Synthesis and transformations of metallacycles 38.* the Cp 2ZrCl2-catalyzed cyclometallation of α,α- diynes upon the action of RMgR' or RnAlCl3-n

Article abstract of DOI:10.1007/s11172-011-0244-2

The Cp₂ZrCl₂-catalyzed cyclometallation of a,(a-alkadiynes upon the action of RMgR' or RnAlCl_3-n was accomplished to yield unsaturated di- and tricyclic (magnesa)aluminacarbocycles in up to 85% yield.

Full text of DOI:10.1007/s11172-011-0244-2

Russian Chemical Bulletin, International Edition, Vol. 60, No. 8, pp. 1633—1639, August, 2011
1633
Synthesis and transformations of metallacycles
38.* The Cp2ZrCl2ꢀcatalyzed cyclometallation of α,ωꢀdiynes
upon the action of RMgR´ or RnAlCl3–n
V. A. D´yakonov, R. A. Tuktarova, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347) 284 2750. Eꢀmail: ink@anrb.ru
The Cp2ZrCl2ꢀcatalyzed cyclometallation of α,ωꢀalkadiynes upon the action of RMgR´ or
RnAlCl3–n was accomplished to yield unsaturated diꢀ and tricyclic (magnesa)aluminacarbocycles
in up to 85% yield.
Key words: organoaluminum and ꢀmagnesium compounds, metallocomplex catalysis,
aluminacyclopentadiene, magnesacyclopentadiene, diynes, cycloalumination, cyclomagnation.
It is known2—6 that catalytic cyclometallation of
alkynes with simple organoaluminum and ꢀmagnesium
compounds in the presence of transition metal (Zr, Ti,
Co, Hf) complexes is an efficient method for the synthesis
of unsaturated threeꢀ and fiveꢀmembered aluminaꢀ and
magnesacarbocycles: aluminacyclopropenes, aluminaꢀ
cyclopentꢀ2ꢀenes, aluminacyclopentaꢀ2,4ꢀdienes, and
magnesacyclopentaꢀ2,4ꢀdienes (Scheme 1).
literature information on catalytic cycloalumination or
cyclomagnation of α,ωꢀdiynes.
Meanwhile, accomplishment of these reactions, in our
opinion, would have led to the development of efficient
methods for the synthesis of new classes of biꢀ, triꢀ, or
macrocyclic organoaluminum and ꢀmagnesium comꢀ
pounds, which are of practical interest in the development
of oneꢀpot methods for the synthesis of poorly available
carboꢀ and heterocycles.
In continuation of the studies mentioned above, as
well as for the study a possibility of running intraꢀ and
intermolecular cyclometallation of diacetylenes and synꢀ
thesis of new classes of organoaluminum and ꢀmagnesium
compounds, in the present work we for the first time atꢀ
tempted to accomplish catalytic cyclometallation of α,ωꢀdiꢀ
acetylenes using Cp2ZrCl2, as a catalyst precursor, which
displays high catalytic activity and selectivity in cycloꢀ
metallation of unsaturated compounds.16—23
Scheme 1
We have chosen α,ωꢀbis(trimethylsilyl, methyl, phenyl)ꢀ
diacetylenes as objects of our studies, as well as available
Mg and Al alkyl and alkyl halide derivatives.
Initially, we studied a Cp2ZrCl2ꢀcatalyzed cycloaluꢀ
mination and cyclomagnation of α,ωꢀbis(trimethylsilyl)ꢀ
diacetylenes, chosen as the model compounds, upon the
action of alkylhaloalanes and Grignard reagents.
It was found that the reaction of 1,8ꢀbis(trimethylꢀ
silyl)octaꢀ1,7ꢀdiyne (1b) with EtAlCl2 or AlCl3 in the presꢀ
ence of 10 mol.% of Cp2ZrCl2 under developed conditions
(diyne : EtAlCl2 : Mg : Cp2ZrCl2 = 10 : 40 : 80 : 1, 22 °C,
THF, 24—72 h) results in the intramolecular cyclization
at the two acetylene bonds of the alkadiyne molecule
with the formation of 8ꢀethylꢀ7,9ꢀbis(trimethylsilyl)ꢀ8ꢀ
aluminabicyclo[4.3.01,6]nonaꢀ1(9),6(7)ꢀdiene (2b´)
or 8ꢀchloroꢀ7,9ꢀbis(trimethylsilyl)ꢀ8ꢀaluminabicycloꢀ
R = R´ = Me3Si, Alk, Ar, —(CH2)n—;
R = H, Ph, Alk, Me3Si, R´ = Ph, Alk; n = 0, 1;
[Zr] = Cp2ZrCl2, (MeCp)2ZrCl2, ZrCl4; [Ti] = Cp2TiCl2;
[Hf] = Cp2HfCl2; [Co] = CoCl2 + 2 Ph3P, Co(acac)2 + 2 Ph3P
Despite the fact that cycloalumination of acetylenes
was for the first time accomplished back in 1990 2,7 and at
the present time is widely used in the synthesis of carboꢀ
and heterocyclic compounds,8—12 as well as macrocyclic
tetraꢀ and polyketones,13—15 until recently there was no
* For Part 37, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1607—1613, August, 2011.
1066ꢀ5285/11/6008ꢀ1633 © 2011 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 60, No. 8, August, 2011
D´yakonov et al.
Scheme 2
1—5
a
b
R
n
1
2
1—5
c
d
R
n
3
4
1—5
e
f
R
Me
Ph
n
2
2
Me3Si
Me3Si
Me3Si
Me3Si
R´ = Cl (2a—f), Et (2b´); X = H (4a—f), D (5a—f)
[4.3.01,6]nonaꢀ1(9),6(7)ꢀdiene (2b), respectively (Scheme 2).
Subsequent acidic hydrolysis or deuterolysis of compounds
2b and 2b´ furnished 1,2ꢀbis(trimethylsilylmethylidene)ꢀ
cyclohexane (4b) and 1,2ꢀbis(trimethylsilyldeuteromethylꢀ
idene)cyclohexane (5b), respectively, in 79% yield.
Similar result was achieved in cycloalumination of
1,8ꢀbis(trimethylsilyl)octaꢀ1,7ꢀdiyne (1b) upon the action
of Et3Al in the presence of 5 mol.% of Cp2ZrCl2. Aluminaꢀ
cyclopentadiene 2b´ was formed in 34% yield instead of
expected organoaluminum compound containing two aluꢀ
minacyclopentene fragments in its structure (according to
the results obtained earlier2,3 on cycloalumination of disꢀ
ubstituted acetylenes).
For more reliable confirmation of the structures of
the synthesized metallacycles 2b and 3b, comparison of
their relative reactivity in the crossꢀcoupling and transꢀ
metallation reactions, as well as for the development
of new oneꢀpot methods for the synthesis of poorly availꢀ
able carboꢀ and heterocyclic compounds, we accomꢀ
plished a number of transformations of compounds 2b and
3b involving I2, allyl bromide and elementary sulfur
(Scheme 3).
Scheme 3
The reaction of diyne 1b with RMgBr (R = Et, Bu)
under conditions of catalytic cyclomagnation of disubstiꢀ
tuted acetylenes6 (diyne : RMgBr : Cp2ZrCl2 = 10 : 40 : 1,
22 °C, Et2O) within 72 h led to 7,9ꢀbis(trimethylsilyl)ꢀ8ꢀ
magnesabicyclo[4.3.01,6]nonaꢀ1(9),6(7)ꢀdiene (3b) in 72%
yield (see Scheme 2).
The structures of cyclic organometallic compounds
(OMC) 2 and 3 were established based on oneꢀdimenꢀ
sional (1H, 13C, Dept 135) and twoꢀdimensional (HSQC,
HMBC, and HH COSY) NMR spectra for the hydrolysis
4 and deuterolysis 5 products.
For example, the 13C NMR spectrum of compound 4b
due to the symmetry of the molecule exhibits four signals
at δ 161.57, 121.96, 34.51, and 26.66 corresponding to the
molecular framework, as well as a highꢀfield signal charꢀ
acteristic of the methyl groups at the Si atom (δ 0.13). For the
partially deuterated compound 5b, a triplet splitting of the
signals for the carbon atoms of the double bond at δ 121.64
(JC,D = 23.0 Hz) was observed in the 13C NMR spectrum, as
well as disappearance of the downfield signal for the hyꢀ
drogen atoms at the double bond in the 1H NMR spectrum.
M = AlEt (2b´), Mg (3b)

Cp2ZrCl2ꢀcatalyzed cyclometallation of α,ωꢀdiynes Russ.Chem.Bull., Int.Ed., Vol. 60, No. 8, August, 2011
1635
Table 1. Catalytic cycloalumination and cyclomagnation of diꢀ
acetylenes 1a—f
We showed that magnesacyclopentadiene 3b quantitaꢀ
tively enter the iodonolysis reaction and crossꢀcoupling
with allyl bromide catalyzed with monovalent copper comꢀ
plexes to yield 1,2ꢀbis(trimethylsilyliodomethylidene)ꢀ
cyclohexane (6) and 1,2ꢀbis(trimethylsilylpropenꢀ2ꢀylꢀ
methylidene)cyclohexane (7), respectively, whereas treatꢀ
ment of this compound with thionyl chloride at –40 °C or
its reflux with S8 in benzene according to procedures deꢀ
veloped earlier10 lead to 2,4ꢀbis(trimethylsilyl)ꢀ3ꢀthiaꢀ
bicyclo[4.3.01,5]nonaꢀ1(2),4(5)ꢀdiene (8) in 85 and 72%
yields, respectively. It is possible that, due to the higher
polarization of the Mg—C bond as compared to the Al—C
bond, aluminacyclopentadiene 2b´ is considerably less acꢀ
tive with respect to both I2 (diiodine derivative 6 was obꢀ
tained in 14% yield) and allyl bromide or elementary sulꢀ
fur in the crossꢀcoupling reactions (the yields of the correꢀ
sponding compounds 7 and 8 were only 7 and 11%).
We also studied behavior of α,ωꢀbis(trimethylsilyl)ꢀ
diacetylenes 1a,c,d with different distances between the
triple bonds and diacetylenes 1e,f with Me and Ph substitꢀ
uents at the triple bond in the cycloalumination and cycloꢀ
magnation reactions developed above. It was found that
either decrease or increase in the number of methylene
units binding the acetylene groups in the starting α,ωꢀdiꢀ
ynes lead to a decrease in the yields of the target metallaꢀ
cycles 2 and 3 (Table 1).
Further, we found that under conditions developed
above 1,2ꢀ(diheptꢀ2ꢀynꢀ1ꢀyl)benzene (9a) and 1,2ꢀbis(3ꢀtriꢀ
methylsilylꢀ2ꢀpropynyl)benzene (9b), like aliphatic
α,ωꢀdiynes, undergo catalytic cyclometallation upon the
action of BuMgBr or AlCl3 catalyzed with Cp2ZrCl2
(10 mol.%) to give the corresponding tricyclic (magnesa)ꢀ
aluminacarbocycles 10a (61%), 10b (54%), 11a (31%),
and 11b (36%) (Scheme 4).
Taking into account our experimental and literature
data, we suggested that bicyclic compounds 2 are formed
by two possible pathways (Scheme 5). Thus, cycloalumiꢀ
nation of α,ωꢀdiynes using EtAlCl2 or AlCl3 (pathway A)
Entry
Starting
diacetylene
OMC
t/h
Yield of cyclic
OMC* (%)
1
2
3
4
5
6
7
8
1a
1a
1b
1b
1b
1b
1b
1b
1c
1c
1d
1d
1e
1e
1f
AlCl3
72
72
72
12
72
72
72
72
72
72
72
72
8
27 (2a)
14 (3a)
62 (2b´)
34 (2b´)
79 (2b)
53 (3b)
72 (3b)
44 (3b)
60 (2c)
39 (3c)
37 (2d)
25 (3d)
81 (2e)
42 (3e)
76 (2f)
10 (3f)
BuMgBr
EtAlCl2
Et3Al
AlCl3
Bu2Mg
BuMgBr
EtMgBr
AlCl3
BuMgBr
AlCl3
BuMgBr
AlCl3
BuMgBr
AlCl3
9
10
11
12
13
14
15
16
72
24
72
1f
BuMgBr
* Determined by GLC using products of acid hydrolysis.
assumes reduction of zirconocene dichloride with Mg to
zirconocene 14,24 which, in turn, can coordinate two
acetylene groups of the molecules of starting diyne to obꢀ
tain the corresponding zirconacyclopentadiene intermeꢀ
diate 15.25 Transmetallation of the latter upon the action
of EtnAlCl3–n (n = 0, 1) leads to compounds 2 with reꢀ
generation of Cp2ZrCl2.
The second pathway B, which is realized when Et3Al is
used, is based on the suggestion on the initial formation of
Zr,Alꢀbimetallic complex 16 during the reaction course,26
which reacts with the diyne to form a sevenꢀmembered
complex 17 with the bridged Zr—Cl—Al bond,27—30 which
is further transformed to the target bicyclic aluminacycloꢀ
pentadienes 2 with the liberation of zirconocene ethyl chloꢀ
ride (18). The latter reacts with Et3Al, that leads to the
Scheme 4
9—13: R = Bu (a), SiMe3 (b); X = H (12a,b), D (13a,b)

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Russ.Chem.Bull., Int.Ed., Vol. 60, No. 8, August, 2011
D´yakonov et al.
Scheme 5
procedure.31 Commercially available Et3Al and EtAlCl2 (92%)
were purchased from Redkinsk Experimental Factory, AlCl3
from Acrus. Diynes 9a,b were synthesized according to the proceꢀ
dure described earlier.32,33
starting bimetallic complex 16 with elimination of Et—H26
(see Scheme 5).
In conclusion, we for the first time showed that α,ωꢀdiꢀ
ynes can be exclusively involved under developed by us
conditions into intramolecular cyclometallation reaction
with RMgR´ or RnAlCl3–n in the presence of Cp2ZrCl2 as
a catalyst precursor to furnish unsaturated diꢀ and triꢀ
cyclic (magnesa)aluminacarbocycles in high yields.
Cyclomagnation of diacetylenes upon the action of RMgR´
(R = Bu, Et; R´ = Bu, Br) in the presence of a Cp2ZrCl2 catalyst
(general procedure). Diacetylene 1a—f, 9a,b (1.0 mmol), dry
Et2O (10 mL), RMgR´ (4.0 mmol), and Cp2ZrCl2 (0.1 mmol)
were sequentially placed into a glass reactor under dry argon at
room temperature with stirring. The reaction mixture was stirred
for 24—72 h (see Table 1). In order to identify the substituted
magnesacyclopentadienes by their deuterolysis or hydrolysis
products, the reaction mixture was treated with 5% DCl in D2O
or 5% aqueous HCl. The reaction products were extracted with
diethyl ether or hexane, the extracts were dried with MgSO4,
the target compounds (4, 5, 12, 13) were isolated by fractional
distillation.
Cycloalumination of diacetylenes upon the action of EtnAlCl3–n
(n = 0, 1) in the presence of a Cp2ZrCl2 catalyst (general proceꢀ
dure). Powdered Mg (8.0 mmol), dry THF (10 mL), diacetylene
1a—f, 9a,b (1.0 mmol), Cp2ZrCl2 (0.1 mmol), and EtnAlCl3–n
(4.0 mmol) were sequentially placed into a glass reactor under
dry argon at 0 °C with stirring. The temperature was elevated to
ambient and stirring was continued for 8—72 h (see Table 1). In
order to identify substituted aluminacyclopentadienes by their
deuterolysis or hydrolysis products, the reaction mixture was
treated with 5% DCl in D2O or 5% aq. HCl. The products were
extracted with diethyl ether or hexane, dried with MgSO4, the
light fractions were evaporated in vacuo, the target compounds
(4, 5, 12, 13) were isolated by fractional distillation.
Experimental
Chromatographic analysis was carried out on a Shimadzu
GCꢀ9A instrument using a 2000×2 mm column, silicon SEꢀ30
(5%) on Chromaton NꢀAWꢀHMDS (0.125—0.160 mm) was
a stationary phase, helium was a carrier gas (30 mL min–1), the
temperature was programmed from 50 to 300 °C at 8 deg min–1
.
1H and 13C NMR spectra were recorded on a Bruker Avanceꢀ
400 spectrometer (400 and 100 MHz, respectively) in CDCl3,
chemical shifts are given relatively to Me4Si. GLCꢀMS analysis
of compounds were carried out on a Finnigan model 4021 inꢀ
strument (a 50000×0.25 mm glass capillary column, HPꢀ5 was
a stationary phase, helium was a carrier gas, the temperature was
programmed from 50 to 300 °C at 5 deg min–1, the temperature
of injector was 280 °C, the temperature of the source of ions was
250 °C, 70 eV). IR spectra were recorded on a Bruker VERTEX
70V IR Fourierꢀspectrometer in CHCl3 or KBr pellets. Elemenꢀ
tal analysis of the samples was accomplished on a Karlo Erba
model 1106 elemental analyzer. The product yields were deterꢀ
mined by GLC. Purity of the reaction products was monitored by
chromatography on Silufol UVꢀ254 plates, visualizing in iodine
vapors. Reactions with organometallic compounds were carried
out under dry argon. Solvents were dried and distilled before use.
The catalyst Cp2ZrCl2 was synthesized according to the known
Cycloalumination of diacetylene 1b upon the action of Et3Al in
the presence of a Cp2ZrCl2 catalyst. Dry hexane (5 mL), diacetylꢀ
ene 1b (1.0 mmol), Cp2ZrCl2 (0.1 mmol), and Et3Al (3 mmol)
were sequentially placed into a glass reactor under dry argon at
0 °C with stirring. The temperature was elevated to ambient and

Cp2ZrCl2ꢀcatalyzed cyclometallation of α,ωꢀdiynes Russ.Chem.Bull., Int.Ed., Vol. 60, No. 8, August, 2011
1637
stirring was continued for 12 h (see Table 1). In order to identify
substituted aluminacyclopentadienes by their deuterolysis or hyꢀ
drolysis products, the reaction mixture was treated with 5% DCl
in D2O or 5% aq. HCl. The products were extracted with diethyl
ether or hexane, dried with MgSO4, the light fractions were
evaporated in vacuo, the target compounds (4b, 5b) were isolated
by fractional distillation.
1,2ꢀBis(trimethylsilylmethylidene)cyclopentane (4a). B.p.
76—78 °C (5 Torr). Found (%): C, 65.23; H, 10.97. C13H26Si2.
Calculated (%): C, 65.46; H, 10.99. IR, ν/cm–1: 2910, 1710,
1450, 1230, 1060, 850, 750, 700. 1H NMR, δ: 0.12 (s, 18 H, 6 CH3);
1.57—1.62 (m, 2 H, CH2); 2.39—2.49 (m, 4 H, 2 CH2—C=);
5.87 (s, 2 H, 2 CH). 13C NMR, δ: 0.21 (C(8), C(9), C(10),
C(11), C(12), C(13)); 23.93 (C(4)); 32.93 (C(3), C(5)); 116.87
(C(6), C(7)); 157.72 (C(1), C(2)). MS (EI, 70 eV), m/z: 238.
1,2ꢀBis(trimethylsilylmethylidene)cyclohexane (4b). B.p.
89—91 °C (5 Torr). Found (%): C, 66.31; H, 11.16. C14H28Si2.
Calculated (%): C, 66.58; H, 11.18. IR, ν/cm–1: 2940, 1700,
1450, 1250, 1100, 1000, 850, 750, 700, 650. 1H NMR, δ: 0.12
(s, 18 H, 6 CH3); 1.58—1.65 (m, 4 H, 2 CH2); 2.26—2.36 (m, 4 H,
2 CH2—C=); 5.48 (s, 2 H, 2 CH). 13C NMR, δ: 0.13 (C(9),
C(10), C(11), C(12), C(13), C(14)); 26.66 (C(4), C(5)); 34.51
(C(3), C(6)); 121.96 (C(7), C(8)); 161.57 (C(1), C(2)). MS
(EI, 70 eV), m/z: 252.
ν/cm–1: 2210 (C—D), 2171 (C—D). 1H NMR, δ: 0.12 (s, 18 H,
6 CH3); 1.57—1.64 (m, 2 H, CH2); 2.41—2.49 (m, 4 H,
2 CH2—C=). 13C NMR, δ: 0.21 (C(8), C(9), C(10), C(11), C(12),
C(13)); 23.95 (C(4)); 32.93 (C(3), C(5)); 116.56 (t, C(6), C(7),
J = 24.5 Hz); 157.70 (C(1), C(2)). MS (EI, 70 eV), m/z: 240.
1,2ꢀBis(trimethylsilyldeuteromethylidene)cyclohexane (5b).
B.p. 89—92 °C (5 Torr). Found (%): C, 65.91; H + D, 11.74.
C14H26D2Si2. Calculated (%): C, 66.06; H, 10.30; D, 1.58. IR,
ν/cm–1: 2165 (C—D). 1H NMR, δ: 0.12 (s, 18 H, 6 CH3);
1.55—1.64 (m, 4 H, 2 CH2); 2.24—2.37 (m, 4 H, 2 CH2—C=).
13C NMR, δ: 0.13 (C(9), C(10), C(11), C(12), C(13), C(14));
26.63 (C(4), C(5)); 34.52 (C(3), C(6)); 121.64 (t, C(7), C(8),
J = 23.0 Hz); 161.54 (C(1), C(2)). MS (EI, 70 eV), m/z: 254.
1,2ꢀBis(trimethylsilyldeuteromethylidene)cycloheptane (5c).
B.p. 68—70 °C (1 Torr). Found (%): C, 67.01; H + D, 11.84.
C15H28D2Si2. Calculated (%): C, 67.08; H, 10.51; D, 1.50. IR,
ν/cm–1: 2212 (C—D), 2167 (C—D). 1H NMR, δ: 0.13 (s, 18 H,
6 CH3); 1.57—1.63 (m, 6 H, 3 CH2); 2.40—2.45 (m, 4 H,
2 CH2—C=). 13C NMR, δ: 0.22 (C(10), C(11), C(12), C(13),
C(14), C(15)); 29.71 (C(4), C(6)); 31.4 (C(5)); 34.37 (C(3),
C(7)); 124.11 (t, C(8), C(9), J = 23.5 Hz); 163.15 (C(1), C(2)).
MS (EI, 70 eV), m/z: 268.
1,2ꢀBis(trimethylsilyldeuteromethylidene)cyclooctane (5d).
B.p. 86—89 °C (1 Torr). Found (%): C, 67.92; H + D, 11.87.
C16H30D2Si2. Calculated (%): C, 68.00; H, 10.70; D, 1.42. IR,
ν/cm–1: 2211 (C—D), 2160 (C—D). 1H NMR, δ: 0.13 (s, 18 H,
6 CH3); 1.53—1.64 (m, 8 H, 4 CH2); 2.22 (t, 4 H, 2 CH2—C=,
J = 7.2 Hz). 13C NMR, δ: 0.16 (C(11), C(12), C(13), C(14), C(15),
C(16)); 26.77 (C(4), C(7)); 28.21 (C(5), C(6)); 34.92 (C(3),
C(8)); 122.95 (t, C(9), C(10), J = 24.0 Hz); 161.37 (C(1), C(2)).
MS (EI, 70 eV), m/z: 282.
1,2ꢀBis(trimethylsilylmethylidene)cycloheptane (4c). B.p.
68—70 °C (1 Torr). Found (%): C, 67.31; H, 11.32. C15H30Si2.
Calculated (%): C, 67.58; H, 11.34. IR, ν/cm–1: 2920, 1720,
1
1450, 1250, 1100, 1075, 1050, 920, 850, 760, 700. H NMR, δ:
0.14 (s, 18 H, 6 CH3); 1.55—1.61 (m, 6 H, 3 CH2); 2.41 (m, 4 H,
2 CH2—C=); 5.72 (s, 2 H, 2 CH). 13C NMR, δ: 0.21 (C(10),
C(11), C(12), C(13), C(14), C(15)); 29.73 (C(4), C(6)); 31.4
(C(5)); 34.36 (C(3), C(7)); 124.11 (C(8), C(9)); 163.13 (C(1),
C(2)). MS (EI, 70 eV), m/z: 266.
1,2ꢀBis(trimethylsilylmethylidene)cyclooctane (4d). B.p.
86—88 °C (1 Torr). Found (%): C, 68.25; H, 11.47. C16H32Si2.
Calculated (%): C, 68.49; H, 11.49. IR, ν/cm–1: 2920, 1710,
1450, 1250, 1100, 1050, 850, 770, 700, 650. 1H NMR, δ: 0.14
(s, 18 H, 6 CH3); 1.53—1.61 (m, 8 H, 4 CH2); 2.23 (t, 4 H,
2 CH2—C=, J = 7.2 Hz); 5.34 (s, 2 H, 2 CH). 13C NMR, δ: 0.16
(C(11), C(12), C(13), C(14), C(15), C(16)); 26.78 (C(4), C(7));
28.20 (C(5), C(6)); 34.92 (C(3), C(8)); 123.23 (C(9), C(10));
161.39 (C(1), C(2)). MS (EI, 70 eV), m/z: 280.
1,2ꢀBis(ethylidene)cyclohexane (4e). B.p. 84—85 °C (40 Torr).
Found (%): C, 87.96; H, 11.82. C10H16. Calculated (%): C, 88.16;
H, 11.84. IR, ν/cm–1: 1650, 900, 800. 1H NMR, δ: 1.56 (d, 6 H,
2 CH3, J = 8 Hz); 1.46—2.40 (m, 8 H, 4 CH2); 5.20—5.45 (m, 2 H,
2 CH). 13C NMR, δ: 13.95 (C(8), C(10)); 26.50 (C(4), C(5));
28.73 (C(3), C(6)); 116.05 (C(7), C(9)); 142.50 (C(1), C(2)).
MS (EI, 70 eV), m/z: 136.
1,2ꢀBis(1ꢀdeuteroethylidene)cyclohexane (5e). B.p. 84—86 °C
(40 Torr). Found (%): C, 86.67; H + D, 13.09. C10H14D2. Calꢀ
culated (%): C, 86.88; H, 10.21; D, 2.91. IR, ν/cm–1: 2165
(C—D). 1H NMR, δ: 1.54 (s, 6 H, 2 CH3); 1.45—2.42 (m, 8 H,
4 CH2). 13C NMR, δ: 13.97 (C(8), C(10)); 26.51 (C(4), C(5));
28.73 (C(3), C(6)); 115.79 (t, C(7), C(9), J = 23.5 Hz); 142.52
(C(1), C(2)). MS (EI, 70 eV), m/z: 138.
1,2ꢀBis(phenyldeuteromethylidene)cyclohexane (5f). Rf 0.52
(SiO2, pentane—benzene (7 : 1)). Found (%): C, 91.36; H + D,
8.38. C20H18D2. Calculated (%): C, 91.55; H, 6.91; D, 1.53. IR,
1
ν/cm–1: 2165 (C—D). H NMR, δ: 1.68 (m, 4 H, 2 CH2); 2.64
(m, 4 H, 2 CH2); 7.26 (m, 4 H, Ph); 7.35 (m, 6 H, Ph). 13C NMR,
δ: 26.28 (C(4), C(5)); 29.97 (C(3), C(6)); 123.88 (t, C(7), C(14),
J = 24.5 Hz); 128.06 (C(9), C(13), C(16), C(20)); 129.49 (C(10),
C(12), C(17), C(19)); 138.01 (C(8), C(15)); 144.51 (C(1), C(2)).
MS (EI, 70 eV), m/z: 262.
2,3ꢀDipentylideneꢀ1,4ꢀdihydronaphthalene (12a). Rf 0.49
(SiO2, pentane—benzene (10 : 1)). Found (%): C, 89.29; H,
10.49. C20H28. Calculated (%): C, 89.49; H, 10.51. IR, ν/cm–1
:
1,2ꢀBis(phenylmethylidene)cyclohexane (4f). Rf 0.52 (SiO2,
pentane—benzene (7 : 1)). Found (%): C, 92.06; H, 7.72. C20H20
.
3020, 2950, 1450, 920, 860, 695. 1H NMR, δ: 1.04 (t, 6 H,
2 CH3, J = 7.0 Hz); 1.36—1.57 (m, 8 H, 4 CH2); 2.26 (q, 4 H,
2 CH2, J = 7.2 Hz); 3.63 (s, 4 H, 2 CH2); 5.78 (t, 2 H, 2 CH,
J = 7.6 Hz); 7.24 (s, 4 H, 4 CH). 13C NMR, δ: 14.22 (C(15), C(20));
22.52 (C(14), C(19)); 27.83 (C(12), C(17)); 32.04 (C(13), C(18));
32.68 (C(1), C(4)); 122.81 (C(11), C(16)); 126.06 (C(7), C(8));
127.69 (C(6), C(9)); 136.67 (C(2), C(3)); 137.02 (C(5), C(10)).
MS (EI, 70 eV), m/z: 268.
Calculated (%): C, 92.26; H, 7.74. IR, ν/cm–1: 3050, 2850, 1450,
930, 850, 700. 1H NMR, δ: 1.68 (m, 4 H, 2 CH2); 2.65 (m, 4 H,
2 CH2); 6.65 (s, 2 H, 2 CH); 7.27 (m, 4 H, Ph); 7.33 (m, 6 H, Ph).
13C NMR, δ: 26.29 (C(4), C(5)); 29.99 (C(3), C(6)); 124.15
(C(7), C(14)); 128.07 (C(9), C(13), C(16), C(20)); 129.49 (C(10),
C(12), C(17), C(19)); 138.01 (C(8), C(15)); 144.50 (C(1), C(2)).
MS (EI, 70 eV), m/z: 260.
1,2ꢀBis(trimethylsilyldeuteromethylidene)cyclopentane (5a).
B.p. 75—77 °C (5 Torr). Found (%): C, 64.79; H + D, 11.67.
C13H24D2Si2. Calculated (%): C, 64.92; H, 10.06; D, 1.67. IR,
2,3ꢀBis(trimethylsilylmethylidene)ꢀ1,4ꢀdihydronaphthalene
(12b). Rf 0.52 (SiO2, pentane—benzene (10 : 1)). Found (%):
C, 71.72; H, 9.37. C18H28Si2. Calculated (%): C, 71.92; H, 9.39.

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D´yakonov et al.
IR, ν/cm–1: 3050, 2954, 1450, 922, 890 (Si(CH3)3), 860. 1H
NMR, δ: 0.05 (s, 18 H, 6 CH3); 2.25 (s, 4 H, 2 CH2); 7.42
(s, 2 H, 2 CH); 7.19—7.41 (m, 2 H, C6H4); 7.59—7.74 (m, 2 H,
C6H4). 13C NMR, δ: –1.34 (C(12), C(13), C(14), C(16), C(17),
C(18)); 24.55 (C(1), C(4)); 124.26 (C(7), C(8)); 126.06 (C(11),
C(15)); 126.59 (C(6), C(9)); 131.55 (C(5), C(10)); 137.05 (C(2),
C(3)). MS (EI, 70 eV), m/z: 300.
C(5)Ha); 1.89—1.92 (m, 2 H, C(4)Hb, C(5)Hb); 2.00—2.06
(m, 2 H, C(3)Ha, C(6)Ha); 2.55—2.61 (m, 2 H, C(8)Ha, C(12)Ha);
2.66—2.69 (m, 2 H, C(3)Hb, C(6)Hb); 2.92—2.98 (m, 2 H,
C(8)Hb, C(12)Hb); 4.88—4.95 (m, 4 H, 2 CH2); 5.68—5.75
(m, 2 H, 2 CH—C=). 13C NMR, δ: 0.92 (C(15), C(16), C(17),
C(18), C(19), C(20)); 29.81 (C(4), C(5)); 36.88 (C(8), C(12));
38.16 (C(3), C(6)); 114.06 (C(10), C(14)); 126.66 (C(7), C(11));
138.42 (C(9), C(13)); 155.04 (C(1), C(2)). MS (EI, 70 eV), m/z: 332.
2,4ꢀBis(trimethylsilyl)ꢀ3ꢀthiabicyclo[4.3.01,5]nonaꢀ1(2),
4(5)ꢀdiene (8). A. A reaction mixture obtained by the procedure
described above and containing 8ꢀethylꢀ7,9ꢀbis(trimethylsilyl)ꢀ
8ꢀaluminabicyclo[4.3.01,6]nonaꢀ1(9),6(7)ꢀdiene (2b´) or 7,9ꢀbisꢀ
(trimethylsilyl)ꢀ8ꢀmagnesabicyclo[4.3.01,6]nonaꢀ1(9),6(7)ꢀdiene
(3b) were cooled to –20 °C, followed by addition of S8 (4.8 mmol)
in benzene (10 mL). The reaction mixture was stirred for 8 h at
40 °C, then treated with 7—10% aq. HCl, the reaction product
was extracted with hexane, dried with MgSO4, and isolated by
vacuum distillation. Rf 0.54 (SiO2, pentane—benzene (6 : 1)).
Found (%): C, 59.30; H, 9.25. C14H26SSi2. Calculated (%): C,
59.50; H, 9.27. IR, ν/cm–1: 1490, 1450, 1410 (thiophene ring),
890, 790 (Si(CH3)3). 1H NMR, δ: 0.33 (s, 18 H, 6 CH3);
1.50—1.60 (m, 4 H, 2 CH2); 2.18 (m, 4 H, 2 CH2—C=).
13C NMR, δ: 0.55 (C(10), C(11), C(12), C(13), C(14), C(15));
31.11 (C(7), C(8)); 39.14 (C(6), C(9)); 137.08 (C(2), C(4));
146.93 (C(1), C(5)). MS (EI, 70 eV), m/z: 282.
2,3ꢀDi(1ꢀdeuteropentylidene)ꢀ1,4ꢀdihydronaphthalene (13a).
Rf 0.48 (SiO2, pentane—benzene (10 : 1)). Found (%): C, 88.67;
H + D, 11.27. C20H26D2. Calculated (%): C, 88.82; H, 9.69;
1
D, 1.49. IR, ν/cm–1: 2210 (C—D), 2164 (C—D). H NMR, δ:
1.03 (t, 6 H, 2 CH3, J = 7.0 Hz); 1.36—1.55 (m, 8 H, 4 CH2);
2.24 (t, 4 H, 2 CH2, J = 7.2 Hz); 3.62 (s, 4 H, 2 CH2); 7.26
(s, 4 H, 4 CH). 13C NMR, δ: 14.21 (C(15), C(20)); 22.53 (C(14),
C(19)); 27.83 (C(12), C(17)); 32.05 (C(13), C(18)); 32.68 (C(1),
C(4)); 122.57 (t, C(11), C(16), J = 24.0 Hz); 126.06 (C(7), C(8));
127.68 (C(6), C(9)); 136.67 (C(2), C(3)); 137.01 (C(5), C(10)).
MS (EI, 70 eV), m/z: 270.
2,3ꢀBis(trimethylsilyldeuteromethylidene)ꢀ1,4ꢀdihydronaphꢀ
thalene (13b). Rf 0.52 (SiO2, pentane—benzene (10 : 1)). Found (%):
C, 71.34; H + D, 9.98. C18H26D2Si2. Calculated (%): C, 71.45;
H, 8.66; D, 1.33. IR, ν/cm–1: 2210 (C—D), 2164 (C—D).
1H NMR, δ: 0.05 (s, 18 H, 6 CH3); 2.24 (s, 4 H, 2 CH2); 7.19—7.38
(m, 2 H, C6H4); 7.59—7.68 (m, 2 H, C6H4). 13C NMR, δ: –1.32
(C(12), C(13), C(14), C(16), C(17), C(18)); 24.55 (C(1), C(4));
124.26 (C(7), C(8)); 125.82 (t, C(11), C(15), J = 24.0 Hz); 126.58
(C(6), C(9)); 131.55 (C(5), C(10)); 137.02 (C(2), C(3)). MS
(EI, 70 eV), m/z: 302.
1,2ꢀBis(trimethylsilyliodomethylidene)cyclohexane (6). Reacꢀ
tion mixtures obtained by the procedures described above and
containing 8ꢀethylꢀ7,9ꢀbis(trimethylsilyl)ꢀ8ꢀaluminabicycloꢀ
[4.3.01,6]nonaꢀ1(9),6(7)ꢀdiene (2b´) or 7,9ꢀbis(trimethylsilyl)ꢀ
8ꢀmagnesabicyclo[4.3.01,6]nonaꢀ1(9),6(7)ꢀdiene (3b) were cooled
to 0 °C, followed by addition of CuCl (0.11 mmol) and a dropꢀ
wise addition of the ethereal solution of I2 (4.2 mmol). The
temperature was raised to ambient and the mixture was stirred
for 10 h. Then, hexane and 7—10% aq. HCl were added. The
organic layer was separated, treated with aq. Na2S2O3, and dried
with MgSO4. The reaction product 6 was isolated by vacuum
distillation. Rf 0.39 (SiO2, pentane). Found (%): C, 33.14;
H, 5.18. C14H26I2Si2. Calculated (%): C, 33.34; H, 5.20. IR,
ν/cm–1: 2930 (cyclohexane), 1600 (C=C), 1450 (cyclohexane),
840, 745 (Si(CH3)3), 620, 490, 450 (C—I). 1H NMR, δ: 0.32
(s, 18 H, 6 CH3); 1.26—1.53 (m, 4 H, 2 CH2); 2.17—2.88 (m, 4 H,
2 CH2—C=). 13C NMR, δ: 0.39 (C(9), C(10), C(11), C(12),
C(13), C(14)); 29.12 (C(4), C(5)); 36.44 (C(3), C(6)); 107.00
(C(7), C(8)); 165.94 (C(1), C(2)). MS (EI, 70 eV), m/z: 504.
1,2ꢀBis(trimethylsilylpropenꢀ2ꢀylmethylidene)cyclohexane (7).
Reaction mixtures obtained by the procedures described above
and containing 8ꢀethylꢀ7,9ꢀbis(trimethylsilyl)ꢀ8ꢀaluminabiꢀ
cyclo[4.3.01,6]nonaꢀ1(9),6(7)ꢀdiene (2b´) or 7,9ꢀbis(trimethylꢀ
silyl)ꢀ8ꢀmagnesabicyclo[4.3.01,6]nonaꢀ1(9),6(7)ꢀdiene (3b) were
cooled to –20 °C, followed by addition of CuCl (0.1 mmol) and
slow dropwise addition of allyl bromide (4.5 mmol). The temꢀ
perature was elevated to ambient and the reaction mixture was
stirred for 6 h, treated with 7—10% aq. HCl, the reaction prodꢀ
uct was extracted with hexane, dried with MgSO4, and isolated
by distillation. B.p. 125—127 °C (1 Torr). Found (%): C, 72.01;
H, 10.71. C20H36Si2. Calculated (%): C, 72.21; H, 10.91. IR,
ν/cm–1: 3078, 2978, 1635, 1260, 913, 890 (Si(CH3)3), 820, 760.
1H NMR, δ: 0.19 (s, 18 H, 6 CH3); 1.46—1.58 (m, 2 H, C(4)Ha,
B. A reaction mixture obtained by the procedure described
above and containing 8ꢀethylꢀ7,9ꢀbis(trimethylsilyl)ꢀ8ꢀaluminaꢀ
bicyclo[4.3.01,6]nonaꢀ1(9),6(7)ꢀdiene (2b´) or 7,9ꢀbis(trimethylꢀ
silyl)ꢀ8ꢀmagnesabicyclo[4.3.01,6]nonaꢀ1(9),6(7)ꢀdiene (3b) was
cooled to –40 °C, followed by a dropwise addition SOCl2
(2.4 mmol). The temperature was raised to ambient, and the
reaction mixture was stirred for 8 h and treated with 7—10% aq.
HCl. The reaction product was extracted with hexane, dried
with MgSO4, and isolated by vacuum distillation.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 10ꢀ03ꢀ00046)
and the Russian Science Support Foundation.
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Received July 20, 2010;
in revised form January 31, 2011