H)-one (1a) was syn-
thesized according to the reported methods.46,47
The X-ray diffraction data for the crystal of 5f$Pb(ClO4)2 (see
Section 4.4.6) were collected on a Bruker Smart Apex II CCD dif-
ꢀ
fractometer using graphite monochromated MoKa
(
l
¼0.71073 A)
radiation at 296(2) K. The structure was solved by direct method
using SHELXS48 program and refined by the full-matrix least-
squares using SHELXL49 programs. All non-hydrogen atoms were
refined anisotropically. The hydrogen atoms were inserted at cal-
culated positions and refined as riding atoms. Data collection: im-
ages were indexed and integrated using the APEX2 data reduction
package.50 All calculations were performed on PC using WinGX51
suit of programs. Analysis of the intermolecular interactions was
performed using the program PLATON.52 Mercury program pack-
age53 was used for figures preparation.
4.2.2. 1,10-Diphenyl-2,20-di[5-methylquinoxalin-2-on-3-yl]-3,30-biin-
dolizine (2b). Yellow powder, mp 317e319 ꢂC. IR (nmax, cmꢀ1, Nujol
mull): 1662, 1602, 1586, 1522, 1339, 1312, 1280, 1235, 1220, 1161,
1101, 1089, 1035, 977, 953, 925, 890, 759, 730, 701, 538. Found: C,
78.77; H, 4.80; N, 11.87. C46H32N6O2 requires: C, 78.84; H, 4.60; N,
11.99. dH NMR (600.1 MHz, DMSO-d6): 3.21 (6H, s, Me), 6.80 (2H,
ddd, J 7.2, 6.9, 1.0 Hz, H6 Ind), 7.00 (2H, ddd, J 9.1, 6.9, 1.0 Hz, H7
Ind), 7.04 (2H, dd, J 7.5, 1.1 Hz, H5 Qx), 7.11 (2H, td, J 8.3, 1.5 Hz, H4
Ph), 7.13 (2H, ddd, J 7.7, 7.5, 1.0 Hz, H6 Qx), 7.23 (4H, dd, J 8.3, 7.6,
Hz, H3 Ph), 7.26 (4H, dd, J 7.6, 1.5 Hz, H2 Ph), 7.36 (2H, dd, J 7.0,
1.0 Hz, H8 Qx), 7.49 (2H, ddd, J 7.7, 7.0, 1.1 Hz, H7 Qx), 7.51 (2H, d, J
7.2, 1.0 Hz, H5 Ind), 7.68 (2H, dd, J 9.1, 1.0 Hz, H8 Ind); dC (151 MHz,
DMSO-d6): 28.7 (Me), 112.1 (C6 Ind), 113.6 (C3 Ind), 113.9 (C1 Ind),
114.1 (C8 Qx), 117.7 (C8 Ind), 119.6 (C7 Ind), 122.6 (C6 Qx), 124.1 (C5
Ind), 125.4 (C4 Ph and C2 Ind), 128.1 (C3 Ph), 128.8 (C3 Ph), 129.0
(C5 Qx), 130.0 (C7 Qx), 130.1 (C8a Ind), 132.0 (C4a Qx), 133.0 (C8a
Qx), 134.5 (C1 Ph), 153.1 (C3 Qx), 153.4 (C2 Qx). MS (MALDI TOF)
(MH)þ 729.
Crystallographic data (excluding structure factors) for the
structure 5f$Pb(ClO4)2 have been deposited in the Cambridge
Crystallographic Data Centre as supplementary publication number
CCDC 884152. Copies of the data can be obtained free of charge
upon application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK,
(fax: þ44(0)1223 336033 or e-mail: deposit@ccdc.cam.ac.uk).
4.2. General procedure (a) for the synthesis of 1,10-diphenyl-
2,20-di(quinoxalin-2-on-3-yl)-3,30-biindolizines 2
A solution of I2 (150 mg, 0.591 mmol) in CH2Cl2 (30 mL) at room
temperature was added to a stirred solution of the appropriate
indolizine 1 (0.40 mmol) in CH2Cl2 (15 mL).
4.3. General procedure for the synthesis of a,u-bis[3-(1-
When synthesizing 2a while stirring the reaction mixture for 1 h
at room temperature there occurs the precipitation of dark violet
color crystals. EtOH (10 mL) was added to the reaction mixture and
then refluxed. In the course of the reaction the crystals gradually
dissolved during 10 min. After evaporation of the solvent the
phenylindolizin-2-yl)quinoxalin-2-on-1-yl]oxaalkanes 4
A suspension of compound 1a (0.55 g, 1.630 mmol), KOH (0.18 g,
3.214 mmol), dibromide 3 (0.80 mmol), and dioxane (25 mL) was
refluxed for 24 h.

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V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
When synthesizing 4a the reaction mixture was left overnight at
J 7.1 Hz, H1), 6.62 (2H, td, J 6.9, 1.0 Hz, H6 Ind), 6.74 (2H, ddd, J 9.1,
6.9, 1.0 Hz, H7 Ind), 7.22e7.35 (16H, ArH), 7.54 (4H, m, H7 and H8
Qx), 8.35 (2H, d, J 6.9 Hz, H5 Ind), 8.53 (2H, s, H3 Ind); dC (151 MHz,
DMSO-d6): 26.0 (C3), 26.6 (C2), 28.4 (C4), 28.5 (C5), 41.5 (C1), 111.3
(C6 Ind), 113.9 (C1 Ind), 114.0 (C8 Qx), 117.1 (C3 Ind), 117.3 (C8 Ind),
118.5 (C7 Ind), 121.1 (C2 Ind), 122.9 (C6 Qx), 125.2 (C4 Ph), 125.9
(C5 Ind), 127.4 (C2 Ph), 128.9 (C5 Qx), 129.6 (C8a Ind), 129.7 (C7
Qx), 129.9 (C3 Ph), 131.5 (C8a Qx), 132.2 (C4a Qx), 135.4 (C1 Ph),
150.5 (C3 Qx), 153.3 (C2 Qx). MS (MALDI TOF) 813 (MHþ), 835
(MþNa)þ, 851 (MþK)þ.
room temperature, the yellow precipitate was filtrated and washed
with EtOH (5 mL) and water (5 mL) and dried in vacuo to afford the
product.
When synthesizing 4bel the temperature was allowed to
slowly warm to room temperature, the reaction mixture was
quenched with water (100 mL), and neutralized with AcOH. The
yellow solid was filtrated and washed with water (5 mL), dried in
vacuo and purified by flash column chromatography on silica gel
(hexane/CH2Cl2, 3:1/CH2Cl2 (aec); CH2Cl2/CH2Cl2/EtOH, 100:1
(del)).
4.3.3. 1,5-Bis[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]-3-
oxapentane (4c). Yellow powder, mp 240e242 ꢂC. Found: C, 77.29;
H, 4.81; N, 11.39. C48H36N6O3 requires: C, 77.40; H, 4.87; N, 11.28%.
IR (nmax, cmꢀ1, Nujol mull): 1654, 1602, 1581, 1544, 1528, 1311, 1229,
1083, 1123, 762, 670, 586; dH NMR (600.1 MHz, DMSO-d6): 3.76 (4H,
t, J 5.7 Hz, H2), 4.40 (4H, t, J 5.7 Hz, H1), 6.61 (2H, td, J 7.0, 1.0 Hz, H6
Ind), 6.74 (2H, ddd, J 9.1, 7.0, 1.0 Hz, H7 Ind), 7.19 (2H, t, J 7.7, H6 Qx),
7.23 (4H, m, H5 Qx and H4 Ph), 7.29e7.38 (12H, ArH), 7.47 (2H, d, J
8.1 Hz, H8 Qx), 8.32 (2H, dd, J 7.0, 1.1 Hz, H5 Ind), 8.51 (2H, s, H3
Ind); dH (151 MHz, DMSO-d6): 41.6 (C1), 67.2 (C2), 111.5 (C6 Ind),
113.9 (C1 Ind), 114.5 (C8 Qx), 117.2 (C3 Ind), 117.5 (C8 Ind), 118.7 (C7
Ind), 121.0 (C2 Ind), 123.1 (C6 Qx), 125.4 (C4 Ph), 126.0 (C5 Ind),
127.5 (C2 Ph),128.8 (C5 Qx),129.4 (C7 Qx),129.7 (C8a Ind),130.1 (C3
Ph), 132.1 (C8a Qx), 132.2 (C4a Qx), 135.5 (C1 Ph), 150.4 (C3 Qx),
153.6 (C2 Qx); MS (MALDI TOF) 745 (MHþ), 767 (MþNa)þ, 783
(MþK)þ.
4.3.1. 1,3-Bis[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]xylene
(4a). Yellow powder, mp 234e236 ꢂC. Found: C, 80.29; H, 4.71;
N, 10.89. C52H36N6O2 requires: C, 80.39; H, 4.67; N, 10.82%. IR
(
nmax, cmꢀ1, KBr): 3055, 2957, 2912, 2886, 2853, 1647, 1600, 1577,
1549, 1525, 1494, 1450, 1438, 1422, 1365, 1314, 1284, 1251, 1227,
1177, 1121, 1082, 1047, 1007, 949, 874, 754, 704, 672, 583, 425. dH
NMR (600.1 MHz, DMSO-d6): 5.48 (4H, s, CH2), 6.61 (2H, td, J 6.9,
1.0 Hz, H6 Ind), 6.75 (2H, dd, J 9.1, 6.9 Hz, H7 Ind), 7.11 (2H, dd, J
7.9, 1.0 Hz, H4 Xy), 7.20 (2H, t, J 7.5 Hz, H6 Qx), 7.21e7.42 (20H,
ArH), 8.29 (2H, d, J 6.9 Hz, H5 Ind), 8.48 (2H, br s, H3 Ind); dC
(151 MHz, DMSO-d6): 44.8 (CH2), 111.4 (C6 Ind), 113.9 (C1 Ind),
114.5 (C8 Qx), 117.2 (C3 Ind), 117.4 (C8 Ind), 118.6 (C7 Ind), 121.1
(C2 Ind), 123.2 (C6 Qx), 125.3 (C4 Ph), 125.5 (C2 Xy), 125.7 (C4
Xy), 125.9 (C5 Ind), 127.5 (C2 Ph), 128.9 (C5 Qx), 129.0 (C5 Xy),
129.4 (C7 Qx), 129.7 (C8a Ind), 130.0 (C3 Ph), 131.5 (C8a Qx),
132.3 (C4a Qx), 135.5 (C1 Ph), 136.4 (C1 Xy), 150.7 (C3 Qx), 153.7
(C2 Qx). MS (MALDI TOF) 777 (MHþ), 799 (MþNa)þ, 815
(MþK)þ.
4.3.4. 1,8-Bis[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]-3,5-
dioxaoctane (4d). Yellow powder, mp 225e227 ꢂC. Found: C,
76.20; H, 5.05; N, 10.48. C50H40N6O4 requires: C, 76.12; H, 5.11;
N, 10.65%. IR (nmax, cmꢀ1, KBr): 3143, 3045, 2961, 2923, 2894,
2870, 2855, 1654, 1600, 1581, 1527, 1492, 1452, 1440, 1310, 1280,
1255, 1182, 1124, 1102, 1082, 764, 750, 701, 672, 557. dH NMR
(600.1 MHz, DMSO-d6): 3.49 (4H, m, H4), 3.65 (4H, t, J 5.9 Hz,
H2), 4.37 (4H, t, J 5.9 Hz, H1), 6.61 (2H, td, J 6.9, 1.0 Hz, H6 Ind),
6.74 (2H, ddd, J 9.1, 6.9, 1.0 Hz, H7 Ind), 7.19 (2H, t, J 7.7, H6 Qx),
7.20e7.38 (14H, ArH), 7.43 (2H, t, J 7.7 Hz, H7 Qx), 7.52 (2H, d, J
7.7 Hz, H8 Qx), 8.32 (2H, dd, J 6.9, 1.0 Hz, H5 Ind), 8.52 (2H, s, H3
Ind); dC (151 MHz, DMSO-d6): 41.6 (C1), 67.1 (C2), 69.9 (C4), 111.4
(C6 Ind), 113.9 (C1 Ind), 114.6 (C8 Qx), 117.2 (C3 Ind), 117.4 (C8
Ind), 118.6 (C7 Ind), 120.9 (C2 Ind), 123.0 (C6 Qx), 125.3 (C4 Ph),
4.3.2. 1,10-Bis[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]dec-
ane (4b). Yellow powder, mp 221e223 ꢂC. Found: C, 79.79; H,
5.99; N, 10.48. C54H48N6O2 requires: C, 79.78; H, 5.95; N, 10.34%. IR
(
nmax, cmꢀ1, KBr): 3051, 2927, 2852, 1650, 1580, 1528, 1461, 1313,
1284, 1184, 1139, 764, 745, 700, 429. dH NMR (600.1 MHz, DMSO-
d6): 1.24e1.36 (12H, m, H3eH5), 1.60e1.69 (4H, m, H2), 4.24 (4H, t,

V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
10683
126.0 (C5 Ind), 127.4, 127.5 (C2 Ph), 128.7 (C5 Qx), 129.3 (C7 Qx),
129.6 (C8a Ind), 130.0 (C3 Ph), 132.0 (C8a Qx), 132.2 (C4a Qx),
135.4 (C1 Ph), 150.4 (C3 Qx), 153.5 (C2 Qx); MS (MALDI TOF) 789
(MHþ), 811 (MþNa)þ, 827 (MþK)þ.
70.0 (C6), 111.4 (C6 Ind), 113.9 (C1 Ind), 114.1 (C8 Qx), 117.2 (C3 Ind),
117.4 (C8 Ind), 118.6 (C7 Ind), 121.1 (C2 Ind), 123.0 (C6 Qx), 125.3 (C4
Ph), 126.0 (C5 Ind), 127.4 (C2 Ph), 129.0 (C5 Qx), 129.6 (C7 Qx), 129.6
(C8a Ind),130.0 (C3 Ph),131.5 (C8a Qx),132.2 (C4a Qx),135.5 (C1 Ph),
150.5 (C3 Qx), 153.3 (C2 Qx); MS (EI, 70 eV): m/z (%) 945 (Mþþ1, 3),
945 (Mþ, 5), 525 (19), 464 (22), 437 (25), 436 (48), 421 (20), 420 (17),
407 (18), 378 (15), 365 (11), 364 (26), 352 (10), 351 (30), 350 (11), 339
(17), 338 (62), 337 (70), 336 (34), 323 (13), 322 (30), 321 (12), 320
(22), 310 (12), 309 (28), 308 (100), 307 (39), 306 (15).
4.3.5. 1,11-Bis[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]-
3,6,9-trioxaundecane (4e). Yellow powder, mp 192e194 ꢂC. Found:
C, 75.07; H, 5.38; N,10.00. C52H44N6O5 requires: C, 74.98; H, 5.32; N,
10.09%. IR (nmax, cmꢀ1, Nujol mull): 1652, 1602, 1581, 1529, 1494,
1311, 1289, 1228, 1183, 1125, 1007, 753, 702, 670. dH NMR
(600.1 MHz, DMSO-d6): 3.39 (2H, m, H5), 3.47 (2H, m, H4), 3.71 (2H,
t, J¼5.5 Hz, H2), 4.41 (2H, t, J¼5.5 Hz, H1), 6.60 (1H, ddd, J¼6.8, 6.1,
0.7 Hz, H6 Ind), 6.72 (1H, dd, J 6.8, 6.1, 0.7 Hz, H7), 7.22e7.28 (3H, m,
H5 Qx, H6 Qx, and H4 Ph), 7.29e7.38 (5H, m, H8 Ind, H2 Ph, and H3
Ph), 7.46 (1H, td, J¼7.8, 1.4 Hz, H7 Qx), 7.55 (1H, d, J¼7.8 Hz, H8 Qx),
8.32 (1H, dd, J¼6.8, 0.7 Hz, H5 Ind), 8.52 (1H, s, H3 Ind). dC NMR
(150.9 MHz, DMSO-d6): 41.5, 66.9, 69.5, 69.7, 113.8, 114.5, 117.0,
117.3, 118.4, 120.8, 122.9, 122.9, 125.2, 125.8, 127.3, 128.6, 129.2,
129.5, 129.9, 135.3, 131.9, 132.0, 150.2, 153.4. MS (MALDI TOF) 833
(MHþ), 855 (MþNa)þ, 871 (MþK)þ.
4.3.7. 1,14-Bis[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]-
3,6,9,12-tetraoxatetradecane (4g). Yellow powder, mp 126e128 ꢂC.
Found: C, 73.87; H, 5.39; N, 9.63. C54H48N6O6 requires: C, 73.95; H,
5.52; N, 9.58%. IR (nmax, cmꢀ1, KBr): 3046, 2866, 1653, 1600, 1580,
1527, 1494, 1451, 1310, 1286, 1226, 1182, 1124, 1099, 1082, 1037, 763,
752, 700, 671, 584, 561, 466, 428. dH NMR (400.1 MHz, CDCl3): 3.52
(4H, s, H6), 3.52e3.57 (4H, m, H3), 3.59e3.61 (4H, m, H4), 3.83 (4H,
t, J 6.2 Hz, H2), 4.50 (4H, t, J 6.2 Hz, H1), 6.51 (2H, td, J 6.8, 1.0 Hz, H6
Ind), 6.65 (2H, ddd, J 9.1, 6.8,1.0 Hz, H7 Ind), 7.21 (2H, td, J 7.8,1.0 Hz,
H6 Qx), 7.25e7.52 (18H, ArH), 7.90 (2H, dd, J 6.8, 1.0 Hz, H5 Ind),
8.45 (2H, s, H3 Ind); dC NMR (100.6 MHz, CDCl3) 42.5, 68.0, 70.5,
70.6, 70.8, 111.7, 114.2, 115.1, 116.9, 118.1, 118.6, 121.5, 123.4, 125.2,
125.6, 127.7, 129.2, 129.9, 130.6, 130.9, 132.4, 133.1, 136.0, 150.9,
154.5. MS (MALDI TOF) 877 (MHþ), 899 (MþNa)þ, 915 (MþK)þ.
4.3.8. 1,2-Bis{6-[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]-3-
oxapentoxybenzene (4h). Yellow powder, mp 104e106 ꢂC. Found: C,
75.26; H, 5.25; N 9.14. C58H48N6O6 requires: C, 75.31; H, 5.23; N,
9.08%. IR (nmax, cmꢀ1, Nujol mull): 1654, 1601, 1581, 1528, 1501, 1311,
1288, 1252, 1184, 1124, 1083, 1049, 1015, 960, 920, 763, 752, 704,
672. dH NMR (600.1 MHz, DMSO-d6): 3.70 (4H, t, J 4.7 Hz, H4), 3.76
(4H, t, J 6.1 Hz, H2), 4.00 (4H, t, J 4.7 Hz, H5), 4.43 (4H, t, J 6.1 Hz, H1),
6.60 (2H, td, J 6.9, 1.0 Hz, H6 Ind), 6.72 (2H, ddd, J 9.1, 6.9, 1.0 Hz, H7
Ind), 6.82 (2H, m, H2 Ca), 6.88 (2H, m, H3 Ca), 7.17e7.35 (16H, ArH),
7.41 (2H, dd, J 8.6, 7.8 Hz, H7 Qx), 7.55 (2H, d, J 8.6 Hz, H8 Qx), 8.30
(2H, dd, J 6.9, 1.0 Hz, H5 Ind), 8.51 (2H, s, H3 Ind); dC (151 MHz,
DMSO-d6): 41.6 (C1), 67.2 (C2), 68.3 (C5), 69.1 (C4), 111.4 (C6 Ind),
113.9 (C1 Ind), 114.5 (C8 Qx), 114.8 (C4 Ca), 117.2 (C3 Ind), 117.4 (C8
4.3.6. 1,19-Bis[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]-
7,10,13-trioxanonadecane (4f). Yellow powder, mp 102e105 ꢂC.
Found: C, 76.08; H, 6.33; N, 8.82. C60H60N6O5 requires: C, 76.25; H,
6.40; N, 8.89%. IR (nmax, cmꢀ1, KBr): 3048, 2930, 2857, 1649, 1600,
1579, 1552, 1528, 1494, 1457, 1369, 1311, 1283, 1247, 1221, 1187, 1122,
1086, 1038, 749, 700, 669, 646, 583, 561, 515, 464, 429. dH NMR
(600.1 MHz, DMSO-d6): 1.30e1.36 (8H, m, H3 and H4), 1.46 (4H, m,
H5), 1.62 (4H, m, H2), 3.34 (4H, t, J 6.7 Hz, H6), 3.43 (4H, m, H8), 3.48
(4H, m, H9), 4.22 (4H, t, J 7.7 Hz, H1), 6.60 (2H, td, J 6.9,1.0 Hz, H6 Ind),
6.72 (2H, ddd, J 9.1, 6.9,1.0 Hz, H7 Ind), 7.24 (4H, m, H4 Ph and H6 Qx),
7.28e7.36 (12H, ArH), 7.51 (4H, m, H7 and H8 Qx), 8.33 (2H, dd, J 6.9,
1.0 Hz, H5 Ind), 8.53 (2H, s, H3 Ind); dC (151 MHz, DMSO-d6): 25.2
(C4), 25.9 (C3), 26.7 (C2), 28.9 (C5), 41.6 (C1), 69.3 (C8), 69.7 (C9),

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V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
Ind), 118.6 (C7 Ind), 120.9 (C2 Ind), 121.2 (C3 Ca), 123.0 (C6 Qx),
125.3 (C4 Ph), 125.9 (C5 Ind), 127.4 (C2 Ph), 128.7 (C5 Qx), 129.3 (C7
Qx), 129.6 (C8a Ind), 130.1 (C3 Ph), 132.0 (C8a Qx), 132.1 (C4a Qx),
135.4 (C1 Ph), 148.4 (C1 Ca), 150.3 (C3 Qx), 153.5 (C2 Qx); MS
(MALDI TOF) 789 (MHþ), 811 (MþNa)þ, 827 (MþK)þ.
(150.9 MHz, CDCl3): 24.2, 26.9, 42.2, 61.8, 70.3, 70.5, 70.8, 72.5,111.7,
113.4, 115.1, 116.9, 118.1, 118.6, 121.6, 123.3, 125.2, 125.6, 127.7, 129.4,
130.2, 130.6, 130.9, 131.8, 133.3, 136.0, 151.0, 154.4; MS (MALDI TOF)
(MþH2O)Hþ ¼ 995. MS (EI, 70 eV): m/z (%) 977 (Mþþ1, 0.2), 976
(Mþ, 0.3), 499 (15), 498 (23), 497 (71), 453 (11), 452 (19), 436 (21),
423 (13), 409 (21), 408 (28), 393 (19), 392 (18), 379 (17), 378 (35),
365 (16), 364 (25), 352 (11), 351 (30), 350 (11), 339 (21), 338 (58),
337 (58), 336 (39), 323 (18), 322 (37), 321 (16), 320 (31), 310 (15),
309 (34), 308 (100), 307 (49), 306 (22).
4.4. General procedure (a) 21,31-diphenyl-12,42-dioxo-1,4(3,1)-
diquinoxalina-2(2,3),3(3,2)-diindolizinacycloalkaphanes 5
A solution of I2 (100 mg, 0.424 mmol) in CH2Cl2 (30 mL) at room
temperature was added to a stirred solution of the appropriate
bis-[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]oxaalkane
a,u-
4
(0.20 mmol) in CH2Cl2 (150 mL). The reaction mixture was stirred for
20 h at this temperature and then was washed with aqueous 5%
NaHCO3 (10 mL) and 5% Na2S2O3 (10 mL). The organic layer was dried
over Na2SO4, filtered, and evaporated under reduced pressure. The
residue was purified by flash column chromatography on silica gel
(hexane/CH2Cl2, 1:1/CH2Cl2 (aec); CH2Cl2/CH2Cl2/EtOH, 50:1
(dej)).
4.3.9. 1,3-Bis{6-[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]-3-
oxapentoxybenzene (4i). Yellow powder, mp 116e118 ꢂC. Found: C,
75.28; H, 5.20; N, 9.15. C58H48N6O6 requires: C, 75.31; H, 5.23; N,
9.08%. IR (nmax, cmꢀ1, Nujol mull): 1653, 1601, 1582, 1528, 1491, 1311,
1287, 1248, 1227, 1182, 1157, 1126, 1082, 1057, 856, 763, 751, 723, 702,
668. dH NMR (600.1 MHz, DMSO-d6): 3.72 (4H, t, J 4.0 Hz, H4), 3.79
(4H, t, J 6.2 Hz, H2), 3.97 (4H, t, J 4.0 Hz, H5), 4.47 (4H, t, J 6.2 Hz, H1),
6.37 (1H, t, J 2.0 Hz, H2 Re), 6.42 (2H, td, J 8.3, 2.0 Hz, H4 Re), 6.61 (2H,
td, J 6.6, 0.8 Hz, H6 Ind), 6.73 (2H, ddd, J 9.1, 6.6, 1.0 Hz, H7 Ind), 7.07
(1H, t, J 8.3 Hz, H5 Re), 7.20e7.36 (16H, ArH), 7.47 (2H, td, J 8.4,1.7 Hz,
H7 Qx), 7.60 (2H, d, J 8.4 Hz, H8 Qx), 8.33 (2H, dd, J 6.6,1.0 Hz, H5 Ind),
8.52 (2H, s, H3 Ind); dC (151 MHz, DMSO-d6): 41.6 (C1), 67.0 (C5), 67.1
(C2), 68.9 (C4), 101.2 (C2 Re), 106.8 (C4 Re), 111.4 (C6 Ind), 113.9 (C1
Ind), 114.6 (C8 Qx), 117.2 (C3 Ind), 117.4 (C8 Ind), 118.6 (C7 Ind), 121.0
(C2 Ind), 123.1 (C6 Qx), 125.3 (C4 Ph), 126.0 (C5 Ind), 127.4 (C2 Ph),
128.8 (C5 Qx), 129.4 (C7 Qx), 129.6 (C8a Ind), 129.6 (C5 Re), 130.0 (C3
Ph),132.0 (C8a Qx),132.2 (C4a Qx),135.4 (C1 Ph),150.4 (C3 Qx),153.5
(C2 Qx), 159.5 (C1 Re); MS (MALDI TOF) (MH)þ¼925.
4.4.1. 21,31-Diphenyl-12,42-dioxo-1,4(3,1)-diquinoxalina-
2(2,3),3(3,2)-diindolizina-6-(1,3)benzacyclo-heptaphane
(5a). Yellow powder, mp >360 ꢂC. Found: C, 80.77; H, 4.48; N,
10.72. C52H34N6O2 requires: C, 80.60; H, 4.42; N, 10.85%. IR (nmax
,
cmꢀ1, KBr): 3047, 2923, 2852, 1666, 1602, 1581, 1519, 1488, 1440,
1364, 1348, 1307, 1281, 1250, 1237, 1196, 1164, 1148, 1100, 1065,
1046, 1013, 944, 757, 728, 700, 671, 567, 429. dH NMR (400.1 MHz,
DMSO-d6): 4.98 and 5.12 (4H, d, J 16.0 Hz, CH2), 5.76 (1H, s, H2 Xy),
6.83 (2H, dd, J 7.1, 6.9 Hz, H6 Ind), 7.06 (2H, dd, J 9.1, 6.9 Hz, H7 Ind),
7.12 (2H, dd, J 6.9, 6.6 Hz, H6 Qx), 7.15 (2H, d, J 6.9 Hz, H5 Qx),
7.16e7.33 (13H, m, ArH), 7.34 (2H, d, J 7.9 Hz, H8 Qx), 7.39 (2H, t, J
7.9 Hz, H7 Qx), 7.73 (2H, d, J 7.1 Hz, H5 Ind), 7.76 (2H, d, J 9.1 Hz, H8
Ind); dC (151 MHz, DMSO-d6): 44.3, 109.7, 110.0, 112.4, 113.9, 114.6,
114.7, 117.9, 120.7, 121.7, 123.8, 125.1, 125.7, 125.9, 126.7, 128.5, 128.8,
129.9, 130.7, 132.5, 133.1, 136.0, 136.3, 153.1, 153.4. MS (MALDI TOF)
(MH)þ 775.
4.3.10. 1,21-Bis[3-(1-phenylindolizin-2-yl)quinoxalin-2-on-1-yl]-
5,8,11,14,17-pentaoxaheneicosane monohydrate (4j). Yellow powder,
mp 132e134 ꢂC. Found: C, 71.39; H, 6.38; N, 8.33. C60H62N6O8 re-
quires: C, 72.41; H, 6.28; N, 8.44%. IR (nmax, cmꢀ1, KBr): 2937, 2865,
1650, 1559, 1579, 1526, 1460, 1449, 1282, 1249, 1220, 1180, 1121,
1086, 1066, 1039, 1005, 763, 751, 702, 672, 645, 582, 563, 516, 466,
433. dH NMR (600.1 MHz, CDCl3): 1.72e1.77 (4H, m, H2), 1.83e1.88
(4H, m, H3), 3.55 (4H, t, J 6.2 Hz, H4), 3.59e3.65 (8H, m, H6 and H7),
3.66e3.71 (8H, m, H9 and H10), 4.33 (4H, t, J 7.6 Hz, H1), 6.50 (2H,
ddd, J 6.8, 6.6, 0.9 Hz, H6 Ind), 6.64 (2H, ddd, J 9.2, 6.6, 0.9 Hz, H7
Ind), 7.22 (2H, dd, J 7.8, 7.3 Hz, H6 Qx), 7.27e7.47 (18H, m, ArH), 7.90
(2H, dd, J 6.8, 0.9 Hz, H5 Ind), 8.45 (2H, s, H3 Ind). dC NMR
4.4.2. 21,31-Diphenyl-12,42-dioxo-1,4(3,1)-diquinoxalina-
2(2,3),3(3,2)-diindolizinacyclotetradecaphane (5b). Yellow powder,

V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
10685
mp >360 ꢂC. Found: C, 80.07; H, 5.68; N, 10.43. C54H46N6O2 re-
quires: C, 79.97; H, 5.72; N, 10.36%. IR (nmax, cmꢀ1, KBr): 3072, 2928,
2855, 1650, 1601, 1584, 1521, 1487, 1456, 1364, 1348, 1226, 1159,
1097, 760, 728, 706. dH NMR (400.1 MHz, DMSO-d6): 0.90e1.45
(16H, m, H2eH5), 3.69 (4H, m, H1), 6.82 (2H, dd, J 7.2, 6.7 Hz, H6 of
Ind), 7.01 (2H, ddd, J 8.2, 6.7 Hz, H7 of Ind), 7.09 (2H, m, H6 of Qx),
7.15e7.35 (12H, m, ArH), 7.45 (2H, d, J 8.0 Hz, H8 of Qx), 7.51 (2H, dd,
J 8.0, J 7.5 Hz, H7 of Qx), 7.66 (2H, d, J 8.2 Hz, H8 of Ind), 7.83 (2H, d, J
7.2 Hz, H5 of Ind); dC (151 MHz, DMSO-d6): 25.3, 26.4, 26.8, 27.6,
41.6, 110.0, 111.8, 113.3, 114.3, 114.9, 117.8, 120.5, 123.4, 125.9, 126.6,
128.7, 128.9, 129.7, 130.7, 130.7, 132.8, 133.1, 135.4, 153.4, 154.2. MS
(MALDI TOF) (MH)þ 811.
136.2, 153.7, 154.5. MS (MALDI TOF) (MH)þ¼787, (MþNa)þ¼809,
(MþK)þ¼825.
4.4.5. 21,31-Diphenyl-12,42-dioxo-7,10,13-trioxa-1,4(3,1)-diquinox-
alina-2(2,3),3(3,2)-diindolizinacyclopentadecaphane
(5e). Yellow
powder, mp >330 ꢂC. Found: C, 75.03; H, 5.01; N,10.02. C52H42N6O5
requires: C, 75.16; H, 5.09; N, 10.11%. IR (nmax, cmꢀ1, KBr): 2922,
2857, 1649, 1601, 1583, 1524, 1486, 1454, 1366, 1346, 1281, 1251,
1159, 1128, 1103, 762, 729, 704. dH NMR (400.1 MHz, DMF-d7):
3.40e3.49 (10H, m, H5, H2 and H3), 3.50 (2H, m, H3), 3.55 (2H, m,
H2), 3.83 and 4.02 (4H, m, H1), 6.83 (2H, dd, J¼6.9, 6.7 Hz, H6 Ind),
7.02 (2H, dd, J¼9.4, 6.7 Hz, H7 Ind), 7.14 (2H, d, J 7.4 Hz, H4 Ph), 7.20
(2H, ddd, J¼8.0, 5.7, 2.3 Hz, H6 Qx), 7.25 (4H, dd J¼7.8, 7.4 Hz, H3
Ph), 7.30 (2H, d, J¼8.0 Hz, H5 Qx), 7.37 (4H, d, J¼7.8 Hz, H2 Ph),
7.48e7.52 (4H, m, H7 Qx and H8 Qx), 7.62 (2H, d, J¼6.9 Hz, H5 Ind),
7.72 (2H, d, J¼9.4 Hz, H8 Ind). dC NMR (150.9 MHz, DMF-d7): 42.3,
67.6, 70.5, 70.7, 112.4, 114.7, 115.4, 115.3, 118.5, 120.2, 121.3, 123.3,
125.1, 126.1, 128.7, 129.9, 129.9, 130.5, 131.4, 133.5, 134.1, 136.0, 147.9,
154.2. MS (MALDI TOF) (MH)þ¼831. MS (EI, 70 eV): m/z (%) 831.2
(Mþþ1, 61), 830.2 (Mþ, 100), 415.8 (4.6), 415.3 (13.3), 349.7 (3.4),
349.2 (3.1), 97.3 (5.3), 85.3 (4.1), 83.3 (5.7), 81.3 (6.0).
4.4.3. 21,31-Diphenyl-12,42-dioxo-7-oxa-1,4(3,1)-diquinoxalina-
2(2,3),3(3,2)-diindolizinacyclononaphane (5c). Yellow powder, mp
>360 ꢂC. Found: C, 77.49; H, 4.67; N, 11.44. C48H34N6O3 requires:
C, 77.61; H, 4.61; N, 11.31%. IR (nmax, cmꢀ1, KBr): 3072, 3048,
2952, 2854, 1663, 1602, 1583, 1520, 1489, 1459, 1440, 1363, 1346,
1310, 1280, 1249, 1235, 1164, 1123, 1093, 1074, 1038, 1008, 758,
727, 700, 560. dH NMR (400.1 MHz, DMSO-d6): 3.47 (2H, m, H2),
3.76 (2H, m, H2), 3.79 (2H, m, H1), 4.45 (2H, m, H1), 6.80 (2H, t, J
6.9 Hz, H6 Ind), 7.04 (2H, dd, J 8.2, 6.9 Hz, H7 Ind), 7.09 (2H, m,
H6 Qx), 7.15e7.20 (12H, m, ArH), 7.37 (2H, d, J 6.7 Hz, H8 Qx),
7.47 (2H, td, J 6.7, 3.0 Hz, H7 Qx), 7.68e7.81 (4H, m, H5 and H8
Ind); dC (151 MHz, DMSO-d6): 40.4, 67.1, 112.4, 113.7, 114.3, 114.6,
117.9, 120.5, 123.2, 124.8, 125.8, 127.2, 128.5, 128.7, 130.1, 130.5,
130.7, 132.8, 133.1, 135.9, 153.5, 153.7. MS (MALDI TOF)
(MH)þ¼743.
4.4.6. 21,31-Diphenyl-12,42-dioxo-11,13,17-trioxa-1,4(3,1)-diquinox-
alina-2(2,3),3(3,2)-diindolizinacyclotricosaphane (5f). Yellow pow-
der, mp 293e295 ꢂC. Found: C, 76.27; H, 6.17; N, 8.90. C60H58N6O5
requires: C, 76.41; H, 6.20; N, 8.91%. IR (nmax, cmꢀ1, KBr): 2928,
2854, 1647, 1601, 1526, 1454, 1365, 1348, 1307, 1278, 1261, 1097,
1040, 760, 703, 553, 461, 431. dH NMR (400.1 MHz, DMSO-d6):
0.85e1.43 (16H, m, H2eH5), 3.31 (4H, m, H6), 3.44 (4H, m, H9), 3.51
(4H, m, H8), 3.64 (4H, m, H1), 6.79 (2H, t, J 6.4 Hz, H6 Ind), 6.98 (2H,
dd, J 8.9, 6.4 Hz, H7 Ind), 7.10 (2H, t, J 7.0 Hz, H6 of Qx), 7.19e7.24
(12H, m, ArH), 7.41 (2H, d, J 7.9 Hz, H8 Qx), 7.51 (2H, dd, J 7.9, 7.0 Hz,
H7 Qx), 7.59 (2H, d, J 6.4 Hz, H5 Ind), 7.66 (2H, d, J 8.9 Hz, H8 Ind); dC
151 MHz, DMSO-d6: 25.5, 26.0, 26.5, 29.2, 41.0, 69.8, 70.3, 70.4,
112.2, 113.5, 114.2, 114.4, 117.9, 120.0, 123.0,124.7, 125.7, 126.2, 128.4,
129.0, 129.7, 130.4, 130.5, 132.6, 132.8, 134.9, 153.3, 153.8. MS (EI,
4.4.4. 21,31-Diphenyl-12,42-dioxo-7,10-dioxa-1,4(3,1)-diquinoxalina-
2(2,3),3(3,2)-diindolizinacyclododecaphane (5d). Yellow powder,
mp >360 ꢂC. Found: C, 76.46; H, 4.78; N, 10.54. C50H38N6O4 re-
quires: C, 76.32; H, 4.87; N, 10.68%. IR (nmax, cmꢀ1, KBr): 2960, 1651,
1601,1520,1486,1448,1365,1309,1274,1252,1162, 1095, 1050, 986,
760, 703. dH NMR (400.1 MHz, DMSO-d6): 3.30e3.80 (8H, m, H2 and
H3), 3.96 and 4.25 (4H, m, H1), 6.83 (2H, t, J 6.5 Hz, H6 Ind), 7.04
(2H, dd, J 9.1, 6.5 Hz, H7 Ind), 7.13 (2H, m, H6 Qx), 7.14e7.25 (12H, m,
ArH), 7.46e7.57 (4H, m, H7 and H8 Qx), 7.67 (2H, d, J 9.1, H8 Ind),
7.92 (2H, d, J 6.5, H5 Ind); dC (151 MHz, CDCl3 (50%)þDMSO-d6
(50%)): 42.0, 67.3, 70.6, 111.5, 113.5, 114.6, 114.7, 117.9, 120.6, 123.4,
123.6, 126.0, 126.2, 127.0, 128.9, 129.1, 130.3, 130.7, 131.3, 133.3,

10686
V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
70 eV): m/z (%) 943 (Mþþ1, 41), 942 (Mþ, 100), 472 (11), 471 (16),
377 (12), 336 (14), 335 (21).
69.6, 110.0, 112.4, 113.6, 114.4, 115.2, 118.1, 120.4, 121.9, 123.4, 124.9,
125.9, 126.4, 128.7, 129.2, 129.6, 130.6, 130.7, 132.7, 133.5, 135.2,
149.2, 153.7, 154.0. MS (MALDI TOF) (MH)þ¼923.
Crystallographic data for 5fꢁ Pb(ClO4)2: C60H58Cl2N6O13Pb,
2CHCl3, colorless prism crystal, M¼1587.96, monoclinic, a¼16.943
3
ꢂ
ꢀ
ꢀ
ꢀ
ꢀ
(6) A, b¼17.939 (7) A, c¼22.611 (9) A,
b
¼99.753 (5) , V¼6773 (4) A ,
T¼296 (2) K, space group P21/n, Z¼4,
m(l
MoKa)¼2.871 mmꢀ1
,
rcalcd¼1.557 g cmꢀ3, F(000)¼3184, 66,586 reflections measured,
15,678 independent reflections (Rint¼0.0935), full-matrix least-
squares on F2, parameters¼835, restraints¼795. Final indices
R1¼0.0569 (I>2
s
(I)), wR2¼0.1174 (I>2 (I)), R1¼0.1679 (all data),
s
wR2¼0.1567 (all data), goodness-of-fit on F2¼0.962.
4.4.9. 21,31-Diphenyl-12,42-dioxo-7,10,12,15-tetraoxa-1,4(3,1)-diqui-
noxalina-2(2,3),3(3,2)-diindolizina-11(1,3)-benzenacyclooheptadeca-
phane (5i). Yellow powder, mp 249e251 ꢂC. Found: C, 75.37; H,
5.07; N, 9.16. C58H46N6O6 requires: C, 75.47; H, 5.02; N, 9.10%. IR
(
nmax, cmꢀ1, Nujol mull): 1654, 1602, 1559, 1522, 1508, 1489, 1344,
1307, 1285, 1181, 1154, 1128, 1038, 758, 727, 702. 1H NMR
(400.1 MHz, CDCl3): dH NMR (400.1 MHz, DMSO-d6): 3.48e3.62
(12H, m, H2, H4 and H5), 4.01 (4H, m, H1), 5.49 (1H, br s, H2 Re),
6.28 (2H, d, J 6.2 Hz, H4 Re), 6.79 (2H, t, J 6.6 Hz, H6 Ind), 6.91e7.29
(17H, m, ArH), 7.34 (2H, m, H7), 7.43 (2H, m, H8 Qx), 7.52 (2H, d, J
6.6 Hz, H5 Ind), 7.68 (2H, d, J 9.3 Hz, H8 Ind); dC (151 MHz, DMSO-
d6): 42.0, 67.2, 67.9, 69.5, 101.3, 107.9, 110.0, 112.7, 114.4, 115.2, 118.2,
120.3, 123.1, 124.7, 125.8, 126.0, 128.7, 129.2, 129.6, 129.7, 130.2,
130.6, 132.7, 133.3, 135.1, 153.3, 153.9, 159.8. MS (MALDI TOF)
(MH)þ¼923.
4.4.7. 21,31-Diphenyl-12,42-dioxo-7,10,13,16-tetraoxa-1,4(3,1)-diqui-
noxalina-2(2,3),3(3,2)-diindolizinacyclooctadecaphane (5g). Yellow
powder, mp 309e311 ꢂC (DMSO-d6). Found: C, 74.04; H, 5.17; N,
9.65. C54H46N6O6 requires: C, 74.13; H, 5.30; N, 9.60%. IR (nmax, cmꢀ1
,
KBr): 3072, 2923, 2868, 1654, 1602, 1583, 1529, 1520, 1488, 1444,
1363, 1347, 1308, 1278, 1424, 1125, 768, 727, 700, 608, 560, 507, 434.
dH NMR (400.1 MHz, DMSO-d6): 3.32e3.39 (12H, m, H4, H5 and
H7), 3.41 (4H, m, H2), 3.88e4.09 (4H, m, H1), 6.79 (2H, dd, J 7.2,
5.4 Hz, H6 of Ind), 6.99 (2H, dd, J 8.9, 7.2 Hz, H7 of Ind), 7.12 (2H, t, J
6.9 Hz, H6 of Qx), 7.13e7.22 (12H, m, ArH), 7.49 (4H, m, H7 and H8
Qx), 7.55 (2H, d, J 5.4 Hz, H5 Ind), 7.68 (2H, d, J 8.9 Hz, H8 Ind); dC
(151 MHz, DMSO-d6): 41.5, 67.0, 69.8, 70.1, 70.2, 112.3, 113.7, 114.4,
114.9, 1187.0, 120.1, 123.0, 124.5, 125.6, 126.0, 128.5, 129.1, 129.5,
130.2, 130.4, 132.6, 133.3, 135.1, 153.4, 153.5. MS (MALDI TOF) (MH)þ
875, (MþNa)þ¼897, (MþK)þ¼913.
4.4.10. 21,31-Diphenyl-12,42-dioxo-9,12,15,18,21-pentaoxa-1,4(3,1)-
diquinoxalina-2(2,3),3(3,2)-diindolizinacyclopentacosaphane mono-
hydrate (5j). Yellow powder, mp 130e132 ꢂC. Found: C, 72.43; H,
5.95; N, 8.36. C60H60N6O8 requires: C, 72.56; H, 6.09; N, 8.46%. IR
4.4.8. 21,31-Diphenyl-12,42-dioxo-7,10,12,15-tetraoxa-1,4(3,1)-diqui-
noxalina-2(2,3),3(3,2)-diindolizina-11(1,2)-benzenacyclooheptadeca-
phane (5h). Yellow powder, mp 220e222 ꢂC. Found: C, 75.39; H,
5.06; N, 9.08. C58H46N6O6 requires: C, 75.47; H, 5.02; N, 9.10%. IR
(
nmax, cmꢀ1, KBr): 2924, 2855, 1644, 1600, 1582, 1519, 1455, 1365,
1348, 1307, 1278, 1221, 1093, 1068, 761, 704, 559, 446, 463, 430. dH
NMR (400.1 MHz, DMSO-d6): 1.25e1.51 (8H, m, H2 and H3),
3.36e3.48 (20H, m, H4, H6, H7, H8, H9 and H10), 3.76 and 3.91 (4H,
m, H1), 6.80 (2H, t, J 6.7 Hz, H6 Ind), 6.88 (2H, d, J 6.8 Hz, H5 Qx),
6.99 (2H, dd, J 9.1, 6.7 Hz, H7 of Ind), 7.01 (2H, dd, J 7.7, 6.8 Hz, H6
Qx), 7.07e7.31 (10H, m, ArH), 7.39 (2H, d, J 8.1 Hz, H8 Qx), 7.44 (2H,
dd, J 8.1, 7.7 Hz, H7 of Qx), 7.51 (2H, d, J 6.7 Hz, H5 of Ind), 7.67 (2H, d,
J 9.1 Hz, H8 Ind); dC (151 MHz, DMSO-d6): 23.9, 26.4, 41.3, 60.7, 69.9,
70.1, 70.2, 72.8, 110.0, 112.6, 114.4, 114.5, 114.6, 118.3, 120.0, 123.2,
(
nmax, cmꢀ1, Nujol mull): 1649, 1600, 1583, 1560, 1520, 1504, 1366,
1350, 1308, 1281, 1257, 1222, 1158, 1126, 1040, 1024, 958, 933, 761,
729, 705. dH NMR (400.1 MHz, DMSO-d6): 3.28e3.59 (8H, m, H2 and
H4), 3.89e4.05 (8H, m, H1 and H5), 6.79 (2H, dd, J 7.0, 7.2 Hz, H6
Ind), 6.85e6.95 (4H, m, H2 and H3 Ca), 6.99 (2H, dd, J 9.3, 7.2 Hz, H7
of Ind), 7.07 (2H, t, J 6.9 Hz, H6 Qx), 7.13e7.31 (12H, m, ArH),
7.42e7.49 (4H, m, H7 and H8 Qx), 7.65 (2H, d, J 7.0 Hz, H5 Ind), 7.67
(2H, d, J 9.3 Hz, H8 Ind); dC (151 MHz, DMSO-d6): 41.8, 67.7, 69.3,

V.A. Mamedov et al. / Tetrahedron 69 (2013) 10675e10687
10687
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153.5, 153.7. MS (MALDI TOF) (MþH3O)þ¼993.
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,
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ddd, J 7.2, 6.6, 1.0 Hz, H6 Ind), 6.64 (2H, ddd, J 9.2, 6.6, 0.7 Hz, H7
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Acknowledgements
This work was supported by the Russian Foundation for Basic
Research (grants No. 13-03-00123-a, 09-03-99011-r-ofi, 13-03-
97073) and by the Federal Agency of Science and Innovation (the
state contract No. 02.740.11.0633: 8432).
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Supplementary data
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2013.09.014.
These data include MOL files and InChiKeys of the most important
compounds described in this article.
42. Jiang, Q.; Zhang, H.-Y.; Han, M.; Ding, Z.-J.; Liu, Y. Org. Lett. 2010, 12,
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