Joint cycloalumination of ethylene and other unsaturated compounds with EtAlCl2 in the presence of Cp2ZrCl2. Synthesis of aluminacarbocycles

Article abstract of DOI:10.1134/S1070428010040032

A procedure has been developed for the selective synthesis of five-membered aluminum-containing heterocycles, 2,3-dialkyl-1-ethylaluminacyclopent-2-enes, 3-alkyl-1-ethylaluminacyclopentanes, 2-alkylidene-1-ethylaluminacyclopentanes, and 3-alkyl-1-ethyl-2-methylidenealuminacyclopentanes, via joint cycloalumination of ethylene and other unsaturated compounds (acetylenes, olefins, and allenes) with EtAlCl₂ in the presence of Cp ₂ZrCl₂ as catalyst.

Full text of DOI:10.1134/S1070428010040032

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 4, pp. 474–479. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.G. Ibragimov, L.O. Khafizova, L.I. Khusainova, T.V. Tyumkina, U.M. Dzhemilev, 2010, published in Zhurnal Organicheskoi
Khimii, 2010, Vol. 46, No. 4, pp. 484–489.
Joint Cycloalumination of Ethylene and Other Unsaturated
Compounds with EtAlCl2 in the Presence of Cp2ZrCl2.
Synthesis of Aluminacarbocycles
A. G. Ibragimov, L. O. Khafizova, L. I. Khusainova, T. V. Tyumkina, and U. M. Dzhemilev
Institute of Petroleum Chemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
Received June 17, 2009
Abstract—A procedure has been developed for the selective synthesis of five-membered aluminum-containing
heterocycles, 2,3-dialkyl-1-ethylaluminacyclopent-2-enes, 3-alkyl-1-ethylaluminacyclopentanes, 2-alkylidene-
1-ethylaluminacyclopentanes, and 3-alkyl-1-ethyl-2-methylidenealuminacyclopentanes, via joint cycloalumina-
tion of ethylene and other unsaturated compounds (acetylenes, olefins, and allenes) with EtAlCl2 in the
presence of Cp2ZrCl2 as catalyst.
DOI: 10.1134/S1070428010040032
Increased interest in Cp2ZrCl2--catalyzed cycloalu-
mination of unsaturated compounds (acetylenes [1, 2],
olefins [3, 4], and allenes [5]) with Et3Al is related to
the possibility for synthesizing novel aluminacarbo-
cycles, such as aluminacyclopent-2-enes and alumina-
cyclopentanes. The subsequent one-pot transforma-
tions of aluminacarbocycles generated in situ [6, 7]
into alcohols [8–10], including optically active ones
[11], ethers [12], 1,3-dienes [13], carbo- [14–17] and
heterocycles [18–20], cyclopentenones [21], and bio-
logically active compounds [22, 23] stimulated further
studies on cycloalumination reactions with a view to
replace explosive triethylaluminum by less pyrophoric
organoaluminum compounds. These studies resulted in
the development of a new synthetic approach [24] to
2,3-dialkyl-1-ethylaluminacyclopent-2-enes I based on
cycloalumination of acetylenes with EtAlCl2 in the
presence of ethylene generated from 1,2-dichloro-
ethane and magnesium using Cp2TiCl2 as catalyst.
Apart from 2,3-dialkyl-1-ethylaluminacyclopent-2-
enes I, this reaction led to the formation of consider-
able amounts (up to ~40%) of 2,3-dialkyl-1-ethylalu-
minacycloprop-2-enes II and 2,3,4,5-tetraalkyl-1-ethyl-
aluminacyclopenta-2,4-dienes III [24] (Scheme 1).
Drawbacks of this procedure include the necessity
of generating ethylene (for building up molecule I)
from 1,2-dichloroethane with the aid of magnesium
and low chemoselectivity of the reaction due to forma-
tion of intermediate titanium-containing heterocycles
(titanacyclopropenes and titanacyclopenta-2,4-dienes
[25]) whose transmetalation with EtAlCl2 yields by-
products II and III.
The goal of the present work was to develop
a procedure for selective synthesis of substituted alu-
minacarbocycles (aluminacyclopent-2-enes and alu-
minacyclopentanes) with the use of relatively fire-safe
reagents (EtAlCl2, AlCl3) and accessible ethylene with
participation of other unsaturated compounds (acet-
ylenes, olefins, allenes). While choosing the catalyst,
as well as conditions for the synthesis of alumina-
carbocycles, we presumed [26] that zirconocene gener-
Scheme 1.
R
R
R
R
R
[Cp2TiCl2]
ClCH2CH2Cl
R
R
EtAlCl2
+
Mg
+
+
+
Al
Et
R
R
R
Al
Et
Al
Et
I
II
III
474

JOINT CYCLOALUMINATION OF ETHYLENE
475
Scheme 2.
Mg (THF)
EtAlCl2
R
R
H2C CH2
R
R
Cp2ZrCl2
[Cp2Zr]
R
R
–MgCl2
Zr
Al
Cp
Cp
Et
O
–Cp2ZrCl2
Ia–Ic
R = Pr (a), Bu (b), Ph (c).
ated, e.g., from Cp2ZrCl2 and BuLi [27] is capable of
taking up alkynes in the presence of ethylene, yielding
up to 98% of 2,3-disubstituted zirconacyclopent-2-
enes. These transformations [26] are characterized by
complete absence in the reaction mixture of tetrasub-
stituted zirconacyclopentadienes that are formed as the
major products in the absence of ethylene [28]. There-
fore, a necessary condition for selective formation of
2,3-disubstituted zirconacyclopent-2-enes (precursors
of aluminacyclopent-2-enes) is generation of [Cp2Zr]
in the presence of ethylene taken in excess with respect
to disubstituted acetylene. Metallic magnesium was
used to generate [Cp2Zr] from Cp2ZrCl2 [29], and
transmetalation of zirconacyclopent-2-enes generated
in situ was performed using EtAlCl2 or AlCl3 accord-
ing to Scheme 2.
the yield of by-products like II and III did not exceed
3%. An important condition for selective formation of
targeted compounds Ia–Ic is slow (portionwise) addi-
tion of alkyne to the reaction mixture in the presence
of ethylene. When the reaction was carried out with the
use of more accessible aluminum(III) chloride instead
of EtAlCl2, other conditions being equal, alumina-
cyclopent-2-enes Ia–Ic were formed in 50–65% yield.
As follows from Scheme 2, ethylene and alkyne mole-
cule are involved in construction of the carbon skele-
ton of compounds Ia–Ic. In the cycloalumination with
Et3Al [1, 2], the aluminacyclopent-2-ene fragment is
formed from alkyne molecule and ethyl substituent in
the initial triethylaluminum [30].
The 13C NMR spectrum of aluminacyclopent-2-ene
Ia contained two signals in the region corresponding
to double-bonded carbon atoms, at δC 159.6 and
149.9 ppm. The chemical shifts of sp3-hybridized
carbon atoms in molecule Ia were similar to those
reported in [31] for the same compound in an ether
solvent. An additional support to cyclic structure of
compounds Ia and Ib is provided by their transforma-
tion into 1,2-dialkylbuta-1,3-dienes VIa and VIb [15]
or 1,1-disubstituted cyclopropanes VIIa and VIIb [16]
(Scheme 3).
As shown in Scheme 2, cycloalumination of dialkyl-
(phenyl)acetylenes (oct-4-yne, dec-5-yne, and diphen-
ylacetylene) with EtAlCl2 in ethylene atmosphere
(excess pressure 0.02 MPa) in the presence of magne-
sium powder and Cp2ZrCl2 as catalyst (molar ratio
alkyne–EtAlCl2–Mg–Cp2ZrCl2 10:15:12:0.1, THF,
~20°C, 6 h) gave aluminacyclopent-2-enes Ia–Ic in
65–80% yield. Analysis of their hydrolysis and
deuterolysis products IVa–IVc and Va–Vc showed that
Scheme 3.
R
R
R
H+, H2O
CH2=CHCH2OAc, [Ni]
R
H2C
R
~55%
H
H
IVa–IVc
VIa, VIb
R
Al
Et
O
R
R
R
Ia–Ic
D+, D2O
Me2SO4
~65%
R
Me
D
Me
VIIa, VIIb
D
Va–Vc
R = Pr (a), Bu (b), Ph (c).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010

IBRAGIMOV et al.
476
Scheme 4.
R
D+, D2O
D
D
IXa–IXc
R
R
Mg, [Zr], RCH=CH2, THF
–MgCl2
S8, PhH, 80°C
Al
CH2
H2C
EtAlCl2
+
Et
S
O
Xa–Xc
R
CH2=CHCH2Cl
[Pd]
VIIIa–VIIIc
XIa–XIc
R = C4H9 (a), C6H13 (b), C8H17 (c).
27
The synthesis of 2,3-dialkyl(phenyl)aluminacyclo-
pent-2-enes I with the use of EtAlCl2 and AlCl3
underlay an efficient procedure for the preparation of
3-alkylaluminacyclopentanes VIII. A necessary condi-
tion for selective formation of compounds VIII is
intermediate generation of 3-alkylzirconacyclopentane
complex from ethylene and terminal olefin [32]. We
expected that transmetalation of 3-alkylzirconacyclo-
pentane with EtAlCl2 or AlCl3 should lead to alumina-
cyclopentanes. By slowly (portionwise) adding termi-
nal olefin (hex-1-ene, oct-1-ene, or dec-1-ene) to
EtAlCl2 under an ethylene pressure of 0.02 MPa in
THF in the presence of magnesium and Cp2ZrCl2 as
catalyst (molar ratio olefin–EtAlCl2–Mg–Cp2ZrCl2
10 :15:12:0.1, ~20°C, 6 h) we obtained 3-alkyl-1-
ethylaluminacyclopentanes VIIIa–VIIIc in 55–70%
yield (Scheme 4). Here, the yield of by-products
(3,4-dialkylaluminacyclopentanes [32, 33]) did not
exceed 3–5%. In the reaction with AlCl3 instead of
EtAlCl2, the yields of aluminacyclopentanes VIII were
45–60%. The reaction was less selective when the re-
action mixture contained insufficient amount of ethyl-
ene, for example, if the latter was bubbled through the
mixture under atmospheric pressure or generated from
1,2-dichloroethane by the action of magnesium [34].
the Al NMR spectrum of VIIIa, recorded in an elec-
tron-donating solvent (THF), a signal at δAl 176.8 ppm
was observed (ω1/2 = 6000 Hz). For comparison, the
27Al NMR spectrum of the same aluminacyclopentane
synthesized according to the procedure described in
[36] was recorded in toluene-d8 (δC 153.0 ppm, ω1/2
=
5600 Hz). Displacement of the aluminum signal in
going to polar solvent indicates formation of a com-
plex of aluminacyclopentane with tetrahydrofuran (sol-
vent) molecule via Al···O interaction. The complex
was also characterized by H and 13C NMR data.
1
Coordination of a THF molecule to the aluminum atom
could give rise to two stereoisomeric structures with
1,3-cis and 1,3-trans configurations of alkyl substit-
uents due to appearance of asymmetric center at the
four-coordinate aluminum atom (as in the complex
with pyridine [36]). However, compound VIIIa dis-
played in the 13C NMR spectrum only one set of
signals. This means that only one stereoisomer is
formed preferentially. As noted previously [36], one
stereoisomer also prevailed in excess deuteropyridine,
whereas by portionwise addition of deuteropyridine we
succeeded in detecting splitting (~1:1) of signals from
carbon atoms in molecule VIIIa. Presumably, electron-
donating solvent gives rise to the equilibrium
The structure of 3-alkylaluminacyclopentanes
VIIIa–VIIIc was confirmed by 1H, 13C, and 27Al NMR
spectroscopy (tetrahydrofuran was used as solvent),
including two-dimensional homo- and heteronuclear
correlation techniques (COSYHH, HSQC, HMBC). In
the 13C NMR spectra, the chemical shifts of the C8-
cyclic structure appear in a weaker field relative to the
corresponding carbon signal of dialuminum compound
[35]; therefore, compounds VIII were preliminarily
identified as 3-substituted aluminacyclopentanes. In
cis-VIIIa···THF
trans-VIIIa···THF, which is
displaced toward thermodynamically more stable
stereoisomer in the presence of excess solvent. The
results of molecular mechanics calculations (MM2) of
the pyridine complex showed that its cis stereoisomer
is more stable (by 3.0 kcal/mol). According to DFT
calculations (PBE/3z functional) with account taken of
electron correlation (Priroda 6.0 program), stereo-
isomer cis-VIIIa is more energetically favorable (by
3.2 kcal/mol).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010

JOINT CYCLOALUMINATION OF ETHYLENE
477
Scheme 5.
R
R
EtAlCl2, Mg, [Zr], THF
CH2
Al
Al
CH2
R
·
H2C
+
+
–MgCl2
CH2
Et
Et
O
O
XIIa, XIIb
XIIIa, XIIIb
D
D
D+, D2O
D
D
+
CH2
R
R
XIVa, XIVb
XVa, XVb
R = C6H13 (a), C8H17 (b).
The chemical shifts of the α-carbon atoms (C2 and
C5) in complex VIIIa ···THF are smaller by 3 and
0.5 ppm, respectively, than those of the complex of
VIIIa with pyridine. The doublet signal at δC 43.0 ppm
was assigned to C3, and it displayed correlation with
proton signal at δ 1.12 ppm in the HSQC spectrum.
The COSYHH spectrum showed two couples of
geminal diastereotopic protons which resonated in the
upfield region, from δ 0.1 to –1.0 ppm, and were
assigned to methylene groups in the five-membered
ring, neighboring to the aluminum atom. According to
the HSQC data, the couple of protons resonating at
δ 0.00 and –0.98 ppm (Δδ = 0.98 ppm) gives a cross
peak with C2 (δC 13.6 ppm), while the other couple is
attached to C5 (δC 5.7 ppm). The difference in the
chemical shifts of the latter is somewhat smaller and is
Δδ = 0.38 ppm, which is consistent with the longer
distance to the C3 chiral center. Owing to the presence
of an asymmetric center, protons on C4 and C6 are also
diastereotopic. The presence of cross peaks in the
COSYHH spectrum between the methylene protons on
C2 and C3, as well as on C4 and C5, is consistent with
the expected spin–spin couplings in the aluminacyclo-
pentane molecule.
2-alkylidene-1-ethylaluminacyclopentanes XIIa and
XIIb and 3-alkyl-1-ethyl-2-methylidenealuminacyclo-
pentanes XIIIa and XIIIb at a ratio of ~5:1 (overall
yield 55–75%). Under these conditions, the yield of
by-products (regioisomeric aluminacyclopentanes
formed from two 1,2-diene molecules [37]) did not
exceed 10%. Aluminacyclopentanes XIIa/XIIIa and
XIIb/XIIIb were identified by their transformation
into 1,4-dideuteroolefins XIVa/XVa and XIVb/XVb
(Scheme 5).
EXPERIMENTAL
The hydrolysis and deuterolysis products were
analyzed on a Chrom-5 chromatograph; 1200×3-mm
column packed with 5% of SE-30 or 15% of PEG-
6000 on Chromaton N-AW, carrier gas helium. The
mass spectra (electron impact, 70 eV) were obtained
on an MKh-1306 spectrometer (ion source temperature
200°C). The NMR spectra were measured on a Bruker
1
Avance spectrometer at 400.13 MHz for H,
100.62 MHz for 13C, and 104.22 MHz for 27Al. Two-
dimensional experiments (COSYHH, HSQC, HMBC)
were performed according to standard procedures. The
yields of organoaluminum compounds were deter-
mined by GLC analysis of theit hydrolysis products
using dodecane as internal standard. All reactions with
organometallic compounds were carried out under dry
argon. Tetrahydrofuran was dried by heating under
reflux over metallic sodium and distilled before use.
Commercially available 86% EtAlCl2 was used.
Deuterolysis of compounds VIIIa–VIIIc generated
in situ gave 3-alkyl-1,4-dideuterobutanes IXa–IXc,
and 3-alkyltetrahydrothiophenes Xa–Xc were obtained
by heating aluminacyclopentanes VIIIa–VIIIc with
elemental sulfur in boiling benzene. Carbocyclization
of VIIIa–VIIIc in the presence of palladium com-
plexes and allyl chloride as reoxidant [17] afforded
monosubstituted cyclobutanes XIa–XIc (Scheme 4).
Joint cycloalumination of ethylene and unsatu-
rated compounds (dialkylacetylenes, terminal al-
kenes, and 1,2-dienes) with EtAlCl2 (AlCl3) in the
presence of Cp2ZrCl2 as catalyst (general proce-
dure). A glass reactor was charged under dry argon
By reactions of 1,2-dienes (nona-1,2-diene and un-
deca-1,2-diene) with EtAlCl2 in the presence of magne-
sium powder and Cp2ZrCl2 as catalyst under an ethyl-
ene pressure of 0.02 MPa (20–22°C, THF) we obtained
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IBRAGIMOV et al.
478
under stirring with 3 ml of THF, 12 mmol of magne-
sium powder, and 15 mmol of EtAlCl2 or AlCl3,
1.0 mmol of Cp2ZrCl2 was then added in ethylene
atmosphere, excess ethylene pressure (~0.02 MPa) was
supplied, and a solution of 10 mmol of the correspond-
ing unsaturated compound in 8 ml of THF was slowly
(over a period of ~2 h) added from a dropping funnel
equipped with a pressure-equalization arm. The mix-
ture was stirred for 4 h, treated with a 8–10% aqueous
solution of HCl or DCl, and extracted with diethyl
ether or hexane. The extract was dried over MgSO4,
the solvent was removed, and the products were isolat-
ed by fractional distillation. Hydrolysis and deuterol-
ysis products IVa–IVc, Va–Vc, IXa–IXc, XIVa,
XIVb, XVa, and XVb were identified by comparison
with authentic samples [1–3, 5, 24].
ture was stirred for 12 h at ~20°C, treated with 8–10%
hydrochloric acid, and extracted with hexane (3×
5 ml). The extract was washed with a solution of
Na2CO3 until neutral reaction and dried over CaCl2.
1,1-Disubstituted cyclopropanes VIIa and VIIb were
identified by comparison with authentic samples [16].
3-Alkyltetrahydrothiophenes Xa–Xc (general
procedure). Anhydrous benzene, 10 ml, was added
(after removal of THF) to 3-alkyl-1-ethylalumina-
cyclopentane VIIIa–VIIIc generated in situ from the
corresponding terminal alkene, 45 mmol of cycloocta-
sulfane (C8) was added, and the mixture was stirred for
6 h on heating at ~80°C. The mixture was then treated
with 8–10% hydrochloric acid and extracted with
diethyl ether, the extract was washed with a solution of
sodium carbonate until neutral reaction and dried over
CaCl2, and 3-alkyltetrahydrothiophenes Xa–Xc were
identified by comparison with authentic samples [18].
1-Ethyl-2,3-dipropylaluminacyclopent-2-ene
(Ia). Yield ~80% (according to the GLC data for the
hydrolysis product). 13C NMR spectrum (toluene-d8),
δC, ppm: 0.4 t (C6), 3.1 t (C5), 29.9, 32.2, 22.0, 21.62 t
(C8, C9, C11, C12), 13.78, 13.81 s (C10, C13), 35.5 t (C4),
149.9 s (C2), 159.6 s (C3).
Alkylcyclobutanes XIa–XIc (general procedure).
Anhydrous diethyl ether, 10 ml, was added (after
removal of THF) to 3-alkyl-1-ethylaluminacyclo-
pentane VIIIa–VIIIc generated in situ from the corre-
sponding terminal alkene, the mixture was cooled to
–5°C, 45 mmol of allyl chloride and 5 mol % of
Pd(acac)2–Ph3P were added, and the mixture was
stirred for 6 h at ~20°C, treated with 8–10% hydro-
chloric acid, and extracted with diethyl ether. The ex-
tract was washed with a solution of sodium carbonate
until neutral reaction and dried over CaCl2. Alkyl-
cyclobutanes XIa–XIc were identified by comparison
with authentic samples [17].
3-Butyl-1-ethylaluminacyclopentane (VIIIa).
1
Yield ~65% (GLC). H NMR spectrum (THF-d8), δ,
ppm: –0.78 br.m (1H, 2-H), –0.49 br.m (1H, 5-H),
–0.29 m (2H, 6-H), –0.20 br.m (1H, 5-H), 0.00 br.m
(1H, 2-H), 0.79 m (3H, C11H3), 0.88 t (3H, C7H3, J =
6 Hz), 0.99 m (1H, 8-H), 1.19 m (8H, 3-H, 4-H, 8-H,
9-H, 10-H), 1.76 br.m (CH2 in THF), 3.64 br.m (CH2O
in THF). 13C NMR spectrum, δ, ppm: 0.0 t (C6), 5.7 t
(C5), 13.6 t (C2), 10.0 q (C7), 14.8 q (C11), 23.7 t (C10),
31.5 t (C9), 38.8 t (C4), 42.1 t (C8), 43.1 d (C3), 26.5 t
(CH2 in THF), 67.2 t (CH2O in THF).
This study was performed under financial support
by the President of the Russian Federation (program
for support of leading scientific schools, project
no. NSh-2349.2008.3).
1,2-Dialkylbuta-1,3-dienes VIa and VIb (general
procedure). Allyl acetate, 40 mmol, and Pd(acac)2,
5 mol %, were added under stirring at –5°C to 2,3-di-
alkyl-1-ethylaluminacyclopent-2-ene Ia or Ib generat-
ed in situ from the corresponding dialkylacetylene, and
the mixture was stirred for 10 h at room temperature,
treated with 8–10% hydrochloric acid, and extracted
with diethyl ether or hexane. The organic phase was
separated, washed with a solution of sodium carbonate
until neutral reaction, and dried over CaCl2. 1,2-Dial-
kylbuta-1,3-dienes VIa and VIb were identified by
comparison with authentic samples [15].
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