First examples of the synthesis of macroaluminahetero(N,S)cycles with the participation of metallo(Ti,Zr)cene catalysts

Article abstract of DOI:10.1016/j.tetlet.2015.04.089

An efficient method is developed for the selective synthesis of 4-aryl-2,6,8,11-tetraethyl-1,7-dithia-4-aza-2,6,8,11-tetraaluminacycloundecanes via the reaction of 3-aryl-1,5,3-dithiazepanes with EtAlCl₂ involving the participation of a two-component catalyst based on Cp₂TiCl₂ and Cp₂ZrCl₂.

Full text of DOI:10.1016/j.tetlet.2015.04.089

Accepted Manuscript
First examples of the synthesis of macroaluminahetero(N,S)cycles with the par-
ticipation of metallo(Ti,Zr)cene catalysts
Natalia N. Makhmudiyarova, Liliya V. Mudarisova, Tatiyana V. Tyumkina,
Vasiliy M. Yanybin, Аskhat G. Ibragimov, Usein М. Dzhemilev
PII:
S0040-4039(15)00735-2
DOI:
http://dx.doi.org/10.1016/j.tetlet.2015.04.089
TETL 46228
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
11 November 2014
1 April 2015
21 April 2015
Please cite this article as: Makhmudiyarova, N.N., Mudarisova, L.V., Tyumkina, T.V., Yanybin, V.M., Ibragimov,
А., Dzhemilev, U., First examples of the synthesis of macroaluminahetero(N,S)cycles with the participation of
metallo(Ti,Zr)cene catalysts, Tetrahedron Letters (2015), doi: http://dx.doi.org/10.1016/j.tetlet.2015.04.089
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First examples of the synthesis of macroaluminahetero(N,S)cycles
with the participation of metallo(Ti,Zr)cene catalysts
Natalia N. Makhmudiyarova∗, Liliya V. Mudarisova, Tatiyana V. Tyumkina, Vasiliy M.
Yanybin, Аskhat G. Ibragimov, Usein М. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
141 Prospekt Oktyabrya, Ufa, 450075, Russian Federation, E-mail: ink@anrb.ru
Abstract: An efficient method is developed for the selective synthesis of 4-aryl-2,6,8,11-
tetraethyl-1,7-dithia-4-aza-2,6,8,11-tetraaluminacycloundecanes via the reaction of 3-aryl-1,5,3-
dithiazepanes with EtAlCl
and Cp ZrCl
2 2 2
involving the participation of a two-component catalyst based on Cp TiCl
2
2
.
Keywords: catalysis, 3-aryl-1,5,3-dithiazepanes, magnesium, ethylaluminum dichloride, titanocene dichloride,
zirconocene dichloride, substituted 1,7-dithia-4-aza-2,6,8,11-tetraaluminacycloundecanes.
1
2
3
The discovery of the catalytic cycloalumination of olefins, allenes, and acetylenes
provided a facile route to the selective synthesis of aluminacarbocycles. Aluminacarbocycles
have attracted considerable interest due to their high reactivity in transformations without
4
5
6
preliminary isolation to form cyclopropanes, cyclobutanes, thiophanes, selenophanes,
7
8
9
10
phospholanes, cyclopropanols, cyclopentanols, and cyclopentanecarboxylic esters of
practical importance. Despite a diverse range of methods for the preparation of
1
1
aluminacarbocycles being available,
reports on the selective synthesis of
aluminahetero(N,S)cycles are lacking in the literature. Aluminaheterocycles are not formed upon
1
2
catalytic cycloalumination of N,S,O-containing α-olefins or by reactions of heterocycles with
13
organoaluminum compounds.
With the aim of developing an efficient method for the synthesis of new classes of N,S-
containing metallaheterocycles, and to examine the possibility of the synthesis of
aluminaheterocycles by the insertion of Al atoms into the С-heteroatom bond in S,N-containing
heterocycles, we studied the reaction of EtAlCl
based on metallocene dichlorides - Cp MCl (M = Ti, Zr).
It is known that Cp Ti can insert into the С-S bond of substituted allylsulfanylbenzenes.
We hypothesized that the in situ generation of titanocene by the reduction of Cp TiCl with
magnesium metal in a solution of an N,S-containing heterocycle would lead to the oxidative
insertion of Cp Ti into the С-heteroatom bond of the starting heterocycle (by analogy with the
reaction of Cp TiCl
the titanaheterocycles would react with EtAlCl
heterocycles.
We studied the effect of the nature of the catalyst (Cp
2
with 3-aryl-1,5,3-dithiazepanes using catalysts
2
2
1
4
2
2
2
1
5
2
1
4
2
2
with allylsulfanylbenzenes ), to form titanaheterocycles. We expected that
1
6
2
to afford the corresponding Al-containing
2
TiCl
O, THF), the temperature (0-40 С), and the reactant ratio on the yield of the
resulting metallaheterocycles using the model reaction of 3-phenyl-1,5,3-dithiazepane with
EtAlCl in the presence of magnesium metal (powder) (Tables 1 and 2).
2 2 2
, Cp ZrCl ), the type of
о
ethereal solvent (Et
2
2
∗
Corresponding author. E-mail adress: nataliya.mnn@gmail.com (Makhmudiyarova N.N.)
1

We found that the reaction did not occur in the absence of catalysts or magnesium metal
powder). The Cp TiCl -catalyzed reaction of 3-phenyl-1,5,3-dithiazepane, EtAlCl , and Mg
taken in a molar ratio of 0.05:1:5:5 afforded a mixture of aluminaheterocycles consisting of
(
2
2
2
2
,6,8,11-tetraethyl-4-phenyl-1,7-dithia-4-aza-2,6,8,11-tetraaluminacycloundecane
(1)
and
(2)
2,4,7,9,12-pentaethyl-5-phenyl-1,8-dithia-5-aza-2,4,7,9,12-pentaaluminacyclododecane
(
Scheme 1) in a ratio of 45:55 and overall yield of 54% (Table 1). The overall yield of
aluminaheterocycles 1 and 2 in the reaction catalyzed by Cp ZrCl (5 mol%) was not higher than
%. The reaction using a mixed catalyst composed of Cp TiCl (5 mol%) and Cp ZrCl (5
mol%) gave macroaluminaheterocycles 1 and 2 in a yield of 78% and ratio of ~15:1. It should be
noted that the overall yield of 1 and 2 using γ-Al -supported Cp TiCl and Cp ZrCl as the
catalysts was not higher than 5%. The content of Cp TiCl and Cp ZrCl in the heterogeneous
2
2
8
2
2
2
2
2
O
3
2
2
2
2
2
2
2
2
catalyst was 19.4 and 18.2 wt%, respectively (Table 2). The yields and the ratios of
1
7
aluminaheterocycles 1 and 2 were determined based on hydrolysis products 3 and 4.
Et
Al
Et
Et
Et
Et
S
S
S
S
1
Al
Al
Al
Al
3
11
10
2
[
M]
Ph
N
Ph
N
+5Mg+ 5EtAlCl2
Ph
N
4
+
9
-
MgCl2
5
7
Al
Al
Al
Al
8
Et
S
2
6
S
Et
Et
Et
1
-
OH /H O
D O
2
2
CH3
+ Ph NCH + C H + CH + H S
Ph
N
D
3
2
6
4
2
Ph
N
D
+
Ph
N
CH3
H 4
3
D
6
5
D
Scheme 1.
Therefore, the reaction described above of 3-phenyl-1,5,3-dithiazepane, EtAlCl
TiCl о, and Cp ZrCl in a molar ratio of 1:5:5:0.05:0.05 in a mixture of Et O–THF (1:1, v/v)
at 40 С afforded a mixture of 2,6,8,11-tetraethyl-4-phenyl-1,7-dithia-4-aza-2,6,8,11-
2
, Мg,
Cp
2
2
2
2
2
18
tetraaluminacycloundecane (1) and 2,4,7,9,12-pentaethyl-5-phenyl-1,8-dithia-5-aza-2,4,7,9,12-
pentaaluminacyclododecane (2) in a ratio of 94:6 in 78% yield.
Table 1. Effect of the nature of the catalyst and the reactant ratio on the yield of
macroaluminaheterocycles 1 and 2. Reaction conditions: a mixture of THF and Et
solvent, 40 С, 8 h
2
O as the
о
N-Phenyl-1,5,3-
dithiazepane:EtAlCl2:
[M]
Ratio of
products
Overall
yield of
1+2 (%)
Mg:[M], mmol
1
2
1
:1:0:0
-
-
-
-
1
1
:5:0:0
:5:5:0
-
-
-
-
-
-
-
-
-
-
-
1
1
1
:1:1:0.05
:2:2:0.05
:3:3:0.05
Cp TiCl
2
2
Cp TiCl
-
-
-
-
-
-
2
2
Cp TiCl
2
2
2

1
1
1
:4:4:0.05
:5:0:0.05
:5:5:0.05
Cp TiCl
-
-
-
2
2
Cp TiCl
-
-
-
2
2
Cp TiCl
45
61
94
55
39
6
54
2
2
1
:5:5:0.05
Cp ZrCl
8
2
2
1
1
:5:5:0.05:0.05
Cp TiCl + Cp ZrCl
78
2
2
2
2
:5:5:0.05:0.05
Cp
Cp
2
TiCl
2
/Al
2
O
3
+
3
55
45
5
2
ZrCl
2
/ Al
2
O
Table 2. Effect of the nature of the ethereal solvent and the temperature on the yield of
N-phenylaluminaheterocycles
dithiazepane:EtAlCl :Mg:Cp
1
ZrCl
and
2
(3-phenyl-1,5,3-
2
2
2
TiCl :Cp
2
2
= 1:5:5:0.05:0.05, 8 h)
Solvent
Т (°С)
Ratio of products
Overall
yield of
1
+2 (%)
1
2
THF
THF
0
20
46
65
54
35
50
57
THF
50
0
71
48
55
86
29
52
45
14
68
32
41
55
Et O
2
Et O
20
35
2
Et O
2
THF-Et O
0
54
59
94
46
41
6
44
59
78
2
THF-Et O
20
40
2
THF-Et O
2
To examine the possibility of performing this reaction with other 3-aryl-1,5,3-
dithiazepanes, we studied the insertion of aluminum atoms into 3-[4-methyl(OCH , NO , Cl,
and Mg in the presence of
O–THF mixed solvent (1:1, v/v)
at 40 С. It was found that under the reaction conditions used, p-substituted 3-phenyl-1,5,3-
dithiazepanes reacted with EtAlCl to give the corresponding 4-aryl-2,6,8,11-tetraethyl-1,7-
dithia-4-aza-2,6,8,11-tetraaluminacycloundecanes 9a-d in 73-88% yields (Scheme 2). The
3
2
1
9
Br)phenyl]-1,5,3-dithiazepanes 7a-d via their reactions with EtAlCl
the two-component catalyst, Cp TiCl –Cp ZrCl (1:1) in the Et
2
2
2
2
2
2
о
2
2
0
2
1
yields of 9a-d were determined based on the hydrolysis products 10a-d.
3

Et
Et
Et
Et
S
S
S
Al
Al
Al
Al
[
Cp TiCl + Cp ZrCl ]
2
2
2
2
R
N
+5Mg + 5EtAlCl2
R
N
-
MgCl2
7
a-d
S
R = Ме (a), ОМе (b), Cl (c), Br (d)
9a-d
H O/OH-
2
CH3
R
N
CH3
10a-d
Scheme 2.
1
5,16,22,23
Based on the experimental results and literature data,
the probable mechanism for
the formation of the S,N-containing aluminaheterocycles is as follows. The first step involves
1
5
reduction of the mixed catalyst (Cp
and Cp Zr. Subsequent insertion of the in situ generated metallocene Cp
bonds of the 3-aryl-1,5,3-dithiazepane gives macroheterocycles 8. The catalytic
2
TiCl
2
+ Cp
2
ZrCl
2
) with magnesium metal to give Cp
2
Ti
2
2
M into the active C-S
1
6,22,23
transmetallation
,7-dithia-4-aza-2,6,8,11-tetraaluminacycloundecanes 9, accompanied by regeneration of the
starting metallocene dichlorides (Scheme 3).
of metallaheterocycles 8 with EtAlCl
2
produces 4-aryl-2,6,8,11-tetraethyl-
1
Et
Et
Et
Mg
S
Al
Al
Al
Cp МCl
2
2
Ar
N
Al
MgCl2
S
9
Et
"
Cp М"
M=Ti,Zr
2
Cp2
М
Cp2
М
S
S
S
EtAlCl2
Ar
N
Ar
N
М
М
Cp2
8
Cp
S
2
Scheme 3.
The
structures
of
4-aryl-2,6,8,11-tetraethyl-1,7-dithia-4-aza-2,6,8,11-
2
7
tetraaluminacycloundecanes 9a-d were determined by multinuclear NMR spectroscopy. The Аl
NMR spectrum of macroheterocycles 9a-d showed, in addition to the signal of the starting
EtAlCl
sulfur or nitrogen atom. In the Н NMR spectra of aluminaheterocycles 9a-d, the methylene
protons of the ethyl substituents (CH CH Al) were responsible for the broadened high-field
signals (W = 3.5 kHz) in the range δ –0.18 to 0.10, which is consistent with the literature data
for trialkylalanes. The signals of the methylene protons located between the aluminum atoms
Al-CH -CH -Al) of macrocycles 9a-d were also observed in this δ range. The resonances due to
the protons of the Al-CH -CH -Al and СН -CH -Al groups overlapped, whereas the chemical
2
(δAl = 106), resonances at δ 50–55 characteristic of aluminum atoms bonded directly to a
2
4
1
3
2
½
2
5
(
2
2
2
2
3
2
1
3
shifts of the corresponding carbon atoms of these moieties in the С NMR spectra were
4

substantially different. The carbon signals of the Al-CH
were shifted downfield to ~10 ppm with respect to the signals of the carbon atoms α to the Al
atom in the ethyl substituent (CH -CH -Al). These results are illustrated in Figure 1 with product
c as an example. In the HSQC spectrum, the signals of the methylene protons bonded directly
to the Al atom in the δCH -Al range of -0.18 to 0.10 showed correlations to both the carbon
signals at δ 0.0–0.2 and the carbon signals in the δ range 9.0–10.2. Apparently, the signals at δ
2 2
-CH -Al group in macrocycles 9a-d
3
2
9
2
3 2
0.0–0.2 correspond to the carbon atoms bonded to aluminum (CH -CH -Al), and the signals at δ
9
CH
.0–10.2 can be assigned to the methylene carbon atoms located between the Al atoms (Al-CH
2
-
1
3
2
-Al) in macrocycles 9a-d. The С NMR spectra of macrocycles 9a-d showed signals at δ
28–30 which were assigned to the carbon atoms located between the nitrogen and aluminum
atoms. The fact that these carbon atoms belong to the macroheterocycle was confirmed by their
HMBC cross-peaks with the protons of the ethyl groups at the adjacent Al atom (Figure 1b). The
presence of a series of cross-peaks between the narrow region of δ 9-10 for the carbon atoms and
1
the whole broad region of the H NMR spectrum from δ -0.3 also provided evidence in support
of the heteronuclear couplings presented in Figure 2.
5

Figure 1. Heteronuclear correlation spectra of compound 9с, а) HSQC; b) HMBC
H
H
H
Al
S
Al
S
H
Figure 2. Key HMBC interactions for compound 9c
The above-described differences in the chemical shifts of the ethyl (СН
3 2
-CH -Al) and
1
3
ethane (Al-CH -CH -Al) α-carbon atoms bonded to the Al atoms observed in the С NMR
2
2
spectra can be used additionally to establish the structure of macroaluminaheterocycle 2, which
we have proposed based on analysis of the hydrolysis and deuterolysis products. Since
macrocycle 2 is non-symmetric, we envisaged that the HSQC spectrum of 2,4,7,9,12-pentaethyl-
5
-phenyl-1,8-dithia-5-aza-2,4,7,9,12-pentaaluminacyclododecane (2) would have a series of
cross-peaks. Analysis of the HSQC spectrum of macroaluminaheterocycle 2 confirmed this fact
Figure 3). As can be seen from the spectrum, the signals at δ 9.5-10.5 belong to the
AlCH CH Al group of macrocycle 2, in which the carbon atoms are magnetically nonequivalent,
and the signals at δ 4.0-6.5 were assigned to AlCH Al. The chemical shifts of this spacer appear,
as expected, at higher field compared to the signals of AlCH
aluminum atoms.
(
2
2
2
2
CH
2
Al due to the effect of geminal
6

2
AlCH Al
Figure 3. Fragment of the HSQC spectrum of compound 2.
1
3
It should be noted that in the 1D С NMR spectra of heterocycles 9a-d, multiple splitting
or broadening was observed for the signal of the methylene carbon atom located between the Al
and N atoms (Al-CH
attributed to the formation of diastereomeric complexes in solution. Actually, the coordination of
Et O or THF solvent molecules to Al gives rise to stereogenic centers at each of the four
2
-N); this signal does not coincide with other signals. This result can be
2
aluminum atoms of macrocycles 9a-d and, as a consequence, the number of diastereomeric
complexes increases. Calculations of the thermodynamic parameters of complexation of
macrocycles 9a-d with four THF molecules showed that the formation of stereoisomeric
complexes was energetically favorable. The Gibbs free energy of complexation of each THF
molecule with the non-associated heterocycle is ca. 3.5 kcal/mol. Figure 4 presents the optimized
structure of one of the stable diastereomers.
Figure 4. Optimized structure of the complex of macroaluminaheterocycle 1 with THF.
In the calculated structure corresponding to the minimum in the potential energy surface
of the complex (Figure 4), the bond lengths are as follows: d (Al-S) = 2.26 Å, d (Al-Ccycle) = d
(
Al-Cacycle) = 2.00 Å, d (Al-O) = 2.05 Å.
The structure of tetraaluminaheterocycle 1 was additionally confirmed by MALDI-TOF
mass spectrometry using HCCA as the matrix. The spectrum showed a molecular ion peak at m/z
+
+
4
75.005 [M+K+H] (9%) and fragment ion peaks at m/z 461.327 [M-CH
2
+K+H] (9%), m/z
7

+
+
3
56.347 [M-Ph-2H] (64%), and m/z 342.342 [M-Ph-N] (32%) indicative of the formation of
aluminaheterocycle 1.
In conclusion, we have developed a new method for the selective synthesis of 4-aryl-
,6,8,11-tetraethyl-1,7-dithia-4-aza-2,6,8,11-aluminacycloundecanes by the insertion of Al atoms
into the C–S bonds in 3-aryl-1,5,3-dithiazepanes mediated by EtAlCl , with participation of a
2
2
two-component catalyst based on Cp
2
TiCl
2
and Cp
2
ZrCl .
2
Acknowledgments
This work was supported financially by the Russian Foundation for Basic Research (Grants 13-
3-12027, 14-03-00240, 14-03097023 and 14-03-31420).
0
References and notes
1
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Russ. Chem. Bull., Int. Ed. 2001, 50, 2188.
2
3. Dzhemilev, U. M.; Ibragimov, A. G.; Zolotarev, A. P. Mendeleev Commun. 1992, 2, 135.
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Bull. Akad. Sci. USSR, Div. Chem. Sci. 1990, 39, 1071.
. Dzhemilev, U. M.; Ibragimov, A. G.; Zolotarev, A. P.; Muslukhov, R. R.; Tolstikov, G. A.
Bull. Akad. Sci. USSR, Div. Chem. Sci. 1989, 38, 1981.
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Div. Chem. Sci. 1989, 38, 1324.
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7
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51, 4333. (d) Dzhemilev, U. M.; Ibragimov, A. G.; J. Organomet. Chem. 1994, 466, 1.
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1
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8. Synthesis of 2,6,8,11-tetraethyl-4-phenyl-1,7-dithia-4-aza-2,6,8,11-
tetraaluminacycloundecane (1) and 2,4,7,9,12-pentaethyl-5-phenyl-1,8-dithia-5-aza-2,4,7,9,12-
pentaaluminacyclododecane (2) (general procedure): Cp TiCl (0.0125 g, 0.05 mmol), Cp ZrCl
0.0146 g, 0.05 mmol), Mg powder (0.12 g, 5 mmol), N-phenyl-1,5,3-dithiazepane (1 mmol),
2
2
2
2
(
THF (5 mL), and Et
2
O (5 mL) were placed in a 50 mL glass reaction flask equipped with a
8

о
о
magnetic stir bar under dry Ar at 0 С. The temperature was raised to 40 С and the mixture was
stirred for 8 h. The mixture was quenched by the addition of 25% aq. KOH. The organic layer
2
was separated and the aqueous layer extracted with Et O (3 × 50 ml). The combined organic
layer was dried over MgSO . Compounds 3 and 4 were identified by comparison with known
4
1
7
samples.
,6,8,11-Tetraethyl-4-phenyl-1,7-dithia-4-aza-2,6,8,11-tetraaluminacycloundecane (1): colorless
2
1
crystals (unstable in air). H NMR (400.13 MHz, THF-d
.2 – 1.2 (br s, 8Н, CH , H-12,20,22,24), 0.9 – 1.1 (br s, 12Н, CH
s, 4Н, CH , H-3,5), 6.4 - 6.5 (br s, 2Н, CH, H-15,19), 6.6 – 6.7 (br s, 2Н, CH, H-16,18), 7.0 – 7.2
8 2
): δ -0.0 – 0.1 (br s, 4Н, CH , H-9,10), -
0
2
3
, H-13,21,23,25), 1.5 – 1.7 (br
2
13
(
br s, 1Н, CH, H-17). С NMR (100.62 MHz, THF-d
8
): δ 0.0 – 3.0 (C-12,20,22,24), 8.8 – 10.6
(
C-9,10,13,21,23,25), 28.6 and 30.6 (C-3 and C-5), 113.4 (C-16,18), 117.2 (C-15,19); 129.8 (C-
27
1
1
2
2
7), 150.8 (C-14). Al NMR (400.13 MHz, THF-d
8
): δ 48.7 (W = 3.5 kHz).
½
9. Murzakova, N.N.; Prokof’ev, K.I.; Tyumkina, T.V.; Ibragimov, A.G. Russ. J. Org. Chem.
012, 48, 588.
0.
Synthesis
of
2,6,8,11-tetraethyl-4-(aryl)-1,7-dithia-4-aza-2,6,8,11-
TiCl (0.0125 g, 0.05 mmol),
(0.0146 g, 0.05 mmol), Mg powder (0.12 g, 5 mmol), N-aryl-1,5,3-dithiazepane (1
mmol), THF (5 mL), and Et O (5 mL) were placed in a 50 mL glass reaction flask equipped with
tetraaluminacycloundecanes 9а-d (general procedure): Cp
Cp ZrCl
2
2
2
2
2
о
о
a magnetic stir bar under dry Ar at 0 С. The temperature was raised to 40 С, and the mixture
was stirred for 8 h. The mixture was quenched by the addition of 25% aq. KOH. The organic
layer was separated and the aqueous layer was extracted with Et
2
O (3 × 50 ml). The combined
organic layer was dried over MgSO . Compound 10a was identified by comparison with a
4
1
7
21
known sample; compounds 10b-d were identified by comparison with known samples.
,6,8,11-Tetraethyl-4-(4-methylphenyl)-1,7-dithia-4-aza-2,6,8,11-tetraaluminacycloundecane
2
1
(
C
1
2
9а): colorless crystals unstable (in air) . H NMR (400.13 MHz, C
2
D
5
OC
, H-9,10,12,20,22,24), 0.9 – 1.1 (br s, 12Н, CH
, H-3,5), 2.2 – 2.3 (br s, 3Н, CH , H-26), 6.8 (d, J = 8.4 Hz,
Н, CH, H-16,18); 7.0 (d, 2Н, J = 8.4 Hz, CH, H-15,19). С NMR (100.62 MHz, C OC
OC ): δ 1.1 – 2.6 (C-12,20,22,24), 8.9 – 10.3 (C-9,10,13,21,23,25), 20.6 – 21.1 (C-
6), 30.7 and 31.1 (C-3 and C-5), 117.0 (C-18), 117.1 (C-16), 128.0 (C-17), 130.1 – 130.5 (C-
2
D
5
, THF,
2
H
5
OC
2
H
5
): δ -0.1 – 0.2 (br s, 12Н, CH
2
3
, H-
3,21,23,25), 1.2 – 1.3 (br s, 4Н, CH
2
3
1
3
2
D
5
2 5
D ,
THF, C
2
H
5
2 5
H
2
1
(
27
5,19), 144.9 – 145.5 (C-14). Al NMR (400.13 MHz, C
= 3.5 kHz).
,6,8,11-Tetraethyl-4-(4-methoxyphenyl)-1,7-dithia-4-aza-2,6,8,11-tetraaluminacycloundecane
2 5 2 5 2 5 2 5
D OC D , THF, C H OC H ): δ 54.3
W
½
2
1
(
C
1
1
8
9b): colorless crystals (unstable in air). H NMR (400.13 MHz, C
2
D
5
OC
, H-9,10,12,20,22,24), 1.0 – 1.1 (br s, 12Н, CH
, H-3,5), 2.2 – 2.3 (br s, 3Н, CH , H-26), 6.7 (d, J =8.1 Hz,
Н, CH, H-16); 6.8 (d, J = 8.1 Hz, 1Н, CH, H-18), 7.0 (d, J = 8.1 Hz, 1Н, CH, H-15); 7.1 (d, J =
2
D
5
, THF,
2
H
5
OC
2
H
5
): δ -0.1 – 0.3 (br s, 12Н, CH
2
3
, H-
3,21,23,25), 1.4 – 1.6 (br s, 4Н, CH
2
3
1
3
2 5 2 5 2 5 2 5
.1 Hz, 1Н, CH, H-19). С NMR (100.62 MHz, C D OC D , THF, C H OC H ): δ -0.1 – 1.1
(
5
C-12,20,22,24), 8.0 – 9.7 (C-9,10,13,21,23,25), 19.3 – 20.1 (C-26), 28.4 and 28.6 (C-3 and C-
2
7
), 112.9 (C-18), 113.3 (C-16), 127.9 (C-19), 128.8 (C-15), 129.4 (C-17), 141.4 (C-14). Al
OC , THF, C OC ): δ 54.7 (W = 3.3 kHz).
-(4-Chlorophenyl)-2,6,8,11-tetraethyl-1,7-dithia-4-aza-2,6,8,11-tetraaluminacycloundecane
NMR (400.13 MHz, C
4
2
D
5
2
D
5
2
H
5
2
H
5
½
1
(
9с): colorless crystal (unstable in air). H NMR (400.13 MHz, THF-d
CH , H-9,10), -0.2 – 1.2 (br s, 8Н, CH , H-12,20,22,24), 0.9 – 1.0 (br s, 12Н, CH
3,21,23,25), 1.3 – 1.4 (br s, 4Н, CH , H-3,5), 6.5 – 6.9 (br s, 2Н, CH, H-16,18), 6.9 – 7.0 (br s,
Н, CH, H-15,19). С NMR (100.62 MHz, THF-d ,): δ = 1.0 – 3.1 (C-12,20,22,24), 8.9 – 10.4
8
): δ -0.1 – 0.1 (br s, 4Н,
2
2
3
, H-
1
2
2
1
3
8
(
1
C-9,10,13,21,23,25), 28.5 and 30.0 (C-3 and C-5), 113.7 – 114.4 (C-16,18), 129.0 – 129.9 (C-
2
7
8 ½
5,19), 141.5 (C-14), 153.4 (C-17). Al NMR (400.13 MHz, THF-d ): δ = 53.1 (W = 3.1 kHz).
4
-(4-Bromophenyl)-2,6,8,11-tetraethyl-1,7-dithia-4-aza-2,6,8,11-tetraaluminacycloundecane
1
(
9d): colorless crystal (unstable in air). H NMR (400.13 MHz, THF-d
8
): δ -0.0 (br s, 12Н, CH ,
2
9

H-9,10,12,20,22,24), -0.6 – 2.8 (br s, 12Н, CH
,5), 6.5 (br s, 2Н, CH, H-16,18), 7.0 (br s, 2Н, CH, H-15,19). С NMR (100.62 MHz, THF-d
δ 0.6 – 2.9 (C-12,20,22,24), 9.1 – 10.0 (C-9,10,13,21,23,25), 28.6 and 29.7 (C-3 and C-5), 114.5
3
, H-13,21,23,25), 1.2 – 1.4 (br s, 4Н, CH
2
, H-
1
3
3
8
):
2
7
(
C-16,18), 129.5 (C-15,19), 144.0 (C-14), 151.0 (C-17). Al NMR (400.13 MHz, THF-d ): δ =
8
½
41.6 (W = 3.1 kHz).
2
1. (a) Lee, B. K.; Biscore, M. R.; Buchwald, S. L. Tetrahedron Lett. 2009, 50, 3672. (b)
Thomas, D. J.; Billman, J. H.; Davis, C. E. J. Am. Chem. Soc. 1946, 68, 895. (c) Borch, R. F.;
Hassid, A.I. J. Org. Chem. 1972, 37, 1673.
2
2. Dzhemilev, U. M.; Ibragimov, A. G.; Morozov, A. B.; Muslukhov, R. R.; Tolstikov, G. A.
Bull. Akad. Sci. USSR, Div. Chem. Sci. 1991, 40, 1425.
3. Dzhemilev, U. M.; Ibragimov, A. G.; Morozov, A. B.; Muslukhov, R. R.; Tolstikov, G. A.
Bull. Akad. Sci. USSR, Div. Chem. Sci. 1992, 41, 1089.
2
2
2
2
4. Gálvez-Ruiz, J. C.; Guadarrama-Pérez, C.; Nöth, H.; Flores-Parra, A. Eur. J. Inorg. Chem.
004, 3, 601;
5. Ibragimov, A. G.; Khafizova, L. O.; Khusainova, L. I.; Tyumkina, T. V.; Dzhemilev, U. M.
Russ. J. Org. Chem. 2010, 46, 474.
10

Graphical Abstract
First examples of the synthesis of
macroaluminahetero(N,S)cycles
Et
Et
Et
Et
S
S
S
Al
Al
Al
Al
with
the
participation
of
[
M]
metallo(Ti,Zr)cene catalysts
Ar
N
+5Mg+ 5EtAlCl2
Ar
N
-
MgCl2
S
Natalia
N.
Makhmudiyarova,
Liliya V. Mudarisova, Tatiyana V.
Tyumkina, Vasiliy M. Yanybin,
Аskhat G. Ibragimov, Usein М.
Dzhemilev
Ar = C H , p-MeC H , p-MeOC H , p-ClC H , p-BrC H
4
6
5
6
4
6
4
6
4
6
11