Synthesis and transformations of metallacycles 35.* joint cycloalumination of cyclic 1,2-dienes with disubstituted acetylenes and terminal allenes under the action of EtAlCl 2 catalyzed by Ti and Zr complexes

Article abstract of DOI:10.1007/s11172-009-0344-4

Catalytic intermolecular cycloalumination of cyclic 1,2-dienes with terminal allenes or disubstituted acetylenes mediated by EtAlCl₂ in the presence of complexes based on transition metals was accomplished. The yield of unsaturated bicyclic alu

Full text of DOI:10.1007/s11172-009-0344-4

Russian Chemical Bulletin, International Edition, Vol. 58, No. 12, pp. 2456—2464, December, 2009
2456
Synthesis and transformations of metallacycles
35.* Joint cycloalumination of cyclic 1,2ꢀdienes with disubstituted acetylenes
and terminal allenes under the action of EtAlCl catalyzed by Ti and Zr complexes
2
V. A. D´yakonov, R. K. Timerkhanov, T. V. Tyumkina, 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
Catalytic intermolecular cycloalumination of cyclic 1,2ꢀdienes with terminal allenes or
disubstituted acetylenes mediated by EtAlCl2 in the presence of complexes based on transition
metals was accomplished. The yield of unsaturated bicyclic aluminacarbocycles was up to 85%.
Key words: organoaluminum compounds, metallocomplex catalysis, aluminacyclopentane,
cyclic and acyclic 1,2ꢀdienes, disubstituted acetylenes, cycloalumination, zirconocene dichloride.
Earlier,2,3 we have demonstrated that catalytic cycloꢀ
Cyclononaꢀ1,2ꢀdiene, cyclotridecaꢀ1,2ꢀdiene, disubꢀ
stituted acetylenes, and terminal allenes with different
length of the alkyl chain that contain different substiꢀ
tuents were chosen as the subjects of the investigation.
First, the reaction of joint intermolecular cycloꢀ
alumination of cyclic 1,2ꢀdienes with disubstituted acetyꢀ
lenes was studied.
alumination of cyclic 1,2ꢀdienes or joint cycloalumination
of cyclic 1,2ꢀdienes with αꢀolefins under the action of
EtAlCl2 in the presence of Cp2ZrCl2 as a catalyst and
metallic Mg as an acceptor of halogen ions led to biꢀ and
tricyclic organoaluminum compounds (OAC) (Scheme 1).
It was established that cycloalumination of equimolar
amounts of cyclononаꢀ1,2ꢀdiene with octꢀ4ꢀyne that have
been chosen as model compounds under the action of
EtAlCl2 in the presence of Mg and catalyst Cp2ZrCl2
(Scheme 2) resulted in three types of aluminacarbocycles
1—3, namely, the target aluminacyclopentene 1b and
symmetrical aluminacarbocycles 2b, 3 (total yield 78%).
The latter can be obtained by the reaction of homoꢀ
cycloalumination of the alkyne and the allene. The target
nonsymmetrical aluminacyclopentene 1b could be obꢀ
tained in 70% yield by varying the ratio of the reactants,
the solvent, time and temperature of the reaction: under the
optimized reaction conditions (cyclononаꢀ1,2ꢀdiene :
octꢀ4ꢀyne : EtAlCl2 : Mg : Cp2ZrCl2 = 10 : 11 : 15 : 22 : 2,
20 °С, THF, 5 h), the total yield of homocycloalumination
products of the starting allene and alkyne was less than
10—15%.
Scheme 1
NMR experiments, both oneꢀdimensional (1H, 13C,
DEPTꢀ135°) and twoꢀdimensional (HSQC, HMBC and
HH COSY), were carried out to confirm reliably the strucꢀ
ture of OAC 1b.
The carbon atom common to both rings, C(9), whose
signal in the 13C NMR spectrum should differ in multiꢀ
plicity from the signals for other carbon atoms of comꢀ
pound 1b, was chosen as the starting point for the assignꢀ
ment of signals. Indeed, oneꢀdimensional 13C NMR
We investigated cycloalumination of cyclic 1,2ꢀdienes
with terminal allenes and disubstituted acetylenes under
the action of EtAlCl2 in the presence of metallic Mg (as
acceptor of the chloride ions) and catalysts based on tranꢀ
sition metal (Ti and Zr) complexes aimed at extending
the scope of these reactions and synthesis of novel biꢀ
cyclic OAC.
* For Part 34, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2378—2385, December, 2009.
1066ꢀ5285/09/5812ꢀ2456 © 2009 Springer Science+Business Media, Inc.

Cycloalumination of cyclic 1,2ꢀdienes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2457
Scheme 2
[ Zr] = Cp2ZrCl ; n = 2 (1a—e, 3, 5a—e, 6a—e, 9, 11), 6 (1f,g, 4, 5f,g, 6f,g, 10, 12);
2
R = R´ = Et (1a,f, 2a, 5a,f, 6a,f, 7a, 8a), Prn (1b,g, 2b, 5b,g, 6b,g, 7b, 8b), Bun (1c, 2c, 5c, 6c, 7c, 8c), Ph (1d, 2d, 5d, 6d, 7d, 8d);
R = Bun, R´ = SiMe3 (1e, 2e, 5e, 6e, 7e, 8e); X = H (5a—g, 7a—e, 9, 10), D (6a—g, 8a—e, 11, 12)
of the С(3) atom are diastereotropic (δH 2.9 and δH 1.8).
a
b
The signal for the carbon atom bearing no protons at
δ 153.6 was assigned to the С(1) atom because of the presꢀ
ence of a crossꢀpeak with the H(2) proton at the double
bond in the HMBC spectrum. The assignments for the
two propyl substituents at С(10) (δ 163.1) and С(11)
(δ 144.5) has also been done from the detailed analysis
of the twoꢀdimensional spectra. The considerably posiꢀ
tive value of the βꢀincrement of the Al atom for one of the
alkyl substituents4 became apparent from the lowꢀfield
shift of the signal for the C(13) atom to δ 39.9. The signals
for the carbon atoms of the ethyl group connected with
the Al atom were observed in the high field5 at δ 8.2 and
0.2 in the 13C NMR spectrum of OAC 1b, and the signals
for the protons of the ethyl group were observed at δ 0.7
and 0.12 in the 1H NMR spectrum. The 27Al NMR specꢀ
trum of compound 1b consists of a single signal at δ 126,
which is characteristic of the fourꢀcoordinate Al atom.
The lowꢀfield signals characteristic of the double bonds
of compound 1b disappear in the 1H and 13C NMR specꢀ
tra of compounds 5b and 6b obtained by acid hydrolysis or
deuterolysis of OAC 1b, respectively. Transformation of
the two singlets into doublets is observed in the 13C NMR
spectrum of the hydrolysis product 5b in comparison with
the spectrum of the starting OAC 1b, which is connected
with the replacement of the metal atom by the hydrogen
atoms. ZꢀConfiguration was assigned to compound 5b
judging from the vicinal SSCC of the protons at the double
spectrum for aluminacyclopentene 1b recorded in a
DEPTꢀ135° mode contained a doublet of the C(9) atom
at δ 50.4, which correlated with a doublet at δ 2.90 in the
HSQC experiment. This assigment allowed determinaꢀ
tion of vicinal homonuclear interactions from the COSY
HH spectra, as well as of longꢀrange heteronuclear
С—H interactions from the HMBC experiments. Thus
the signal that corresponds to the H(9) atom had crossꢀ
peaks with four resonances in the low field at δ 163.1,
153.6, 144.2, 134.7 in the HBMC spectrum. As the latter
signal is the doublet of the C(2) atom and the correspondꢀ
ing H atom resonates as a doublet of doublets at δ 5.7 in
the 1H NMR spectrum, it is possible to infer that the three
remaining signals unequivocally correspond to the carbon
atoms bearing no protons that form the aluminacycloꢀ
pentene fragment of the molecule. At the same time, the
HMBC experiment allowed us to determine the chemical
shifts of the C(7) and С(8) atoms of the cyclononene
fragment, which resonate at δ 25.1 and 34.4, respectively.
From the COSY HH spectra, it became clear that the
protons at the С(8) atom are highly shielded and, in spite
of proximity of the double bonds in the β position, resonate
at δ 0.7. The observed effect can be caused by location of
these protons in the shielding zone formed by the THF
molecules bound to the Al atom with formation of the
donorꢀacceptor complexes of the 1b type. Allylic protons
3
bond in the cyclononene fragment JHC(1),HC(2) = 10 Hz
(see Ref. 6). All the signal assignments in the spectrum
of compound 5b were confirmed by 2Dꢀexperiments.
Thus, taking into account the aboveꢀmentioned data,
the structures 3ꢀ(1ꢀnꢀpropylpentꢀ1ꢀenꢀ1ꢀyl)cyclononene
and 3ꢀ(1ꢀnꢀpropylꢀ2ꢀdeuteriopentꢀ1ꢀenꢀ1ꢀyl)ꢀ2ꢀdeuterioꢀ

2458
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
D´yakonov et al.
Table 1. Joint cycloalumination of cyclic 1,2ꢀdienes with disubstituted acetylenes
1,2ꢀDiene
Acetylene
Hexꢀ3ꢀyne
Octꢀ4ꢀyne
Decꢀ5ꢀyne
Tolane
Butylsilylacetylene
Hexꢀ3ꢀyne
Octꢀ4ꢀyne
Product (yield (%))*
Total yield (%)
Cyclononaꢀ1,2ꢀdiene
Cyclononaꢀ1,2ꢀdiene
Cyclononaꢀ1,2ꢀdiene
Cyclononaꢀ1,2ꢀdiene
Cyclononaꢀ1,2ꢀdiene
Cyclotridecaꢀ1,2ꢀdiene
Cyclotridecaꢀ1,2ꢀdiene
1a (74) + 2a (10) + 3 (1)
1b (70) + 2b (7) + 3 (3)
1c (68) + 2c (7) + 3 (4)
1d (56) + 2d (5) + 3 (9)
1e (77) + 2e (8) + 3 (3)
1f (66) + 2a (10) + 4 (1)
1g (61) + 2b (12) + 4 (2)
85
80
79
70
88
77
75
* Here and in the Table 2, the yields of metallacycles were determined by GLC of the acid hydrolysis products.
cyclononene were assigned to compounds 5b and 6b,
respectively, and the structure 10,11,12ꢀtriethylꢀ12ꢀ
aluminabicyclo[7.3.01,9]dodecꢀ1(2),10(11)ꢀene was assigned
to OAC 1b.
Cp2ZrCl2 as a catalyst, which leads to the corresponding
fiveꢀmembered OAC 1f,g in 61—66% yields.
Having got promising results on joint cycloaluminꢀ
ation of cyclic 1,2ꢀdienes with allenes, we tried to involve
acyclic 1,2ꢀdienes into the same reaction. By an example
of the reaction of cyclononаꢀ1,2ꢀdiene with heptaꢀ
1,2ꢀdiene in equimolar amounts, it was demonstrated that
a mixture of OAC 13—16 in the ratio 13 : 14 : 15 : 16 =
6 : 3 : 3 : 1 (Scheme 3) is formed under conditions that
have been previously used for cycloalumination of the
cyclic allenes2 (cyclononаꢀ1,2ꢀdiene : heptaꢀ1,2ꢀdiene :
EtAlCl2 : Mg : Cp2ZrCl2 = 10 : 10 : 12 : 24 : 1, THF,
21—23 °С, 4 h); acid hydrolysis of this mixture gave four
isomeric dienes. Lowꢀfield signals, which are characterisꢀ
tic of the terminal and methine carbon atoms and also
of diꢀ and trisubstituted double bonds appeared in the
13С NMR spectrum for a mixture of hydrolysis products,
i.e., hydrocarbons 17—20. Compounds 17—20 were isolꢀ
Analogously to octꢀ4ꢀyne, hexꢀ3ꢀyne, decꢀ5ꢀyne,
tolane, and nꢀbutyltrimethylsilylacetylene were involved
in the reaction of the joint intermolecular cycloaluminꢀ
ation with cyclononаꢀ1,2ꢀdiene. It was established that
these reaction follow the regularities discussed above. The
homocycloalumination products of cyclononаꢀ1,2ꢀdiene
and the disubstituted acetylenes mentioned formed along
with the target aluminacyclopentenes 1a,c—g in each of
the experiments in 10—15% yields. Total yields and ratios
of the cycloalumination products are presented in Table 1.
Under the conditions chosen by us, cyclotridecaꢀ
1,2ꢀdiene, like cyclononаꢀ1,2ꢀdiene, undergoes joint inꢀ
termolecular cycloalumination reaction with disubstituted
acetylenes under the action of EtAlCl2 in the presence of
Scheme 3

Cycloalumination of cyclic 1,2ꢀdienes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2459
ated by preparative GLC with purities 94—97% and were
investigated by oneꢀ and twoꢀdimensional NMR specꢀ
troscopy and mass spectrometry. As a result, the following
structures were assigned to these compounds: (Z)ꢀ3ꢀ[(Z)ꢀ
heptꢀ2ꢀenꢀ1ꢀyl]cyclononene (17), (Z)ꢀ3ꢀ(heptꢀ1ꢀenꢀ
2ꢀyl)cyclononene (18), (Z)ꢀ3ꢀ(heptꢀ1ꢀenꢀ3ꢀyl)cyclononꢀ
ene (19), and (Z)ꢀ3ꢀ(heptꢀ2ꢀenꢀ2ꢀyl)cyclononene (20).
These facts allow us to suggest that isomeric aluminacycloꢀ
pentanes 13—16 are formed in the reaction (see Scheme 3).
We explored also complex Zrꢀbased catalysts such as
Ind2ZrCl2, Py2ZrCl6, (BunO)2ZrCl2, (Et2N)2ZrCl2, ZrCl4,
ZrOCl2 in order to increase the regioselectivity of this
reaction, and to investigate the influence of the nature
and the structure of the ligand environment of the central
atom, but we did not succeed to direct the reaction to the
formation of only one isomer in either case. The yield of
hydrocarbons varied in the range 5—15%.
The influence of the nature of the central atom of the
catalyst on the yield and selectivity of the aboveꢀmenꢀ
tioned reactions was investigated using Tiꢀ and Coꢀbased
complexes which, along with Zr complexes, are active in
cycloalumination reactions.7—9 However, the yields of the
cyclic OAC with catalyst TiCl4, (PriO)4Ti, (BunO)4Ti,
CoCl2—2Ph3P, Co(acac)2—2Ph3P were less than 10%.
The use of Cp2TiCl2 as a catalyst in joint cycloaluminꢀ
ation of cyclononаꢀ1,2ꢀdiene with heptaꢀ1,2ꢀdiene under
the action of EtAlCl2 in the presence of Mg allowed us
to increase significantly the selectivity of the reaction
with respect to OAC 13. Thus the reaction at the ratio
cyclononаꢀ1,2ꢀdiene : heptaꢀ1,2ꢀdiene : EtAlCl2 : Mg :
Cp2TiCl2 = 10 : 10 : 12 : 24 : 1 (THF, 20—21 °C, 4 h) led
to two isomeric cyclic OAC 13 and 22a (3 : 1) in 73% total
yield judging by the GLC analysis of the hydrolysis
products 17 and 26a (Scheme 4). Isomeric hydrocarbons
17 and 26a were isolated by preparative gas chromatoꢀ
graphy with purity ~98% and characterized by spectral
methods. Compound 17, as has been pointed above, is
(Z)ꢀ3ꢀ[(Z)ꢀheptꢀ2ꢀenꢀ1ꢀyl]cyclononene, the structure
of 1ꢀ[(Z)ꢀheptꢀ2ꢀenꢀ1ꢀyl]cyclononene was assigned to
hydrocarbon 26a. The total yield of the symmetrical
aluminacyclopentanes 23a and 3 was ~9% (see Scheme 4).
The structures of the obtained OAC was confirmed by
the 1H and 13C NMR spectra for the hydrolysis product of
17, 24b—d, 26a—d, 28a—d and the deuterolysis products
25a—d, 27a—d, 29a—d.
Oneꢀdimensional (1H, 13C, DEPTꢀ135°) and twoꢀ
dimensional (HH COSY, HSQC, HMBC) NMR experiꢀ
ments were carried out for compounds 17, 24b, 25a, 26a,
1
27a; total assignment of signals in the H and 13C NMR
spectra was made; this allowed us to determine unequivoꢀ
cally the positions and configurations of bonds in the
cyclic and acyclic fragments. Thus the allyl position of
the alkenyl substituent in compound 17 was confirmed by
the presence of the crossꢀpeaks between the H(C(1)) proꢀ
ton (δ 5.52) and the С(3) atom in the HMBC spectrum.
ZꢀConfigurations of the double bonds at the С(1) and
С(11) atoms were unequivocally determined from the
3
value of the vicinal SSCC JHC(1),HC(2) = 10 Hz and
3JHC(11),HC(12) = 11 Hz (see Ref. 6). The position of the
deuterium atoms at the С(2) and С(11) atoms in the
partially deuterated compound 25a was determined from
the absence of the signals for the corresponding protons
at δ 5.15 and 5.34, and also from the triplet splitting of
the signals for the С(2) and С(11) atoms with SSCC
1JC,D = 23 Hz in the 13С NMR spectrum.
Judging from analysis of the NMR spectra of comꢀ
pounds 17 and 26a, a conclusion about migration of the
multiple bond which has been located in the cyclononene
Scheme 4
[Ti] = Cp2TiCl ; n = 2 (3, 13, 17, 21b—d, 22a—d, 24b—d, 25a—d, 26a—d, 27a—d), 6 (4, 21e, 22e, 24e, 25e, 26e, 27e);
2
R = Bun (13, 17, 21e, 22a,e, 23a, 24e, 25a,e, 26a,e, 27a,e, 28a, 29a), nꢀC6H13 (21b, 22b, 23b, 24b, 25b, 26b, 27b, 28b, 29b),
Ph (21c, 22c, 23c, 24c, 25c, 26c, 27c, 28c, 29c), Bn (21d, 22d, 23d, 24d, 25d, 26d, 27d, 28d, 29d);
X = H (9, 10, 17, 24b—e, 26a—e, 28a—d), D (11, 12, 25a—e, 27a—e, 29a—d)

2460
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
D´yakonov et al.
Table 2. Joint cycloalumination of cyclic and terminal 1,2ꢀdienes
Cyclic 1,2ꢀdiene
Terminal 1,2ꢀdiene
Product (yield (%))
Total yield (%)
Cyclononaꢀ1,2ꢀdiene
Cyclononaꢀ1,2ꢀdiene
Cyclononaꢀ1,2ꢀdiene
Cyclononaꢀ1,2ꢀdiene
Cyclotridecaꢀ1,2ꢀdiene
Heptaꢀ1,2ꢀdiene
Nonaꢀ1,2ꢀdiene
Phenylallene
Benzylallene
Heptaꢀ1,2ꢀdiene
c13 (55) + 22a (18) + 23a (6) + 3 (3)
21b (52) + 22b (18) + 23b (4) + 3 (4)
21c (51) + 22c (16) + 23c (5) + 3 (4)
21d (50) + 22d (16) + 23d (4) + 3 (3)
21e (38) + 22e (11) + 23a (7) + 4 (1)
82
78
76
74
57
analysis was carried out on a Carlo Erba 1106 analyzer. Yields of
products were determined with the use of GLC analysis. Control
of purity of products was carried out on Silufol UVꢀ254 plates,
compounds were visualized in iodine vapor. Reactions with
organometallic compounds were carried out in a flow of dry
argon. Solvents were dried and used freshly distilled. Cp2ZrCl2
was obtained from ZrCl4 by the described method.17 Comꢀ
mercially available Cp2TiCl2 (Aldrich) and EtAlCl2 (92%)
(Red´kinskii opytnyi zavod Ltd) were used.
Joint cycloalumination of cyclic 1,2ꢀdienes with disubstituted
acetylenes (general procedure). Сp2ZrCl2 (2 mmol), Mg (powder)
(22 mmol), cyclic 1,2ꢀdiene (cyclononaꢀ1,2ꢀdiene, cyclotriꢀ
decaꢀ1,2ꢀdiene) (10 mmol), disubstituted acetylene (hexꢀ3ꢀyne,
octꢀ4ꢀyne, decꢀ5ꢀyne, tolane, butyltrimethylsilylacetylene)
(11 mmol), THF (15 mL), and EtAlCl2 (15 mmol) were placed
with stirring into a glass reactor in an atmosphere of dry argon
at 0 °C. The temperature of the reaction mixture was raised to
20—21 °C, the reaction mixture was stirred for 5 h and treated
with 7—10% aqueous HCl (compounds 5a—g were obtained) or
DCl in D2O (compounds 6a—g were obtained); the reaction
products were extracted with hexane, dried with MgSO4, and
isolated by vacuum distillation.
10,11,12ꢀTriethylꢀ12ꢀaluminabicyclo[7.3.01,9]dodecaꢀ1(2),
10(11)ꢀdiene (1b). 1H NMR (С7D8), δ: 5.70 (dd, 1 H, 3J = 10.8 Hz,
3J = 5.7 Hz); 2.90 (d, 1 H, 3J = 8.4 Hz); 2.30—2.41 (m, 2 H);
2.17 (m, 2 H); 1.8 (m, 1 H); 1.75 (m, 1 H); 1.5—1.7 (m, 4 H);
1.0—1.12 (m, 7 H); 0.82 (m, 6 H); 0.7 (m, 2 H); 0.12 (m, 2 Н).
13С NMR (С7D8), δ: 163.1 (C(10)); 153.6 (C(1)); 144.5 (C(11));
134.7 (C(2)); 50.4 (C(9)); 39.9 (C(13)); 34.9 (C(16)); 34.4
(C(8)); 33.6 (C(3)); 29.9 (C(4)); 28.0 (C(6)); 25.5 (C(5)); 25.1
(C(7)); 24.5, 25.0 (С(14), C(17)); 13.8, 14.8 (С(15), C(18)); 8.2
(C(20)); 0.2 (С(19)).
fragment of the molecule of 13 inside the aluminacycloꢀ
pentane ring resulting in product 22a has been made. This
follows from the presence of the signals for a trisubstituted
double bond at δ 125.1 and 139.2 in the 13С NMR specꢀ
trum of compound 26a, and also of a doublet of protons
of НС(10) at δ 2.72, which has crossꢀpeak with the methꢀ
ylene C(10) atom at δ 37.3 in the HSQC spectrum, which
is transformed into the singlet in the spectrum of the
partially deuterated analog 27a.
Thus, judging from spectral data, structures of 12ꢀethylꢀ
11ꢀpentylideneꢀ12ꢀaluminabicyclo[7.3.01,9]dodecꢀ1(2)ꢀ
ene and 12ꢀethylꢀ11ꢀpentylideneꢀ12ꢀaluminabicycloꢀ
[7.3.01,2]dodecꢀ1(2)ꢀene were suggested for OAC 13 and
22a, respectively.
Phenylꢀ, benzylꢀ, and hexylallenes, as well as cycloꢀ
tridecaꢀ1,2ꢀdiene and heptaꢀ1,2ꢀdiene were involved into
the joint intermolecular cycloalumination with cyclononаꢀ
1,2ꢀdiene. The yields of the corresponding OAC are preꢀ
sented in Table 2.
Thus, for the first time, we carried out intermolecular
cycloalumination of cyclic 1,2ꢀdienes with disubstituted
acetylenes and terminal allenes under the action of
EtAlCl2 catalyzed by Zr and Ti complexes. Effective methꢀ
ods for the preparation of novel classes of unsaturated
bicyclic aluminacyclopentenes, aluminacyclopentanes,
and aluminacyclopentadienes of the predetermined
structure were developed, which can be used in the
synthesis of practically important carboꢀ10—12 and heteroꢀ
cyclic, 13,14 as well as bifunctional2,15,16 compounds.
3ꢀ(1ꢀEthylbutꢀ1ꢀenꢀ1ꢀyl)cyclononene (5a). Yield 74%,
b.p. 119—121 °C (5 Torr). Found (%): C, 87.12; H, 12.65.
C15H26. Calculated (%): C, 87.30; H, 12.70. 1H NMR, δ: 5.51
(m, 1 H); 5.24 (m, 1 H); 5.12 (t, 1 H, J = 7.2 Hz); 3.15 (m, 1 H);
2.19 (m, 1 H); 2.03 (m, 5 H); 1.68 (m, 2 H); 1.15—1.61 (m,
8 H); 0.96 (t, 3 H, J = 6.8 Hz); 0.93 (t, 3 H, J = 6.8 Hz).
13С NMR, δ: 144.7 (C(10)); 134.1 (C(2)); 129.4 (C(1)); 124.9
((С11)); 42.7 (C(3)); 32.8 (C(4)); 27.7 (C(9)); 26.9 (C(8)); 26.3
(C(7)); 26.2 (C(6)); 24.5 (C(5)); 23.5 (C(14)); 21.1 (C(12));
14.9 (C(13)); 14.3 (С(15)). MS (EI, 70 eV), m/z (Irel (%)):
206 [M+] (19), 177 (26), 135 (33), 121 (37), 107 (69), 95 (73),
81 (100), 79 (91), 67 (64), 55 (71), 41 (74).
3ꢀ(2ꢀDeuterioꢀ1ꢀethylbutꢀ1ꢀenꢀ1ꢀyl)ꢀ2ꢀdeuteriocyclononene
(6a). Yield 73%, b.p. 119—121 °C (5 Torr). Found (%): C, 86.21;
H + D, 12.71. C15H24D2. Calculated (%): C, 86.46; H, 11.61;
D, 1.93. 1H NMR, δ: 5.58 (t, 1 H, J = 8 Hz); 3.17 (m, 1 H); 2.2
(m, 1 H); 2.04 (m, 5 H); 1.74 (m, 2 H); 1.21—1.61 (m, 8 H);
0.98 (t, 3 H, J = 6.8 Hz); 0.96 (t, 3 H, J = 6.8 Hz). 13С NMR, δ:
Experimental
Chromatographic analysis was carried out on a Chromꢀ5
chromatograph, column 1200×3 mm, silicon SEꢀ30 (5%) on
Сhromaton NꢀAWꢀHMDS (0.125—0.160 mm) was used as a
stationary phase, helium was used as a carrier gas (47 mL min–1),
temperature was programmed from 50 to 250 °C at a rate of
8 °C min–1. 1H and 13C NMR spectra (in CDCl3) were recorded
on a Bruker Avanceꢀ400 spectrometer (100 MHz for 13C and
400 MHz for 1H), SiMe4 was used as the internal standard.
Analysis by chromatoꢀmass spectrometry was carried out on a
Finigan 4021 apparatus (glass capillary column 50000×0.25 mm,
НРꢀ5 was used as a stationary phase, helium was used as a
carrier gas, temperature was programmed from 50 to 300 °C at
a rate of 5 °C min–1, the injector temperature was 280 °C,
temperature of the ion source was 250 °C, 70 eV). Elemental

Cycloalumination of cyclic 1,2ꢀdienes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2461
144.4 (C(10)); 129.0 (C(1)); 42.4 (C(3)); 32.6 (C(4)); 27.5
(C(9)); 26.7 (C(8)); 26.1 (C(7)); 26.0 (C(6)); 24.2 (C(5)); 23.2
(C(14)); 20.8 (C(12)); 14.7 (C(13)); 14.1 (С(15)) (signals for
the C(2) and C(11) atoms were not observed). MS (EI, 70 eV),
m/z (Irel (%)): 208 [M+] (53), 179 (58), 164 (40), 137 (61), 123
(60), 108 (100), 93 (99), 79 (99), 67 (99), 55 (90), 42 (99).
3ꢀ(1ꢀnꢀPropylpentꢀ1ꢀenꢀ1ꢀyl)cyclononene (5b). Yield 80%,
3ꢀ(2ꢀDeuterioꢀ1,2ꢀdiphenylethenyl)ꢀ2ꢀdeuteriocyclononene
(6d). Yield 67%, Rf 0.62. Found (%): C, 90.41; H + D, 8.09.
C23H24D2. Calculated (%): C, 90.73; H, 7.95; D, 1.32. 1H NMR,
δ: 7.34 (m, 10 H, Ph); 5.55 (m, 1 H); 3.14 (m, 1 H); 2.03 (m,
2 H); 1.68 (m, 2 H); 1.14—1.63 (m, 8 H). 13С NMR, δ: 146.9
(C(10)); 137.7, 137.8 (С(12), C(18)); 129.8 (C(1)); 128.5, 127.8,
127.6 (С(13), C(14), C(16), C(17), C(19), C(20), C(22), C(23));
b.p. 111—112 °C (1 Torr). Found (%): C, 86.93; H, 12.77. C17H30
Calculated (%): C, 87.10; H, 12.90. 1H NMR, δ: 5.52 (m, 1 H);
5.23 (m, 1 H); 5.12 (t, 1 H, J = 7.0 Hz); 3.12 (m, 1 H); 2.21 (m,
1 H); 2.04 (m, 5 H); 1.67 (m, 2 H); 1.15—1.61 (m, 12 H); 0.91
(t, 3 H, J = 6.8 Hz); 0.89 (t, 3 H, J = 7.0 Hz). 13С NMR, δ:
141.8 (C(10)); 134.1 (C(2)); 129.5 (C(1)); 126.0 (С(11)); 41.9
(C(3)); 32.7 (C(4)); 30.5 (C(12)); 30.1 (C(15)); 27.9 (C(9));
26.9 (C(8)); 26.3 (C(7)); 26.2 (C(6)); 24.5 (C(5)); 23.6 (С(13));
22.1 (С(16)); 14.5 (C(14)); 13.8 (С(17)). MS (EI, 70 eV),
m/z: 234.
.
126.1, 126.6 (С(15), C(21)); 45.8 (C(3)); 32.8 (C(4)); 27.8
(C(9)); 26.8 (C(8)); 26.2 (C(7)); 25.9 (C(6)); 24.4 (С(5)) (signals
for the C(2) and С(11) atoms were not observed). MS (EI, 70 eV),
m/z: 302.
[2ꢀ(Cyclononꢀ2ꢀenꢀ1ꢀyl)hexꢀ1ꢀenꢀ1ꢀyl]trimethylsilane (5e).
Yield 77%, b.p. 127—129 °C (1 Torr). Found (%): C, 77.49;
H, 12.12. C18H34Si. Calculated (%): C, 77.61; H, 12.30; Si,
10.08. 1H NMR, δ: 5.56 (m, 1 H); 5.24 (m, 1 H); 5.22 (s, 1 H);
3.20 (m, 1 H); 2.05—2.25 (m, 4 H); 1.24—1.62 (m, 14 H); 0.91
(t, 3 H, J = 7.2 Hz); 0.08 (s, 9 H). 13С NMR, δ: 164.3 (C(11));
134.2 (C(2)); 129.2 (C(3)); 120.3 (С(10); 43.4 (C(1)); 36.5
(C(12)); 33.2 (C(9)); 31.9 (C(13)); 27.4 (C(4)); 26.8 (C(5));
26.1 (C(6)); 26.0 (C(7)); 24.3 (C(8)); 23.1 (C(14)); 14.1 (C(15));
0.5 (С(16)—C(18)). MS, m/z: 278 [M]+.
3ꢀ(2ꢀDeuterioꢀ1ꢀnꢀpropylpentꢀ1ꢀenꢀ1ꢀyl)ꢀ2ꢀdeuteriocycloꢀ
nonene (6b). Yield 80%, b.p. 123—124 °C (2 Torr). Found (%):
C, 86.09; H + D, 12.51. C17H28D2. Calculated (%): C, 86.36;
1
H, 11.94; D, 1.70. H NMR, δ: 5.57 (t, 1 H, J = 7.0 Hz); 3.16
(m, 1 H); 2.22 (m, 1 H); 2.04 (m, 5 H); 1.73 (m, 2 H); 1.22—1.64
(m, 12 H); 0.92 (t, 3 H, J = 6.8 Hz); 0.90 (t, 3 H, J = 6.8 Hz).
13С NMR, δ: 141.6 (C(10)); 129.5 (C(1)); 41.7 (C(3)); 32.7
(C(4)); 30.7 (C(12)); 30.3 (C(15)); 27.8 (C(9)); 26.9 (C(8));
26.4 (C(7)); 26.2 (C(6)); 24.5 (C(5)); 23.5 (С(13)); 22.2 (С(16));
14.4 (C(14)); 13.8 (С(17)) (signals for the C(2) and С(11) atoms
were not observed). MS (EI, 70 eV), m/z: 236.
3ꢀ(1ꢀnꢀButylhexꢀ1ꢀenꢀ1ꢀyl)cyclononene (5c). Yield 79%,
b.p. 134—135 °C (1 Torr). Found (%): C, 86.75; H, 12.92.
C19H34. Calculated (%): C, 86.94; H, 13.06. 1H NMR, δ: 5.57
(m, 1 H); 5.29 (m, 1 H); 5.17 (t, 1 H, J = 6.8 Hz); 3.16 (m, 1 H);
2.19 (m, 1 H); 2.05 (m, 5 H); 1.72 (m, 2 H); 1.17—1.59 (m,
16 H); 0.91 (t, 3 H, J = 6.8 Hz); 0.90 (t, 3 H, J = 6.8 Hz).
13С NMR, δ: 143.5 (C(10)); 134.2 (C(2)); 129.1 (C(1)); 123.4
(С(11)); 42.6 (C(3)); 32.8 (C(4)); 32.5 (C(17)); 31.5 (C(13));
30.3 (С(12), C(16)); 27.5 (C(9)); 26.9 (C(8)); 26.1 (C(7)); 26.0
(C(6)); 24.3 (C(5)); 23.0 (C(18)); 22.0 (C(14)); 14.1 (С(15),
C(19)). MS (EI, 70 eV), m/z: 262.
3ꢀ(1ꢀnꢀButylꢀ2ꢀdeuteriohexꢀ1ꢀenꢀ1ꢀyl)ꢀ2ꢀdeuteriocycloꢀ
nonene (6c). Yield 78%, b.p. 133—135 °C (1 Torr). Found (%):
C, 86.01; H + D, 13.71. C19H32D2. Calculated (%): C, 86.28;
H, 12.20; D, 1.52. 1H NMR, δ: 5.56 (t, 1 H, J = 8 Hz); 3.17 (m,
1 H); 2.20 (m, 1 H); 2.05 (m, 5 H); 1.73 (m, 2 H); 1.19—1.60
(m, 16 H); 0.90 (t, 3 H, J = 6.8 Hz); 0.89 (t, 3 H, J = 6.8 Hz).
13С NMR, δ: 143.6 (C(10)); 129.1 (C(1)); 42.5 (C(3)); 32.8
(C(4)); 32.5 (C(17)); 31.5 (C(13)); 30.3 (С(12), C(16)); 27.6
(C(9)); 26.9 (C(8)); 26.2 (C(7)); 26.0 (C(6)); 24.3 (C(5)); 23.1
(C(18)); 22.1 (C(14)); 14.1 (С(15), C(19)) (signals for the
C(2) and С(11) atoms were not observed). MS (EI, 70 eV),
m/z: 264.
3ꢀ(1,2ꢀDiphenylethenyl)cyclononene (5d). Yield 67%, Rf 0.62.
Found (%): C, 91.17; H, 8.49. C23H26. Calculated (%): C, 91.34;
H, 8.66. 1H NMR, δ: 7.33 (m, 10 H, Ph); 6.41 (d, 1 H, J = 7.0 Hz);
5.55 (m, 1 H); 5.27 (m, 1 H); 3.15 (m, 1 H); 2.05 (m, 2 H); 1.68
(m, 2 H); 1.17—1.66 (m, 8 H). 13С NMR, δ: 146.9 (C(10));
137.7, 137.9 (С(12), C(18)); 132.3 (C(2)); 129.8 (C(1)); 128.4,
127.8, 127.7 (С(13), C(14), C(16), C(17), C(19), C(20), C(22),
C(23)); 126.1, 126.6 (С(15), C(21)); 126.2 (C(11)); 45.9 (C(3));
32.8 (C(4)); 27.7 (C(9)); 26.8 (C(8)); 26.1 (C(7)); 25.9 (C(6));
24.3 (С(5)). MS (EI, 70 eV), m/z: 302.
[1ꢀDeuterioꢀ2ꢀ(2ꢀdeuteriocyclononꢀ2ꢀenꢀ1ꢀyl)hexꢀ1ꢀenꢀ
1ꢀyl]trimethylsilane (6e). Yield 75%, b.p. 127—129 °C (1 Torr).
Found (%): C, 76.89; H, 12.42. C18H32D2Si. Calculated (%):
C, 77.06; H, 11.50; D, 1.43; Si, 10.01. 1H NMR, δ: 5.58 (t, 1 H,
J = 8 Hz); 3.21 (m, 1 H); 2.08—2.23 (m, 4 H); 1.24—1.57 (m,
14 H); 0.93 (t, 3 H, J = 7.2 Hz); 0.1 (s, 9 H). 13С NMR, δ: 164.3
(C(11)); 129.2 (C(3)); 43.4 (C(1)); 36.6 (C(12)); 33.4 (C(9));
32.0 (C(13)); 27.5 (C(4)); 26.9 (C(5)); 26.2 (C(6)); 26.1 (C(7));
24.4 (C(8)); 23.2 (C(14)); 14.2 (C(15)); 0.6 (С(16)—C18))
(signals for the C(2) and С(10) atoms were not observed).
MS, m/z: 280 [M]+.
3ꢀ(1ꢀEthylbutꢀ1ꢀenꢀ1ꢀyl)cyclotridecene (5f). Yield 77%,
b.p. 139—141 °C (1 Torr). Found (%): C, 86.81; H, 12.88.
C19H34. Calculated (%): C, 86.94; H, 13.06. 1H NMR, δ: 5.31
(m, 1 H); 5.18 (m, 1 H); 5.14 (t, 1 H, J = 6.0 Hz); 3.02 (m, 1 H);
2.41 (m, 1 H); 2.13 (m, 5 H); 1.15—1.71 (m, 18 H); 0.94 (t, 3 H,
J = 7.2 Hz); 0.92 (t, 3 H, J = 7.2 Hz). 13С NMR, δ: 143.4
(C(14)); 135.1 (C(2)); 129.7 (C(1)); 123.4 (С(15)); 41.7 (C(3));
35.1 (C(4)); 27.8 (C(13)); 27.1 (C(12)); 33.1, 28.4, 27.3, 26.0,
25.7, 25.5 (С(6)—C(11)); 23.5 (C(5)); 23.5 (C(18)); 21.2
(C(16)); 14.5 (C(17)); 13.9 (С(19)). MS (EI, 70 eV), m/z: 262.
3ꢀ(2ꢀDeuterioꢀ1ꢀethylbutꢀ1ꢀenꢀ1ꢀyl)ꢀ2ꢀdeuteriocyclotriꢀ
decene (6f). Yield 76%, b.p. 139—141 °C (1 Torr). Found (%):
C, 86.10; H + D, 13.61. C19H32D2. Calculated (%): C, 86.28;
H, 12.20; D, 1.52. 1H NMR, δ: 5.33 (m, 1 H); 3.01 (m, 1 H);
2.43 (m, 1 H); 2.12 (m, 5 H); 1.15—1.73 (m, 18 H); 0.95 (t, 3 H,
J = 7.2 Hz); 0.93 (t, 3 H, J = 7.2 Hz). 13С NMR, δ: 143.6
(C(14)); 129.7 (C(1)); 41.7 (C(3)); 35.2 (C(4)); 27.8 (C(13));
27.2 (C(12)); 33.1, 28.4, 27.2, 26.0, 25.8, 25.5 (С(6)—C(11));
23.6 (C(5)); 23.5 (C(18)); 21.3 (C(16)); 14.3 (C(17)); 13.8 (С(19))
(signals for the C(2) and С(15) atoms were not observed).
MS (EI, 70 eV), m/z: 264.
3ꢀ(1ꢀnꢀPropylpentꢀ1ꢀenꢀ1ꢀyl)cyclotridecene (5g). Yield 75%,
b.p. 154—156 °C (1 Torr). Found (%): C, 86.67; H, 12.09.
C21H38. Calculated (%): C, 86.82; H, 13.18. 1H NMR, δ: 5.35
(m, 1 H); 5.21 (m, 1 H); 5.12 (t, 1 H, J = 6.0 Hz); 2.99 (m, 1 H);
2.43 (m, 1 H); 1.97 (m, 5 H); 1.21—1.74 (m, 18 H); 0.91 (t, 3 H,
J = 7.2 Hz); 0.89 (t, 3 H, J = 7.2 Hz). 13С NMR, δ: 143.3
(C(14)); 135.1 (C(2)); 130.7 (C(1)); 123.8 (С(15)); 41.7 (C(3));
33.7 (C(4)); 31.3 (C(19)); 30.3 (C(16)); 27.8 (C(13)); 27.1

2462
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
D´yakonov et al.
(C(12)); 33.1, 28.5, 27.3, 26.2, 25.8, 25.4 С(6)—C(11)); 23.6
(C(17)); 23.5 (C(5)); 22.2 (C(20)); 14.3 (C(18)); 13.8 (С(21)).
MS (EI, 70 eV), m/z: 290.
2ꢀDeuterioꢀ3ꢀ[(Z)ꢀ2ꢀdeuterioheptꢀ2ꢀenꢀ1ꢀyl]cyclononene
(25a). Yield 54%. B.p. 102—103 °C (1 Torr). Found (%):
C, 86.23; H + D, 13.55. C16H26D2. Calculated (%): C, 86.41;
H, 11.78; D, 1.81. 1H NMR, δ: 5.52 (t, 1 H, J = 8.0 Hz); 5.36 (t,
1 H, J = 8.0 Hz); 2.49 (m, 1 H); 2.05—2.18 (m, 6 H); 1.20—1.54
(m, 12 H); 1.63 (m, 2 H); 0.89 (t, 3 H, J = 7.0 Hz). 13С NMR, δ:
135.1 (t, (C(2), JC,D = 23.0 Hz); 130.8 (C(12)); 129.5 (С(1));
128.2 (t, C(11), JC,D = 23.0 Hz); 37.5 (C(3)); 34.9 (C(9)); 33.8
(C(4)); 32.1 (C(14)); 27.3 (C(10)); 27.1 (C(13)); 26.7 (C(8));
26.3 (C(7)); 26.2 (C(6)); 24.7 (C(5)); 22.6 (C(15)); 14.1 (С(16)).
MS (EI, 70 eV), m/z: 222.
3ꢀ(2ꢀDeuterioꢀ1ꢀnꢀpropylpentꢀ1ꢀenꢀ1ꢀyl)ꢀ2ꢀdeuteriocycloꢀ
tridecene (6g). Yield 75%, b.p. 154—156 °C (1 Torr). Found (%):
C, 86.03; H + D, 13.71. C21H36D2. Calculated (%): C, 86.22;
H, 12.40; D, 1.37. 1H NMR, δ: 5.35 (m, 1 H); 2.99 (m, 1 H);
2.44 (m, 1 H); 1.98 (m, 5 H); 1.20—1.75 (m, 18 H); 0.91 (t, 3 H,
J = 7.2 Hz); 0.88 (t, 3 H, J = 7.2 Hz). 13С NMR, δ: 143.2
(C(14)); 130.7 (C(1)); 41.6 (C(3)); 33.7 (C(4)); 31.3 (C(19));
30.4 (C(16)); 27.8 (C(13)); 27.1 (C(12)); 33.2, 28.5, 27.3, 26.2,
25.9, 25.4 (С(6)—C(11)); 23.6 (C(17)); 23.5 (C(5)); 22.2
(C(20)); 14.4 (C(18)); 13.8 (С(21)) (signals for the C(2) and
С(15) atoms were not observed). MS (EI, 70 eV), m/z: 292.
Joint cycloalumination of cyclic 1,2ꢀdienes with terminal
allenes (general procedure). Сp2ZrCl2, (1 mmol) Mg (powder)
(24 mmol), cyclic 1,2ꢀdiene (cyclononaꢀ1,2ꢀdiene, cyclotridecaꢀ
1,2ꢀdiene) (10 mmol), terminal allene (heptaꢀ1,2ꢀdiene, nonaꢀ
1,2ꢀdiene, phenylallene, benzylallene) (10 mmol), THF (15 mL),
and EtAlCl2 (12 mmol) were placed with stirring into a glass
reactor in an atmosphere of dry argon at 0 °C. The temperature
of the reaction mixture was raised to 20—21 °C, the reaction
mixture was stirred for 4 h and treated with 7—10% aqueous
HCl (compounds 24a—d were obtained) or DCl in D2O (comꢀ
pounds 25a—d were obtained); the reaction products were
extracted with hexane, dried with MgSO4, and isolated by
vacuum distillation.
3ꢀ[(Z)ꢀNonꢀ2ꢀenꢀ1ꢀyl]cyclononene (24b). Yield 52%,
b.p. 131—133 °C (1 Torr). Found (%): C, 86.91; H, 12.87.
C18H32. Calculated (%): C, 87.02; H, 12.98. 1H NMR, δ: 5.55
(m, 1 H, 3J = 10.0 Hz, 3J = 8.0 Hz); 5.36 (m, 1 H, 3J = 10.8 Hz,
3J = 7.0 Hz); 5.33 (m, 1 H, 3J = 10.7 Hz, 3J = 6.0 Hz); 5.14
3
3
(m, 1 H, J = 9.0 Hz, J = 10.1 Hz); 2.51 (m, 1 H); 2.03—2.18
(m, 6 H); 1.45 (m, 5 H); 1.22—1.64 (m, 13 H); 0.90 (t, 3 H,
J = 7.0 Hz). 13С NMR, δ: 135.5 (C(2)); 130.9 (C(12)); 129.7
(С(1)); 128.4 (C(11)); 37.5 (C(3)); 35.2 (C(9)); 33.7 (C(4));
32.1 (C(16)); 29.2 (C(15)); 29.1 (C(14)); 27.5 (C(10)); 27.2
(C(13)); 26.8 (C(8)); 26.2 (C(7)); 26.1 (C(6)); 24.8 (C(5)); 22.5
(C(17)); 14.2 (С(18)). MS (EI, 70 eV), m/z: 248.
2ꢀDeuterioꢀ3ꢀ[(Z)ꢀ2ꢀdeuteriononꢀ2ꢀenꢀ1ꢀyl]cyclononene
(25b). Yield 52%, b.p. 131—133 °C (1 Torr). Found (%):
C, 86.07; H + D, 13.58. C18H30D2. Calculated (%): C, 86.32;
1
H, 12.07; D, 1.61. H NMR, δ: 5.53 (t, 1 H, J = 8.0 Hz); 5.34
3ꢀ[(Z)ꢀHeptꢀ2ꢀenꢀ1ꢀyl]cyclononene (17). Yield 55%,
b.p. 102—103 °C (1 Torr). Found (%): C, 87.01; H, 12.76.
C16H28. Calculated (%): C, 87.19; H, 12.81. H NMR, δ,: 5.52
(t, 1 H, J = 8.0 Hz); 2.49 (m, 1 H); 2.02—2.18 (m, 6 H); 1.64
(m, 2 H); 1.21—1.56 (m, 16 H); 0.92 (t, 3 H, J = 7.0 Hz).
13С NMR, δ: 135.1 (t, C(2), JC,D = 23.0 Hz); 130.8 (C(12));
129.5 (С(1)); 128.2 (t, C(11), JC,D = 23.5 Hz); 37.4 (C(3));
35.0 (C(9)); 33.8 (C(4)); 32.1 (C(16)); 29.2 (C(14)); 29.1 (C(15));
27.3 (C(10)); 27.1 (C(13)); 26.7 (C(8)); 26.5 (C(7)); 26.2
(C(6)); 24.7 (C(5)); 22.6 (C(17)); 14.4 (С(18)). MS (EI, 70 eV),
m/z: 250.
3ꢀ[(Z)ꢀ3ꢀPhenylpropꢀ2ꢀenꢀ1ꢀyl]cyclononene (24c). Yield
51%, b.p. 144—146 °C (1 Torr). Found (%): C, 89.77; H, 9.98.
C18H24. Calculated (%): C, 89.94; H, 10.06. 1H NMR, δ:
7.01—7.35 (m, 5 H, Ph); 6.51 (d, 1 H, J = 8 Hz); 5.48 (m, 1 H);
5.20 (m, 1 H); 5.11 (m, 1 H); 2.53 (m, 1 H); 1.94—2.17 (m,
6 H); 1.42—1.71 (m, 8 H). 13С NMR, δ: 136.6 (C(2)); 135.1
(C(13)); 133.8 (C(11)); 129.6 (С(1)); 128.05 (С(14), C(18));
128.0 (С(15), C(17)); 126.4 (C(12)); 126.3 (C(16)); 37.5 (C(3));
36.6 (C(9)); 33.5 (C(4)); 26.9 (C(10)); 26.5 (C(8)); 26.3 (C(7));
26.1 (C(6)); 25.7 (С(5)). MS (EI, 70 eV), m/z: 240.
1
(m, 1 H, 3J = 10.0 Hz, 3J = 8.0 Hz); 5.36 (m, 1 H, 3J = 10.8 Hz,
3J = 7.0 Hz); 5.34 (m, 1 H, 3J = 10.8 Hz, 3J = 6.2 Hz); 5.15 (m,
1 H, 3J = 9.0 Hz, 3J = 10.1 Hz); 2.5 (m, 1 H); 2.0—2.17 (m, 6 H);
1.45 (m, 5 H); 1.24—1.63 (m, 9 H); 0.91 (t, 3 H, J = 7.0 Hz).
13С NMR, δ: 135.4 (C(2)); 130.8 (C(12)); 129.6 (С(1)); 128.5
(C(11)); 37.5 (C(3)); 35.0 (C(9)); 33.7 (C(4)); 32.1 (C(14));
27.3 (C(10)); 27.0 (C(13)); 26.7 (C(8)); 26.3 (C(7)); 26.2 (C(6));
24.8 (C(5)); 22.6 (C(15)); 14.2 (С(16)). MS (EI, 70 eV), m/z: 220.
3ꢀ(Heptꢀ1ꢀenꢀ2ꢀyl)cyclononene (18). 1H NMR, δ: 5.32—5.51
(m, 2 H); 4.77 (m, 2 H); 2.54 (m, 1 H); 2.01—2.25 (m, 4 H);
1.24—1.71 (m, 16 H); 0.91 (t, 3 H, J = 7.0 Hz). 13С NMR, δ:
154.3 (C(10)); 132.9 (C(2)); 128.9 (С(1)); 107.0 (C(16)); 45.5
(C(3)); 35.7 (C(11)); 33.5 (C(4)); 31.8 (C(13)); 29.6 (C(12));
26.8 (C(8)); 26.6 (C(7)); 26.1 (C(6)); 25.4 (C(5)); 22.6 (C(14));
14.4 (С(15)). MS (EI, 70 eV), m/z: 220.
3ꢀ(Heptꢀ1ꢀenꢀ3ꢀyl)cyclononene (19). 1H NMR, δ: 5.34—5.55
(m, 2 H); 5.24 (m, 1 H); 4.92 (m, 2 H); 2.55 (m, 1 H); 1.93—2.17
(m, 3 H); 1.22—1.67 (m, 16 H); 0.90 (t, 3 H, J = 7.0 Hz).
13С NMR, δ: 141.0 (C(15)); 133.1 (C(2)); 127.7 (С(1)); 115.1
(C(16)); 49.6 (C(10)); 40.1 (C(3)); 32.7 (C(9)); 32.5 (C(11));
32.1 (C(4)); 31.8 (C(12)); 26.8 (C(8)); 26.1 (C(7)); 26.0 (C(6));
24.5 (C(5)); 22.8 (C(13)); 14.5 (С(14)). MS (EI, 70 eV),
m/z: 220.
3ꢀ[(E)ꢀHeptꢀ2ꢀeneꢀ2ꢀyl]cyclononene (20). 1H NMR, δ: 5.31—5.52
(m, 2 H); 5.18 (t, 1 H, J = 7.6 Hz); 2.46 (m, 1 H); 2.01—2.15
(m, 4 H); 1.57 (m, 3 H); 1.22—1.65 (m, 14 H); 0.92 (t, 3 H,
J = 7.0 Hz). 13С NMR, δ: 142.4 (C(10)); 130.6 (C(2)); 128.8
(C(1)); 125.3 (C(11)); 43.1 (C(3)); 34.1 (C(9)); 32.7 (C(12));
32.2 (C(4)); 31.9 (C(13)); 26.6 (C(8)); 26.3 (C(7)); 26.1
(C(6)); 24.9 (C(5)); 22.6 (C(14)); 22.1 (C(16)); 14.2 (С(15)).
MS (EI, 70 eV), m/z: 220.
2ꢀDeuterioꢀ3ꢀ[(Z)ꢀ2ꢀdeuterioꢀ3ꢀphenylpropꢀ2ꢀenꢀ1ꢀyl]ꢀ
cyclononene (25c). Yield 50%, b.p. 144—146 °C (1 Torr).
Found (%): C, 89.01; H + D, 10.08. C18H22D2. Calculated (%):
C, 89.19; H, 9.15; D, 1.66. 1H NMR, δ: 7.01—7.35 (m, 5 H,
Ph); 6.43 (s, 1 H); 5.55 (t, 1 H, J = 8.0 Hz); 2.54 (m, 1 H);
1.95—2.15 (m, 6 H); 1.42—1.72 (m, 8 H). 13С NMR, δ: 136.3
(t, (C(2), JC,D = 23.0 Hz); 135.1 (C(13)); 133.6 (t, C(11),
JC,D = 23.0 Hz); 129.6 (С(1)); 128.05 (С(14), C(18)); 128.0
(С(15), C(17)); 126.3 (C(12)); 126.2 (C(16)); 37.5 (C(3)); 36.5
(C(9)); 33.5 (C(4)); 26.9 (C(10)); 26.4 (C(8)); 26.3 (C(7));
26.1 (C(6)); 25.8 (С(5)). MS (EI, 70 eV), m/z: 242.
3ꢀ[(Z)ꢀ4ꢀPhenylbutꢀ2ꢀenꢀ1ꢀyl]cyclononene (24d). Yield 50%,
b.p. 148—150 °C (1 Torr). Found (%): C, 89.58; H, 10.26.
C19H26. Calculated (%): C, 89.70; H, 10.30. 1H NMR, δ:
7.23 (m, 5 H, Ph); 5.55 (m, 2 H); 5.22 (m, 2 H); 3.43 (d, 2 H,
J = 7.0 Hz); 2.61 (m, 1 H); 2.40 (m, 1 H); 2.15 (m, 4 H); 2.09

Cycloalumination of cyclic 1,2ꢀdienes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2463
(m, 1 H); 1.29—1.68 (m, 8 H). 13С NMR, δ: 141.3 (C(14));
135.8 (C(2)); 129.8 (С(1)); 129.6 (C(12)); 128.8 (С(15), С(19));
128.7 (С(16), C(18)); 128.5 (C(11)); 125.9 (C(16)); 42.1
(C(13)); 37.3 (C(3)); 34.9 (C(9)); 31.8 (C(4)); 26.9 (C(10));
26.6 (C(8)); 26.2 (C(7)); 26.1 (C(6)); 25.7 (С(5)). MS (EI,
70 eV), m/z: 254.
(d, 2 H, J = 7.0 Hz); 1.98—2.37 (m, 4 H); 1.42—1.73 (m, 10 H).
13С NMR, δ: 138.8 (C(13)); 137.9 (C(1)); 134.8 (C(11)); 125.6
(С(2)); 128.2 (С(14), C(18)); 128.1 (С(15), C(17)); 126.4
(C(12)); 126.6 (C(16)); 36.4 (C(10)); 29.5 (C(9)); 26.8 (C(3));
26.1 (C(4)); 26.0, 25.9, 25.3, 25.0 (С(5)—C(8)). MS (EI, 70 eV),
m/z: 240.
2ꢀDeuterioꢀ3ꢀ[(Z)ꢀ2ꢀdeuterioꢀ4ꢀphenylbutꢀ2ꢀenꢀ1ꢀyl]cycloꢀ
nonene (25d). Yield 50%, b.p. 148—150 °C (1 Torr). Found (%):
C, 88.92; H + D, 10.97. C19H24D2. Calculated (%): C, 89.00;
2ꢀDeuterioꢀ1ꢀ[2ꢀdeuterioꢀ(Z)ꢀ3ꢀphenylpropꢀ2ꢀenꢀ1ꢀyl]ꢀ
cyclononene (27c). Yield 16%. Found (%): C, 89.02; H + D,
10.06. C18H22D2. Calculated (%): C, 89.19; H, 9.15; D, 1.66.
1H NMR, δ: 7.21—7.36 (m, 5 H, Ph); 6.61 (s, 1 H); 2.95 (s,
2 H); 1.96—2.35 (m, 4 H); 1.44—1.76 (m, 10 H). 13С NMR, δ:
138.9 (C(13)); 137.8 (C(1)); 125.8 (t, C(2), JC,D = 23.0 Hz);
128.3 (С(14), C(18)); 128.6 (С(15), C(17)); 126.4 (C(12)); 126.7
(C(16)); 36.6 (C(10)); 29.5 (C(9)); 26.8 (C(3)); 26.2 (C(4));
26.1, 25.9, 25.3, 25.1 (С(5)—C(8)) (the signal for the C(11)
atom was not observed). MS (EI, 70 eV), m/z: 242.
1
H, 9.43; D, 1.57. H NMR, δ: 7.22 (m, 5 H, Ph); 5.54 (t, 1 H,
J = 8.0 Hz); 5.24 (t, 1 H, J = 8.0 Hz); 3.41 (d, 2 H, J = 7.0 Hz);
2.62 (m, 1 H); 2.40 (m, 1 H); 2.15 (m, 4 H); 2.08 (m, 1 H);
1.28—1.67 (m, 8 H). 13С NMR, δ: 141.2 (C(14)); 135.6 (t, C(2),
JC,D = 23.5 Hz); 129.8 (С(1)); 129.7 (C(12)); 128.8 (С(15),
C(19)); 128.7 (С(16), C(18)); 128.2 (t, C(11), JC,D = 23.0 Hz);
125.9 (C(16)); 42.2 (C(13)); 37.3 (C(3)); 34.9 (C(9)); 31.9
(C(4)); 26.9 (C(10)); 26.7 (C(8)); 26.2 (C(7)); 26.1 (C(6));
25.4 (С(5)). MS (EI, 70 eV), m/z: 256.
1ꢀ[(Z)ꢀHeptꢀ2ꢀenꢀ1ꢀyl]cyclononene (26a). Yield 18%.
Found (%): C, 87.04; H, 12.77. C16H28. Calculated (%):
C, 87.19; H, 12.81. 1H NMR, δ: 5.36 (m, 2 H); 5.16 (t, 1 H,
J = 10 Hz); 2.73 (d, 2 H, J = 7.0 Hz); 1.96—2.21 (m, 6 H);
1.22—1.65 (m, 14 H); 0.96 (t, 3 H, J = 7.0 Hz). 13С NMR, δ:
139.2 (C(1)); 130.9 (C(12)); 129.6 (С(11)); 125.2 (C(2)); 35.1
(C(10)); 32.0 (C(14)); 29.0 (C(9)); 26.8 (C(13)); 26.6 (C(3));
26.5 (C(4)); 26.4, 26.0, 25.3, 25.1 (С(5)—C(8)); 22.4 (C(15));
14.3 (С(16)). MS (EI, 70 eV), m/z: 220.
1ꢀ[(Z)ꢀ4ꢀPhenylbutꢀ2ꢀenꢀ1ꢀyl]cyclononene (26d). Yield 11%.
Found (%): C, 89.55; H, 10.27. C19H26. Calculated (%):
1
C, 89.70; H, 10.30. H NMR, δ: 7.18—7.33 (m, 5 H, Ph); 5.46
(m, 2 H); 5.20 (t, 1 H, J = 8 Hz); 3.46 (d, 2 H, J = 7.0 Hz);
2.86 (d, 2 H, J = 7.0 Hz); 2.04—2.32 (m, 4 H); 1.22—1.53 (m,
10 H). 13С NMR, δ: 138.8 (C(14)); 134.9 (C(1)); 129.7 (C(12));
128.5 (С(15), C(19)); 128.4 (С(16), C(18)); 129.1 (C(11)); 125.8
(C(17)); 123.3 (C(2)); 35.1 (C(13)); 33.4 (C(10)); 29.2 (C(9));
26.8 (C(3)); 26.1 (C(4)); 25.3, 25.1, 24.9, 24.3 (С(5)—C(8)).
MS (EI, 70 eV), m/z: 254.
2ꢀDeuterioꢀ1ꢀ[2ꢀdeuterioꢀ(Z)ꢀ4ꢀphenylbutꢀ2ꢀenꢀ1ꢀyl]cycloꢀ
nonene (27d). Yield 11%. Found (%): C, 88.88; H + D, 10.96.
C19H24D2. Calculated (%): C, 89.00; H, 9.43; D, 1.57. 1H NMR,
δ: 7.17—7.32 (m, 5 H, Ph); 5.32 (t, 1 H, J = 8 Hz); 3.46 (d, 2 H,
J = 7.0 Hz); 2.86 (s, 2 H); 2.05—2.32 (m, 4 H); 1.22—1.56 (m,
10 H). 13С NMR, δ: 138.8 (C(14)); 134.9 (C(1)); 129.7 (C(12));
128.5 (С(15), C(19)); 128.4 (С(16), C(18)); 125.8 (C(17)); 35.0
(C(13)); 33.5 (C(10)); 29.4 (C(9)); 26.8 (C(3)); 26.2 (C(4));
25.3, 25.1, 24.8, 24.4 (С(5)—C(8)) (signals for the C(2) and
С(11) atoms were not observed). MS (EI, 70 eV), m/z: 256.
2ꢀDeuterioꢀ1ꢀ[(Z)ꢀ2ꢀdeuterioheptꢀ2ꢀenꢀ1ꢀyl]cyclononene
(27a). Yield 18%. Found (%): C, 86.20; H + D, 13.56. C16H26D2.
1
Calculated (%): C, 86.41; H, 11.78; D, 1.81. H NMR, δ: 5.31
(t, 1 H, J = 8 Hz); 2.48 (s, 2 H); 1.93—2.22 (m, 6 H); 1.20—1.67
(m, 14 H); 0.95 (t, 3 H, J = 7.0 Hz). 13С NMR, δ: 139.3 (C(1));
130.7 (C(12)); 129.3 (t, C(11), JC,D = 23.0 Hz); 125.0 (t, C(2),
JC,D = 23.0 Hz); 35.1 (C(10)); 32.1 (C(14)); 29.0 (C(9)); 26.7
(C(13)); 26.6 (C(3)); 26.5 (C(4)); 26.4, 26.1, 25.4, 25.2
(С(5)—C(8)); 22.4 (C(15)); 14.2 С(16). MS (EI, 70 eV),
m/z: 222.
The work was carried our with the financial support of
Council on Grants at the President of the Russian Federaꢀ
tion (Program of State Support of Leading Scientific
Schools, Grants MKꢀ1039.2007.3 and NShꢀ2349.2008.3)
and the Russian Science Support Foundation.
1ꢀ[(Z)ꢀNonꢀ2ꢀenꢀ1ꢀyl]cyclononene (26b). Yield 18%.
Found (%): C, 86.92; H, 12.91. C18H32. Calculated (%):
C, 87.02; H, 12.98. 1H NMR, δ: 5.41 (m, 2 H); 5.18 (t, 1 H,
J = 10 Hz); 2.74 (d, 2 H, J = 7.0 Hz); 1.92—2.23 (m, 6 H);
1.22—1.65 (m, 18 H); 0.93 (t, 3 H, J = 7.0 Hz). 13С NMR, δ:
140.1 (C(1)); 131.2 (C(12)); 129.7 (С(11)); 125.3 (C(2)); 35.1
(C(10)); 32.1 (C(16)); 29.5 (C(15)); 29.3 (C(14)); 29.0 (C(9));
26.8 (C(13)); 26.6 (C(3)); 26.5 (C(4)); 26.4, 26.1, 25.3, 25.1
(С(5)—C(8)); 22.6 (C(17)); 14.2 (С(18)). MS (EI, 70 eV),
m/z: 248.
References
1. V. A. D´yakonov, O. A. Trapeznikova, A. G. Ibragimov,
U. M. Dzhemilev, Izv. Akad. Nauk, Ser. Khim., 2009, 926
[Russ. Chem. Bull., Int. Ed., 2009, 58, 948]
2. V. A. D´yakonov, R. K. Timerkhanov, U. M. Dzhemilev,
A. G. Ibragimov, Izv. Akad. Nauk, Ser. Khim., 2007, 2156
[Russ. Chem. Bull., Int. Ed., 2007, 56, 2232].
3. V. A. D´yakonov, R. K. Timerkhanov, T. V. Tumkina, A. G.
Ibragimov, U. M. Dzhemilev, Tetrahedron Lett., 2009, 50, 1270.
4. A. A. Panasenko, L. M. Khalilov, A V. Kuchin, G. A.
Tolstikov, Izv. Akad. Nauk, SSSR, Ser. Khim., 1980, 2652 [Bull.
Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.), 1980, 29].
5. R. R. Muslukhov, L. M. Khalilov, I. R. Ramazanov, A. Z.
Sharipova, A. G. Ibragimov, U. M. Dzhemilev, Izv. Akad.
Nauk, Ser. Khim., 1997, 2194 [Russ. Chem. Bull. (Engl.
Transl.), 1997, 46, 2082].
2ꢀDeuterioꢀ1ꢀ[(Z)ꢀ2ꢀdeuteriononꢀ2ꢀenꢀ1ꢀyl]cyclononene
(27b). Yield 17%. Found (%): C, 86.11; H + D, 13.59. C18H30D2.
1
Calculated (%): C, 86.32; H, 12.07; D, 1.61. H NMR, δ: 5.33
(t, 1 H, J = 8 Hz); 2.40 (s, 2 H); 1.94—2.22 (m, 6 H); 1.20—1.69
(m, 18 H); 0.93 (t, 3 H, J = 7.0 Hz). 13С NMR, δ: 140.2 (C(1));
131.3 (C(12)); 129.4 (t, C(11), JC,D = 23.5 Hz); 35.3 (C(10));
32.1 (C(16)); 29.5 (C(15)); 29.4 (C(14)); 29.1 (C(9)); 26.8 (C(13));
26.7 (C(3)); 26.5 (C(4)); 26.4, 26.1, 25.4, 25.2 С(5)—C(8));
22.6 (C(17)); 14.3 (С(18)) (the signal for the C(2) atom was not
observed). MS (EI, 70 eV), m/z: 250.
1ꢀ[(Z)ꢀ3ꢀPhenylpropꢀ2ꢀenꢀ1ꢀyl]cyclononene (26c). Yield
16%. Found (%): C, 89.72; H, 9.96. C18H24. Calculated (%):
1
C, 89.94; H, 10.06. H NMR, δ: 7.21—7.36 (m, 5 H, Ph); 6.58
(d, 1 H, J = 8 Hz); 5.61 (m, 1 H); 5.21 (t, 1 H, J = 10 Hz); 3.02

2464
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
D´yakonov et al.
6. A. J. Gordon, R. A. Ford, in The Chemist´s Companion,
J. Wiley and Sons, New York—London—Sydney—Toronto,
1972, 300 pp.
7. D. B. Millward, A. P. Cole, R. M. Waymouth, Organoꢀ
metalics, 2000, 19, 1870.
13. U. M. Dzhemilev, A. G. Ibragimov, R. R. Gilyazev, L. O.
Khafizova, Tetrahedron, 2004, 60, 1281.
14. U. M. Dzhemilev, A. G. Ibragimov, R. R. Muslukhov, Izv.
Akad. Nauk, Ser. Khim., 1994, 276 [Russ. Chem. Bull. (Engl.
Transl.), 1994, 43, 255].
8. A. G. Ibragimov, L. O. Khafizova, G. N. Gil´fanova, U. M.
Dzhemilev, Izv. Akad. Nauk, Ser. Khim., 2002, 2095 [Russ.
Chem. Bull., Int. Ed., 2002, 51, 2255].
9. U. M. Dzhemilev, A. G. Ibragimov, L. G. Yakovleva, L. O.
Khafizova, A. L. Borisova, L. R. Yakupova, Izv. Akad. Nauk,
Ser. Khim., 2003, 1490 [Russ. Chem. Bull., Int. Ed., 2003, 52,
1573].
10. E. Negishi, J.ꢀL. Montchamp, L. Anastasia, A. Elizarov,
D. Choueiry, Tetrahedron Lett., 1998, 39, 2503.
11. V. A. D´yakonov, E. Sh. Finkelshtein, A. G. Ibragimov,
Tetrahedron Lett., 2007, 48, 8583.
15. D. Y. Kondakov, E. Negishi, J. Am. Chem. Soc., 1996, 118,
1577.
16. U. M. Dzhemilev, A. G. Ibragimov, A. B. Morozov, L. M.
Khalilov, R. R. Muslukhov, G. A. Tolstikov, Izv. Akad. Nauk,
Ser. Khim., 1991, 1141 [Bull. Acad. Sci. USSR, Div. Chem.
Sci. (Engl. Transl.), 1991, 40, 1022].
17. R. Kh. Fre´ydlina, E. M. Bra´nina, A. N. Nesmeyanov,
Dokl. Akad. Nauk SSSR, 1969, 138, 1369 [Dokl. Chem. (Engl.
Transl.), 1969, 138].
Received March 10, 2009;
in revised form July 30, 2009
12. Z. Xi, P. Li, Angew. Chem., Int. Ed. Engl., 2000, 39, 2950.