Cycloalumination of cycloalkynes with triethylaluminum catalyzed by zirconium complexes

Article abstract of DOI:10.1134/S1070428012010010

Cycloalumination of cycloalkynes with triethylaluminum in the presence of zirconium complexes was performed for the first time, and new bicyclic aluminacyclopentenes were obtained in 74-94% yield. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012010010

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 1, pp. 1–7. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.A. D’yakonov, L.F. Galimova, T.V. Tyumkina, U.M. Dzhemilev, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48,
No. 1, pp. 9–15.
Cycloalumination of Cycloalkynes with Triethylaluminum
Catalyzed by Zirconium Complexes
V. A. D’yakonov, L. F. Galimova, T. V. Tyumkina, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
Received June 9, 2011
Abstract—Cycloalumination of cycloalkynes with triethylaluminum in the presence of zirconium complexes
was performed for the first time, and new bicyclic aluminacyclopentenes were obtained in 74−94% yield.
DOI: 10.1134/S1070428012010010
According to published data, disubstituted acety-
lenes react with Et3Al in the presence of Cp2ZrCl2 to
give 2,3-dialkyl(aryl)aluminacyclopent-2-enes in
~90% yield [1−3]; the products are exceptionally
interesting as intermediate products in the development
of one-pot procedures for the synthesis of substituted
cyclopentenones [4, 5], cyclopropanes [6−9], and some
other difficultly accessible carbo- and heterocyclic
compounds [10] (Scheme 1).
Up to now, cycloalumination of cyclic acetylenes
with Et3Al under catalysis by transition metal com-
plexes has not been reported. We believe that such
reactions could give rise to new classes of organo-
aluminum compounds, fused aluminacyclopent-2-enes,
which could be used as a basis for the development of
effective one-pot procedures for the synthesis of
difficultly accessible high-grade fragrant substances,
spirocyclopropanes, and bicyclic heteroatom-contain-
ing compounds.
In continuation of our studies on cycloalumination
of unsaturated compounds in the present work we
examined reactions of some cyclic alkynes (cyclo-
octyne, cyclodecyne, cyclododecyne, and cyclotri-
decyne) with Et3Al in the presence of Cp2ZrCl2 as
catalyst with a view to synthesize the corresponding
aluminacyclopentenes; this catalyst previously showed
Scheme 1.
R
Me2SO4
R'
Me
Me
R
R
CO2
R'
R
Et3Al, [Zr]
O
R
R'
R'
Al
Et
S8
R'
R'
S
R
BrCH2OMe
CH2
R = CH2=CHCH2, Ar; R′ = Alk, Ar, Me3Si.
1

D’YAKONOV et al.
2
Scheme 2.
Et
Et
Et3Al, [Zr]
Al
+
+
+
AlEt2
Et
AlEt2
I
II
III
IV
H+/H2O (D+/D2O)
X
Et
Et
+
+
+
IV
X
X
X
V (VII)
(VIII)
VI (IX)
V, VI, X = H; VII–IX, X = D.
the highest activity in cyclometalation of olefins,
allenes, and acyclic acetylenes [11−16].
clooct-1-ene) (VI), and 1,2:3,4:5,6-tris(hexamethyl-
ene)benzene (IV) at a ratio of 2:6:1 in an overall yield
of 86%. Likewise, deuterolysis of the reaction mixture
gave 1-[(2-2H1)-ethyl]-(2-2H1)cyclooct-1-ene (VII),
(2-2H1)cyclooct-1-ene (VIII), 2-ethyl-(2′-2H1)-1,1′-bi-
(cyclooct-1-ene) (IX), and trimer IV. The presence of
monodueterated hydrocarbons VIII and IX among the
deuterolysis products indicated that the process was
accompanied by side carboalumination.
While studying the effects of various factors on the
product yield and composition, we found that reactions
of cyclooctyne with Et3Al in aliphatic (hexane, cyclo-
hexane) or aromatic solvents (benzene, toluene) in the
absence of catalyst lead to formation of only acyclic
organoaluminum compounds as a result of 1,2-carbo-
Initially, the reaction was carried out with cyclo-
octyne as substrate under the conditions developed
previously for the cycloalumination of acyclic disubsti-
tuted acetylenes (substrate–Et3Al–[Zr] ratio 10:30:0.5,
hexane, 20−25°C, 6 h). The reaction gave a mixture of
cyclic and acyclic organoaluminum compounds I−III
and cyclooctyne cyclic trimer, tris(hexamethylene)ben-
zene (IV) (Scheme 2). The structure of compounds
1
I−III was determined on the basis of the H and 13C
NMR and mass spectra of hydrocarbons V−IX ob-
tained by acid hydrolysis (V, VI) or deuterolysis
(VII−IX) of the reaction mixture. Thus, the hydrolysis
afforded 1-ethylcyclooct-1-ene (V), 2-ethyl-1,1′-bi(cy-
Scheme 3.
Et
AlEt2
Et
Hexane
+
+
IV
AlEt2
II
III
+ Et3Al
Et
[Zr], THF or Et3N
Al
Et
+
AlEt2
I
II
II
III
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012

CYCLOALUMINATION OF CYCLOALKYNES WITH TRIETHYLALUMINUM
Table 1. Reaction of cyclooctyne with triethylaluminum
3
Catalyst
Temperature, °C
Solvent
Molar ratio I–II–III–IV
Overall yield, %
–
–
–
22
22
22
22
22
22
22
00
–
0:0:0:1
0:1:7:1
0:4:6:1
1:1:6:1
1:3:1:1
3:2:0:0
3:4:0:0
2:1:4:0
82
78
76
86
85
73
71
48
Hexane
Benzene
Hexane
Benzene
Benzene
Benzene
Hexane
Cp2ZrCl2
Cp2ZrCl2
Cp2ZrCl2 (Et3Al–Et3N)
Cp2ZrCl2 (Et3Al–THF)
Cp2ZrCl2
alumination of the initial alkyne with Et3Al (compound
II) and intermolecular carboalumination (III) [com-
pound III can also be obtained by reaction of II with
cyclooctyne (Scheme 3)]; trimer IV is also formed
(Table 1). The reaction performed under solvent-free
conditions gave 82% of compound IV.
produce previously unknown bicyclic aluminacyclo-
pentenes XIII−XV in 82–92% yield (Scheme 4,
Table 2). No acyclic organoaluminum compounds
were formed as by-products under these conditions.
The reaction did not occur in the absence of a catalyst.
4
3
5
2
By deactivating Et3Al via complex formation with
an equimolar amount of Et3N or THF we succeeded in
considerably increasing the fraction of 9-ethyl-9-
aluminabicyclo[6.3.01,8]undec-1(8)-ene (I) in the reac-
tion mixture and avoiding formation of by-products III
and IV (Table 1). Reduced temperature also favors
some increase in the yield of bicyclic compound I;
however, in this case the overall yield considerably
decreases despite prolonged reaction (12 h).
15
1
6
7
14
Al13
12
17
8
11
16
Me
9
10
XIV
The structure of new organoaluminum compounds
XIII–XV and products of their acid hydrolysis and
deuterolysis was determined by 1D and 2D 1H and 13C
NMR spectroscopy (the structure of molecule XIV
with atom numbering is shown above). The 13C NMR
spectrum of compound XIV in THF-d8 contained two
singlets at δC 157.0 and 147.1 ppm in the region corre-
sponding to sp2-hybridized carbon atoms. The latter
signal had lesser intensity because of broadening and
was assigned to C12 directly linked to the aluminum
atom. Correspondingly, the signal at δC 157.0 ppm
belongs to C1, which is confirmed by the HMBC data.
The C1 atom gives two cross peaks in the HMBC spec-
trum due to coupling with protons on C2 and C15,
whereas the C12 atom (δC 147.1 ppm) gives only one
cross peak with protons on C11. Analysis of the HSQC
spectrum allowed us to reliably identify signals from
The fractions of cyclo- and carboalumination prod-
ucts were determined by GC–MS from the ratio of di-
and monodeuterated hydrocarbons.
The low selectivity for aluminacyclopentene I is
likely to be related to high reactivity of the triple bond
in cyclooctyne; therefore, we presumed that increase of
the ring size of the initial acetylene should be accom-
panied by increase in the fraction of the target bicyclic
organoaluminum compounds with respect to by-prod-
ucts formed via noncatalytic carboalumination.
We found that cyclodecyne (X), cyclododecyne
(XI), and cyclotridecyne (XII) reacted with 3 equiv of
Et3Al in the presence of a catalytic amount of Cp2ZrCl2
(5 mol %) in aliphatic or aromatic hydrocarbons to
Scheme 4.
Et
Et3Al, [Zr]
H+/H2O or D+/D2O
D
Al
or
Et
( )n
( )n
XVI–XVIII
( )n
( )n
X–XII
XIII–XV
XIX–XXI
X, XIII, XVI, XIX, n = 3; XI, XIV, XVIII, XX, n = 5; XII, XV, XVIII, XXI, n = 6.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012

D’YAKONOV et al.
Table 2. Reaction of cycloalkynes with triethylaluminum in the presence of Cp2ZrCl2
4
Cycloalkyne (no.)
n
Solvent
Time, h
Temperature, °C
Product no. (yield, %)
Cyclodecyne (X)
3
5
5
5
5
5
5
5
5
5
6
Hexane
Hexane
Benzene
Toluene
Hexane
Hexane
Hexane
CH2Cl2
THF
4
4
4
4
7
1
4
4
6
6
4
20–22
20–22
20–22
20–22
00
XII (87)
XIV (91)
XIV (92)
XIV (91)
XIV (82)
XIV (85)
XIV (94)
XIV (74)
XIV (0)
Cyclododecyne (XI)
Cyclododecyne (XI)
Cyclododecyne (XI)
Cyclododecyne (XI)
Cyclododecyne (XI)
Cyclododecyne (XI)
Cyclododecyne (XI)
Cyclododecyne (XI)
Cyclododecyne (XI)
Cyclotridecyne (XII)
40
20–22
20–22
20–22
20–22
20–22
Et2O
XIV (0)
Hexane
XV (89)
carbon nuclei and protons in positions 2, 11, and 15.
The C15 (δC 34.0 ppm) and 15-H signals (δ 2.21 ppm)
were located relatively downfield, the C2 and C11
signals appeared at δC 28−29 ppm, and the 2-H and
11-H protons resonated at δ 2.05−2.11 ppm.
Analysis of the structure of new unsaturated bi-
cyclic organoaluminum compounds led us to presume
that these metallacycles can be used to develop effec-
tive one-pot procedures for the synthesis of difunc-
tional carbo- and heterocyclic compounds, including
those having a spiro structure, via transmetalation,
cross coupling, and carbocyclization reactions reported
by us previously [8−10, 17−19]. For example, reac-
tions of 13-ethyl-13-aluminabicyclo[10.3.0]pentadec-
1(12)-ene (XIV) generated in situ with carbon dioxide,
elemental selenium, bromomethyl methyl ether, and
molecular iodine gave bicyclo[10.3.0]pentadec-1(12)-
en-13-one (XXII), 13-selenabicyclo[10.3.0]pentadec-
1(12)-ene (XXIII), 4-methylidenespiro[2.11]tetra-
decane (XXIV), and 1-iodo-2-(2-iodoethyl)cyclodec-
ene (XXV), respectively, in 74−93% yield (Scheme 5).
Bicyclo[10.3.0]pentadec-1(12)-en-13-one (XXII, yield
84%) is the key intermediate compound in the syn-
thesis of exaltone, muscone, and bicyclo[10.3.0]penta-
decan-13-one that are high-grade fragrant substances
with musk-like odor [20, 21].
According to the COSY HH homonuclear correla-
tion data, methylene protons on C15 are actually cou-
pled with those attached to C14; the 14-H signal is
displaced upfield to –0.38 ppm due to the presence
of neighboring metal atom. Apart from 14-H–15-H
interactions, the COSY HH spectrum displayed
expected 11-H–10-H and 2-H–3-H couplings in the
cyclic fragment (δ 2.05−2.11 to 1.35−1.42 ppm). Thus,
the use of two-dimensional homo- and heteronuclear
correlation techniques allowed us to confirm the struc-
ture of compound XIV as 13-ethyl-13-aluminabicyclo-
[10.3.0]pentadec-1(12)-ene. The aluminum atom in
XIV gave a signal at δAl 157.6 ppm in the 27Al NMR
spectrum (THF). The signal from C10 (in the γ-position
with respect to the aluminum atom) is slightly dis-
placed downfield (δC 29.5 ppm), which clearly fol-
lowed from the HSQC spectrum containing a cross
peak from C10 and ring protons resonating at
δ 1.38 ppm. In addition, the C14 signal (δC 9.0 ppm) is
readily distinguishable in the HSQC spectrum. Al-
though the chemical shift of C14 is very similar to that
of the methyl carbon atom in the AlCH2CH3 fragment,
the chemical shifts of the corresponding protons are
appreciably different (δ –0.37 and 1.0 ppm, respec-
tively). In the 13C NMR spectrum of XIV recorded
from a solution in toluene signals from the double-
bonded carbon atoms were observed at δC 159.8 (C1)
and 139.3 ppm (C12) ppm, whereas the 27Al NMR
spectrum remained almost unchanged (δAl 156.7 ppm).
Among tested zirconium-containing catalysts
[Cp2ZrCl2, (MeCp)2ZrCl2, Ind2ZrCl2, Zr(acac)4,
ZrOCl2, Zr(OBu)4, (Me2N)2ZrCl2, (C5H5N)2ZrCl2,
ZrCl4, (MeO)2ZrCl2], Cp2ZrCl2 showed the highest
catalytic activity in the cycloalumination of cyclic
alkynes with Et3Al. The catalyst concentration strongly
affected the yield of bicyclic organoaluminum com-
pound XIV. Reduction of the amount of Cp2ZrCl2
from 5 to 2 mol % required that the reaction be
prolonged to 8–10 h to attain the complete conversion
and the same yield. Raising the amount of the catalyst
to 15–20 mol % considerably reduced the yield, pre-
sumably due to polymerization of the initial alkyne.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012

CYCLOALUMINATION OF CYCLOALKYNES WITH TRIETHYLALUMINUM
5
Scheme 5.
CO2
BrCH2OMe
CH2
O
( )5
( )5
XXII
XXIV
I
Al
Et
( )5
I2
Se
Se
XIV
I
( )5
( )5
XXIII
XXV
On the basis of our experimental and published data
we proposed the following scheme for the formation
of bicyclic organoaluminum compounds XIII−XV
(Scheme 6). Initially formed Zr–Al complex XXVI
[22] reacts with cycloalkyne to produce seven-mem-
bered cyclic complex XXVII with bridging chlorine
atom. Complex XXVII is transformed into bicyclic
aluminacyclopentenes XIII−XV with liberation of
zirconocene complex XXVIII, and reaction of the
latter with Et3Al regenerates initial complex XXVI via
elimination of ethane [2, 22, 23].
EXPERIMENTAL
Gas chromatographic analysis was performed on
a Shimadzu GC-9A instrument equipped with a 2000×
2-mm column packed with 5% of SE-30 on Chromaton
N-AW-HMDS (0.125−0.160 mm); carrier gas helium,
flow rate 30 ml/min; oven temperature programming
1
from 50 to 300°C at a rate of 8 deg/min. The H, 13C,
and 27Al NMR spectra were recorded from solutions in
CDCl3 on a Bruker Avance-400 spectrometer at 400,
1
100, and 104 MHz, respectively; the H chemical
shifts were measured relative to tetramethylsilane. Gas
chromatographic–mass spectrometric analysis was per-
formed on a Finnigan 4021 instrument (HP-5 glass
capillary column, 50 000 × 0.25 mm; carrier gas
helium; oven temperature programming from 50 to
300°C at a rate of 5 deg/min; injector temperature
To conclude, we were the first to reveal that cyclic
alkynes undergo catalytic cycloalumination by the ac-
tion of triethylaluminum in the presence of zirconium
complexes to give in high yield (>85%) representatives
of a new class of organoaluminum compounds, un-
saturated bicyclic aluminacyclopentenes.
Scheme 6.
Cp2ZrCl2
2Et3Al –Et2AlCl, –EtH
Cp
Zr
( )n
EtH
Cp
Cl AlEt2
XXVI
Et
ZrCp2
Cl
Cp2Zr
Cl
AlEt3
( )n
Al
Et Et
XXVII
Et
Cp2Zr
Et3Al
Cl
Al
XXVIII
Et
( )n
XIII–XV
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012

D’YAKONOV et al.
6
280°C; ion source temperature 250°C; electron impact,
70 eV). The elemental compositions were determined
on a Carlo Erba 1106 analyzer. The yields of organo-
aluminum compounds were determined by GLC anal-
ysis of the hydrolysis products. All reactions with or-
ganometallic compounds were carried out in a stream
of dry argon. Compounds IV−IX, XVI−XVIII, and
XXII−XXIV were identified by comparison with
authentic samples [7, 9, 10, 19−21, 24].
CH2), 2.05 m (6H, CH2CH=C). 13C NMR spectrum,
δC, ppm: 12.7 t (C15, JCD = 19.5 Hz), 26.6 (C14); 24.74,
25.6, 25.64, 25.92, 26.35, 26.48, 26.92, 27.29, 28.34
(2C) (C3–C12); 29.64 (C13), 124.10 t (C2, JCD
=
23.5 Hz), 141.16 (C1). Found, %: C 85.47;
H+D 13.69. m/z 210 [M]+. C15H26D2. Calculated, %:
C 85.63; H 12.46; D 1.91. M 210.
1-Iodo-2-(2-iodoethyl)cyclododecene (XXV). Oily
1
substance. H NMR spectrum, δ, ppm: 1.47−1.57 m
Reaction of cycloalkynes with triethylaluminum
in the presence of Cp2ZrCl2 (general procedure).
A glass reactor was filled with dry argon and charged
at 0°C under stirring with 10 mmol of the correspond-
ing cycloalkyne, 0.5 mmol of Cp2ZrCl2, 15 ml of hex-
ane, and 11 mmol of Et3Al. The mixture was allowed
to warm up to 20–22°C, stirred for 4 h, treated with
a 7−10% solution of HCl in water or of DCl in D2O,
and extracted with hexane. The extract was dried over
MgSO4, and the products were isolated by vacuum
distillation.
(18H), 2.34 t (2H, J = 7 Hz), 2.74−2.81 m (2H), 3.17 t
(2H, CH2I, J = 9 Hz). 13C NMR spectrum, δC, ppm:
1.31 (C14); 25.5, 25.71, 26.04, 26.12, 26.31, 26.63,
27.77, 29.65, 31.58 (C4−C12); 41.46 (C3), 47.70 (C13),
103.91 (C2), 144.12 (C1). Found, %: C 37.53; H 5.21;
I 56.61. m/z 446 [M]+. C14H24I2. Calculated, %:
C 37.69; H 5.42; I 56.89. M 446.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 10-03-00046, 11-03-00103, 11-03-97001).
13-Ethyl-13-aluminabicyclo[10.3.0]pentadec-
1(12)-ene (XIV). Oily substance. 13C NMR spec-
trum, δC, ppm: –0.1 (C16), 1.0 (C17), 9.0 (C14), 24−28
(C3−C9), 28.5 (C2), 28.8 (C11), 29.5 (C10), 34.0 (C15),
147.14 (C12), 157.0 (C1). 27Al NMR spectrum (C7D8):
δAl 156.7 ppm.
1-[(2-2H1)Ethyl](2-2H1)cyclodec-1-ene (XIX).
Oily substance. IR spectrum, ν, cm–1: 3090, 2925,
2850, 2160 (C–D), 1450, 905, 790. 1H NMR spectrum,
δ, ppm: 0.96 m (2H, CH2D), 1.34–1.39 m (12H, CH2),
2.05–2.10 m (6H, CH2CH=C). 13C NMR spectrum, δC,
ppm: 12.69 t (C12, JCD = 19.0 Hz), 27.32 (C11); 22.41,
22.56, 24.16, 24.44, 24.64, 25.20, 25.68 (C3−C9); 27.97
(C10), 140.78 (C1); no C2 signal was observed. Found,
%: C 84.49; H+D 15.21. m/z 168 [M]+. C12H20D2. Cal-
culated, %: C 84.62; H 13.01; D 2.36. M 168.
REFERENCES
1. Dzhemilev, U.M., Ibragimov, A.G., and Zolotarev, A.P.,
Mendeleev Commun., 1992, p. 135.
2. Negishi, E., Kondakov, D.Y., Choueiry, D., Kasai, K.,
and Takahashi, T., J. Am. Chem. Soc., 1996, vol. 118,
p. 9577.
3. D’yakonov, V.A., Dzhemilev Reactions in Organic and
Organometallic Synthesis, New York: NOVA Science,
2010, p. 96.
4. Negishi, E., Montchamp, J.-L., Anastasia, L., Eliza-
rov, A., and Choueiry, D., Tetrahedron Lett., 1998,
vol. 39, p. 2503.
5. D’yakonov, V.A., Tuktarova, R.A., and Dzhemi-
lev, U.M., Tetrahedron Lett., 2010, vol. 51, p. 5886.
6. Dzhemilev, U.M., Ibragimov, A.G., Ramazanov, I.R.,
Luk’yanova, M.P., and Sharipova, A.Z., Izv. Ross. Akad.
Nauk, Ser. Khim., 2001, p. 465.
7. D’yakonov, V.A., Tuktarova, R.A., Khalilov, L.M., and
Dzhemilev, U.M., Tetrahedron Lett., 2011, vol. 52,
p. 4602.
8. D’yakonov, V.A., Tuktarova, R.A., Tyumkina, T.V.,
Khalilov, L.M., and Dzhemilev, U.M., Russ. Chem.
Bull., 2010, vol. 59, p. 1902.
9. D’yakonov, V.A., Tuktarova, R.A., Trapeznikova, O.A.,
Khalilov, L.M., and Popod’ko, N.R., Arkivoc, 2011,
part (viii), p. 20.
10. D’yakonov, V.A., Ibragimov, A.G., Khalilov, L.M., Ma-
karov, A.A., Timerkhanov, R.K., Tuktarova, R.A., and
Galimova, L.F., Khim. Geterotsikl. Soedin., 2009, p. 393.
11. D’yakonov, V.A., Galimova, L.F., Ibragimov, A.G., and
Dzhemilev, U.M., Russ. J. Org. Chem., 2008, vol. 44,
p. 1291.
1-[(2-2H1)Ethyl](2-2H1)cyclododec-1-ene (XX).
Oily substance. IR spectrum, ν, cm–1: 3090, 2925,
2850, 2160 (C–D), 1450, 905, 790. 1H NMR spectrum,
δ, ppm: 0.98 m (2H, CH2D), 1.36–1.41 m (16H, CH2),
2.05–2.10 m (6H, CH2CH=C). 13C NMR spectrum, δC,
ppm: 12.61 t (C14, JCD = 19.5 Hz); 22.36, 22.51, 24.05,
24.40, 24.57, 24.64, 25.08 (2C), 25.68 (C3−C12); 27.47
(C13), 28.77 (C12), 124.11 t (C2, JCD = 24.0 Hz), 140.89
(C1). Found, %: C 86.45; H+D 14.22. m/z 196 [M]+.
C14H24D2. Calculated, %: C 86.63; H 12.32; D 2.05.
M 196.
1-[(2-2H1)Ethyl](2-2H1)cyclotridec-1-ene (XXI).
Oily substance. IR spectrum, ν, cm–1: 3080, 2920,
1
2850, 2160 (C–D), 1450, 910, 790, 720. H NMR
spectrum, δ, ppm: 0.99 m (2H, CH2D), 1.38 m (18H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012

CYCLOALUMINATION OF CYCLOALKYNES WITH TRIETHYLALUMINUM
7
12. Dzhemilev, U.M., Ibragimov, A.G., D’yakonov, V.A.,
and Zinnurova, R.A., Russ. J. Org. Chem., 2007,
vol. 43, p. 176.
18. D’yakonov, V.A., Makarov, M.A., Ibragimov, A.G., and
Dzhemilev, U.M., Russ. J. Org. Chem., 2008, vol. 44,
p. 197.
19. D’yakonov, V.A., Makarov, A.A., and Dzhemilev, U.M.,
13. Dzhemilev, U.M. and Ibragimov, A.G., J. Organomet.
Chem., 2010, vol. 695, p. 1085.
Russ. J. Org. Chem., 2009, vol. 45, p. 1598.
20. Nozaki, H., Mori, T., Noyori, R., and Kawanisi, M.,
Can. J. Chem., 1967, vol. 45, p. 1804.
21. Hiyama, T., Shinoda, M., Tsukanaka, M., and No-
14. D’yakonov, V.A., Timerkhanov, R.K., Tuymkina, T.V.,
Ibragimov, A.G., and Dzhemilev, U.M., Tetrahedron
Lett., 2009, vol. 50, p. 1270.
zaki, H., Bull. Chem. Soc. Jpn., 1980, vol. 53, p. 1010.
15. D’yakonov, V.A., Finkelshtein, E.Sh., and Ibragi-
mov, A.G., Tetrahedron Lett., 2007, vol. 48, p. 8583.
22. Negishi, E., Swanson, D.R., Cederbaum, F.E., and
Takahashi, T., Tetrahedron Lett., 1987, vol. 28, p. 917.
23. Aguel, G. and Negishi, E., J. Am. Chem. Soc., 1991,
16. Lewis, D.P., Whitby, R.J., and Jones, R.V.H., Tetra-
hedron, 1995, vol. 51, p. 4541.
vol. 113, p. 7424.
24. D’yakonov, V.A., Timerkhanov, R.K., and Dzhemi-
17. Dzhemilev, U.M., D’yakonov, V.A., Khafizova, L.O.,
and Ibragimov, A.G., Tetrahedron, 2004, vol. 60,
p. 1287.
lev, U.M., Russ. J. Org. Chem., 2010, vol. 46, p. 807.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012