Cycloalumination of allylbenzenes with triethylaluminum in the presence of Cp2ZrCl2. One-pot synthesis of 2-benzylbutane-1,4-diols as precursors of dibenzylbutane lignans

Article abstract of DOI:10.1134/S107042801612006X

One-pot synthesis of 2-[(hydroxy- and methoxyphenyl)methyl]butane-1,4-diols in an overall yield of 60–65% by cycloalumination of allylbenzenes (4-allyl-1-methoxybenzene, 4-allyl-1,2-dimethoxybenzene, 5-allyl-2-methoxyphenol, and 5-allyl-1,2,3-trimethoxybenzene) with triethylaluminum in the presence of Cp₂ZrCl₂is reported for the first time. The developed procedure opens a new synthetic route to practically important β-substituted butane-1,4-diols that are precursors to dibenzylbutane lignans.

Full text of DOI:10.1134/S107042801612006X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 12, pp. 1750–1755. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © L.V. Parfenova, P.V. Kovyazin, T.V. Tyumkina, L.M. Khalilov, U.M. Dzhemilev, 2016, published in Zhurnal Organicheskoi Khimii,
2016, Vol. 52, No. 12, pp. 1759–1764.
Cycloalumination of Allylbenzenes with Triethylaluminum
in the Presence of Cp2ZrCl2. One-Pot Synthesis
of 2-Benzylbutane-1,4-diols as Precursors
of Dibenzylbutane Lignans
L. V. Parfenova,* P. V. Kovyazin, T. V. Tyumkina, L. M. Khalilov, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
*e-mail: luda_parfenova@mail.ru
Received July 14, 2016
Abstract—One-pot synthesis of 2-[(hydroxy- and methoxyphenyl)methyl]butane-1,4-diols in an overall yield
of 60–65% by cycloalumination of allylbenzenes (4-allyl-1-methoxybenzene, 4-allyl-1,2-dimethoxybenzene,
5-allyl-2-methoxyphenol, and 5-allyl-1,2,3-trimethoxybenzene) with triethylaluminum in the presence of
Cp2ZrCl2 is reported for the first time. The developed procedure opens a new synthetic route to practically
important β-substituted butane-1,4-diols that are precursors to dibenzylbutane lignans.
DOI: 10.1134/S107042801612006X
Synthesis of lignan compounds possessing a broad
spectrum of biological activity, in particular anticancer
and antiviral, constitutes a topical problem of modern
organic chemistry. With respect to their structure,
lignans can be divided into several classes: dibenzyl-
butanes, dibenzylbutanediols, butyrolactones, tetrahy-
drofurans, aryltetrahydronaphthalenes, dibenzooctadi-
enes, etc. [1–8].
steps [1, 4–7]. One of the most frequently used
methods for building up 2,3-disubstituted butane skele-
ton with nonequivalent benzyl groups implies prepara-
tion of 2-benzylbutane-1,4-dicarboxylic acids or
butyrolactones by the Stobbe condensation, followed
by introduction of a benzylidene or benzyl group into
the 3-position (Scheme 1).
A promising synthetic route to dibenzylbutane
lignans may be based on the Dzhemilev reaction, i.e.,
cyclometalation of terminal alkenes with organo-
Presently known methods for the synthesis of di-
benzylbutane lignans generally include a number of
Scheme 1.
Stobbe condensation
O
O
Me
Me
Ar2CHO
O
OR
OR
RO
Ar1
Ar2
+
RO
Ar1
H
O
Ar1
O
HO
Ar1
OH
Ar2
Dzhemilev reaction
OH
OH
(1) AlEt3, [Zr]
(2) [O]
Ar1
Ar2
Ar1
Ar2Hlg
Ar1
O
O
Ar1
CH2
O
O
1750

CYCLOALUMINATION OF ALLYLBENZENES WITH TRIETHYLALUMINUM
1751
Scheme 2.
Ar
4
5
3
2
Et
Cp2ZrCl2, 20°C
H2C
Al
+
Ar
Et3Al
+
+
1
Ar
Et2Al
Ar
Al
Et
2a–2d
1a–1d
3a–3d
4a–4d
D+/D2O
D+/D2O
D+/D2O
Ar
Et
D
Ar
D
Ar
D
D
5a–5d
6a–6d
7a–7d
Ar = 4-MeOC6H4 (a), 3,4-(MeO)2C6H3 (b), 4-HO-3-MeOC6H4 (c), 3,4,5-(MeO)3C6H2 (d).
aluminum or organomagnesium compounds catalyzed
by transition metal complexes. This approach makes it
possible to obtain in one step cyclic organometallic
compounds under mild conditions with high regio- and
stereoselectivity, and their subsequent transformations
via reactions with various electrophiles and nucleo-
philes could led to the formation of diverse monomers,
including 2,3-disubstituted butanes and butane-1,4-
diols [9, 10]. We previously reported cyclometalation
of methoxy-substituted allylbenzenes with ethylalumi-
num and ethylmagnesium halides in the presence of
η5-complexes of zirconium, which afforded dibenzyl-
butane lignans as pure diastereoisomers [11].
The reactions of allylbenzenes 1a–1d with triethyl-
aluminum in the presence of Cp2ZrCl2 (Scheme 2)
were carried out at room temperature for 24 h. The
subsequent deuterolysis showed that the products were
compounds 2a–2d, 3a–3d, and 4a–4d resulting, re-
spectively, from cyclo-, carbo-, and hydroalumination
of alkenes 1a–1d.
The formation of cycloalumination product 2a was
confirmed by multinuclear NMR data for the reaction
mixture in THF-d8. The 13C chemical shifts of the
alumolane ring [δC, ppm: 14.10 (C2), 45.62 (C3), 36.15
(C4), 6.29 (C5)] are similar to those reported in [12] for
benzyl-substituted alumolane. Furthermore, methylene
protons therein characteristically showed diastereo-
topicity intrinsic to five-membered alumacarbocycles,
e.g., 3-substituted alumolanes described previously. In
the 27Al NMR spectrum, we observed a signal at
δAl 172.6 ppm which corresponds to a solvate complex
of alumolane with THF molecule.
Herein we describe one-pot synthesis of benzyl-
substituted butane-1,4-diols by catalytic cycloalumina-
tion of allylbenzenes. The products attract interest as
precursors to dibenzylbutane lignans containing
nonequivalent aromatic rings, and the described
approach can be used as a basis for the development of
enantioselective procedures for the synthesis of
lignans.
The substrate conversion and chemoselectivity of
the reaction strongly depended on such factors as
Scheme 3.
AlEt3, 2–3 equiv
Cp2ZrCl2, 20°C
O
Et
OAlEt2
O
O
O
+
Al
Al
Et
Et
OAlEt2
Et
H2C
1e
8
9
D+/D2O
D+/D2O
O
Et
OD
D
D
D
+
D
OD
O
Et
10
11
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 12 2016

PARFENOVA et al.
1752
Reaction of allylbenzenes 1a–1d with triethylaluminum in the presence of Cp2ZrCl2 (20°C, 24 h)
Yield, %
Run
no.
Conversion, %
(Zr, mol %)
Alkene, ratio [Zr]–alkene–[Al]
Catalyst
Solvent
Hexane
2
3
4
01 1-Allyl-4-methoxybenzene (1a),
Cp2ZrCl2
31 (2)
13
13
5
(1–4):50:60)
02 ” ”
03 ” ”
97 (4)
53
05
26
03
18
02
CH2Cl2
11 (4);
AlEt3, 2.4 equiv
04 ” ”
05 ” ”
–
36 (2)
99 (2)
70
23
71
51
10
23
6
03
05
13
Toluene
Hexane
07 4-Allyl-1,2-dimethoxybenzene (1b),
Cp2ZrCl2
1:50:120
08 ” ”
CH2Cl2
Toluene
Benzene
Toluene
Toluene
00
95
86
96
99
09 ” ”
73
55
75
79
19
08
15
08
03
24
06
12
10 5-Allyl-2-methoxyphenol (1c), 1:50:180
Cp2ZrCl2
Cp2ZrCl2
11 ” ”
12 5-Allyl-1,2,3-trimethoxybenzene (1d),
1:50:180
alkene structure, reactant ratio, and solvent nature. The
reaction of AlEt3 with allylanisole 1a in hydrocarbon
solvents at room temperature in the presence of
Cp2ZrCl2 was characterized by quantitative conversion
and high yield of the cycloalumination product (see
table, run nos. 2, 5). The use of toluene as solvent
improved the chemoselectivity with respect to cyclo-
alumination (yield 71%). When the reaction was
carried out under the conditions described in [13, 14]
for allylbenzene containing no other substituents in the
benzene ring, the substrate conversion was consider-
ably lower (see table, run nos. 1, 3, 4).
process is opening of the five-membered ring in 1e by
the action of AlEt3, and next follows addition of AlEt3
to the exocyclic double bond to form cycloalumination
products 8 and 9.
In order to obtain benzyl-substituted butane-1,4-di-
ols 12a–12d that are promising starting materials for
the preparation of practically important lignans
(γ-butyrolactones [15]), the reaction mixture contain-
ing cyclic compounds 2a–2d was exposed to dry
oxygen over a period of 24 h (Scheme 4). The overall
yield of 12a–12d was 60–65%. The oxidation with
other oxidants, e.g., hydrogen peroxide in aqueous
potassium hydroxide, was characterized by lower yield
of 12a–12d (50–55%). Raising the oxidation tempera-
ture to 40°C or addition of a catalytic amount of
Ti(OPr-i)4 did not improve the yield of 2-benzyl-
butane-1,4-diols to an appreciable extent.
The reactions of triethylaluminum with 4-allyl-1,2-
dimethoxybenzene (1b), 5-allyl-2-methoxyphenol (1c,
eugenol), and 5-allyl-1,2,3-trimethoxybenzene (1d) in
toluene afforded 71–79% of the corresponding cyclo-
alumination products (see table, run nos. 9, 11, 12). In
these cases, 2 or 3 equiv of AlEt3 should be added to
ensure high conversion of the initial alkene and
acceptable yield of 2b–2d.
Thus, the catalytic cycloalumination of allylben-
zenes with triethylaluminum in the presence of
Cp2ZrCl2 leads to the formation of 3-benzyl-substitut-
ed alumolanes whose oxidation and hydrolysis gives
Analogous reaction of 5-allyl-2H-1,3-benzodioxole
(1e) with 2‒3 equiv of AlEt3 gave a mixture of com-
pounds 8 and 9 at a ratio of 2.2:1 in up to 95% yield;
after treatment of the reaction mixture with DCl/D2O,
compounds 10 and 11 were isolated (Scheme 3). The
reaction of 1e with a smaller amount of AlEt3 resulted
in the formation of cycloalumination products 8 and 9
and those resulting from carbometalation of the di-
oxole fragment of 1e. Presumably, the first stage of the
Scheme 4.
Ar
(1) O3
(2) H+/H2O
HO
HO
Ar
Al
Et
2a–2d
12a–12d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 12 2016

CYCLOALUMINATION OF ALLYLBENZENES WITH TRIETHYLALUMINUM
1753
60–65% of 2-[(hydroxy- and methoxyphenyl)methyl]-
butane-1,4-diols. The proposed procedure is anticipat-
ed to constitute the basis for further development of
enantioselective catalytic methods for the synthesis of
lignan compounds.
isolated by column chromatography on silica gel using
acetone–hexane (1:4). Yield of 12a–12d 60–65%.
1-Ethyl-3-(3-methoxybenzyl)alumolane (2a).
1H NMR spectrum (C7H8, THF-d8, 298 K), δ, ppm:
2
3
–0.81 t (1H, 2-Hax, J = J = 13.4 Hz), –0.50 m (1H,
5-Hax), –0.20–0.00 m (4H, 2-Heq, 5-Heq, AlCH2CH3),
0.83–1.00 m (4H, 4-Hax, AlCH2CH3), 1.45 m (1H,
4-Heq), 2.31 m and 2.42 m (2H, CH2Ar), 3.43 m (3H,
OCH3), 6.80–7.00 m (4H, Harom). 13C NMR spectrum
(C7H8, THF-d8), δC, ppm: 0.20–1.50 t (AlCH2CH3),
6.29 br.t (C5), 9.20–10.40 q (AlCH2CH3), 14.10 t (C2),
36.15 t (C4), 45.62 d (C3), 48.1 t (CH2Ar), 55.34 s
(OCH3); 25.31 and 68.59 t (THF); 130.76, 131.07,
136.43, 158.45 (Carom). 27Al NMR spectrum (C7H8,
THF-d8): δAl 176.6 ppm (w1/2 = 6.5 kHz).
EXPERIMENTAL
All operations with organometallic reagents were
carried out under argon using Schlenk techniques.
Solvents were dried and distilled in a stream of argon
before use. Initial allylbenzenes 1a–1c were com-
mercial products (Aldrich). Arylalkenes 1d and 1e
were synthesized according to the procedure described
in [16]. Triethylaluminum was commercial product
(25% solution in toluene), and the complex Cp2ZrCl2
was prepared from ZrCl4 (99.5%, Aldrich) [17].
1-Methoxy-4-{(4-2H1)-2-[(2H1)methyl]butyl}-
1
benzene (5a). H NMR spectrum (CDCl3), δ, ppm:
The NMR spectra were recorded on a Bruker
Avance-400 spectrometer at 400.13 (1H) and
100.62 MHz (13C) using standard 5-mm NMR tubes.
One- and two-dimensional NMR experiments (COSY,
HSQC, HMBC, NOESY) were carried out with
standard pulse sequences.
0.79‒0.88 m (2H, CHCH2D), 0.88‒0.99 m (2H,
CH2D), 1.11‒1.22 m and 1.34‒1.46 m (1H each,
DCH2CH2), 1.56‒1.65 m (1H, CH), 2.38 d.d (2J =
13.2, 3J = 8.0 Hz) and 2.64 d.d (2J = 13.2, 3J = 6.0 Hz)
(1H each, (1H, CHCH2), 3.84 s (3H, OCH3), 6.88 d
3
and 7.12 d (2H each, Harom, J = 8.6 Hz). 13C NMR
The elemental analyses of 12a–12d were obtained
on a Carlo Erba 1106 CHNO analyzer. The hydrolysis
and deuterolysis products were analyzed with a Carlo
Erba gas chromatograph equipped with a flame ioniza-
tion detector (Ultra-1 capillary column 50 000×
0.32 mm; carrier gas helium). GC/MS analysis was
performed with a Shimadzu QP 2010 Ultra spec-
trometer. The components were quantitated by the
internal standard method.
spectrum (CDCl3), δC, ppm: 11.2 t (C4, JCD = 18.9 Hz),
18.6 t (C1, JCD = 19.0 Hz), 29.0 (C3), 36.7 (C2), 42.4
(C5), 55.2 (OCH3), 113.5, 129.8, 132.4, 157.8 (Carom).
Mass spectrum, m/z (Irel, %): 180 (9) [M]+, 121 (100),
91 (7), 78 (11), 77 (10), 32 (32).
3,4-Dimethoxy-4-{(4-2H1)-2-[(2H1)methyl]butyl}-
1
benzene (5b). H NMR spectrum (CDCl3), δ, ppm:
0.81‒0.87 m (2H, DCH2CH), 0.87‒1.00 m (2H,
DCH2CH2), 1.11‒1.23 m and 1.36‒1.45 m (1H each,
DCH2CH2), 1.56‒1.68 m (1H, CH), 2.33 d.d (2J =
13.6, 3J = 8.0 Hz) and 2.59 d.d (2J = 13.6, 3J = 6.0 Hz)
(1H each, CHCH2), 3.87 s (3H, OCH3), 3.89 s (3H,
Cyclometalation of allylbenzenes with triethyl-
aluminum in the presence of zirconocene catalyst
(general procedure). A 10-ml glass reactor equipped
with a magnetic stir bar was charged under argon with
17–35 mg (0.06–0.12 mmol) of Cp2ZrCl2, 3 mmol of
allylbenzene 1a–1e, and 3.6–10.8 mmol of AlEt3
(25% solution in toluene). The mixture was continu-
ously stirred for 16 h at 22°C, and a 0.2-mL sample
was withdrawn and treated with 10% aqueous HCl or
DCl at 0°C. The products were extracted with diethyl
ether, and the extract was dried over Na2SO4. The
yields were determined by GLC and GC/MS. The
remaining reaction mixture was cooled to 0°C, dry
oxygen was bubbled through it over a period of 2 h,
and the mixture was stirred for 24 h more in an oxygen
atmosphere. It was then hydrolyzed with 10% aqueous
HCl and extracted with diethyl ether, the extract was
dried over Na2SO4, and the resulting alcohols were
3
OCH3), 6.69 s (1H, Harom ), 6.70 d (1H, Harom, J =
3
8.4 Hz), 6.80 d (1H, Harom, J = 8.4 Hz). 13C NMR
spectrum (CDCl3), δC, ppm: 11.2 t (C4, JCD = 19.0 Hz),
18.6 t (C1, JCD = 19.1 Hz), 29.0 (C3), 36.7 (C2), 43.0
(C5), 55.8 (OCH3), 55.9 (OCH3); 111.0, 112.4, 121.0,
134.4, 147.0, 148.6 (Carom). Mass spectrum, m/z
(Irel, %): 210 (13) [M]+, 152 (12), 151 (100).
2-Methoxy-4-{(4-2H1)-2-[(2H1)methyl]butyl}-
1
phenol (5c). H NMR spectrum (CDCl3), δ, ppm:
0.82‒0.89 m (2H, DCH2CH), 0.89‒0.99 m (2H,
DCH2CH2), 1.11‒1.23 m and 1.35‒1.47 m (1H each,
DCH2CH2), 1.56‒1.69 m (1H, CH), 2.31 d.d (2J =
13.4, 3J = 8.4 Hz) and 2.58 d.d (2J = 13.4, 3J = 6.0 Hz)
(1H each, CHCH2), 3.90 s (3H, OCH3), 5.49 s (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 12 2016

PARFENOVA et al.
1754
OH), 6.64‒6.71 m (1H, Harom), 6.67 s (1H, Harom),
(CDCl3), δ, ppm: 1.49‒1.61 m and 1.61‒1.72 m (1H
each, OCH2CH2), 1.84‒1.97 m (1H, CH), 2.47 d.d
2
6.87 d (1H, Harom, J = 8.4 Hz). 13C NMR spectrum
3
3
(2J = 13.6, J = 7.60 Hz) and 2.59 d.d (2J = 13.6, J =
(CDCl3), δC, ppm: 11.2 t (C4, JCD = 19.0 Hz), 18.6 t
(C1, JCD = 19.0 Hz), 29.1 (C3), 36.8 (C2), 43.1 (C5),
55.9 (OCH3); 111.6, 113.9, 121.8, 133.7, 143.5, 146.2
(Carom). Mass spectrum, m/z (Irel, %): 196 (13) [M]+,
138 (13), 137 (100), 122 (8), 94 (7), 32 (99).
6.4 Hz) (1H each, PhCH2), 3.42 d.d (1H, OCH2CH,
3
2J = 10.8, J = 7.2 Hz), 3.52‒3.64 m (2H, OCH2CH,
OCH2CH2), 3.65‒3.75 m (1H, OCH2CH2), 3.78 s (3H,
3
OCH3), 6.82 d and 7.08 d (2H each, Harom, J =
8.4 Hz). 13C NMR spectrum (CDCl3), δC, ppm: 35.2
(C3), 37.2 (C5), 41.4 (C2), 55.2 (OCH3), 60.8 (C4), 65.4
(C1), 113.8 (C8), 130.0 (C7), 132.4 (C6), 157.8 (C9).
Found, %: C 68.64; H 8.57. C12H18O3. Calculated, %:
C 68.54; H 8.63.
1,2,3-Trimethoxy-4-{(4-2H1)-2-[(2H1)methyl]-
1
butyl}benzene (5d). H NMR spectrum (CDCl3), δ,
ppm: 0.902‒0.98 m (2H, DCH2CH), 0.86‒0.97 m (2H,
DCH2CH2), 1.15‒1.231 m and 1.244‒1.392 m (1H
each, DCH2CH2), 1.60‒1.74 m (1H, CH), 2.256‒
2.416 m and 2.513‒2.667 m (1H each, CHCH2), 3.87 s
(6H, OCH3), 3.89 s (3H, OCH3), 6.40 s (2H, Harom).
2-[(3,4-Dimethoxyphenyl)methyl]butane-1,4-diol
1
(12b). Yield 242 mg (62%). H NMR spectrum
13C NMR spectrum (CDCl3), δC, ppm: 11.2 t (C4, JCD
=
(CDCl3), δ, ppm: 1.52‒1.64 m and 1.66‒1.76 m (1H
each, OCH2CH2), 1.90‒2.00 (1H, CH), 2.49 d.d (2J =
19.0 Hz), 18.7 t (C1, JCD = 19.1 Hz), 34.0 (C3), 36.6
(C2), 43.3 (C5), 56.1 (OCH3), 60.7 (OCH3); 106.1,
135.1, 137.9, 152.4 (Carom). Mass spectrum, m/z
(Irel, %): 240 (63.6) [M]+, 225 (4), 183 (7), 182 (47),
181 (100), 167 (17), 148 (12).
3
3
14.0, J = 7.60 Hz) and 2.61 d.d (2J = 14.0, J =
6.4 Hz) (1H each, PhCH2), 3.47 d.d (1H, OCH2CH,
3
2J = 10.8, J = 6.8 Hz), 3.58‒3.68 m (2H, OCH2CH,
OCH2CH2), 3.72‒3.80 m (1H, OCH2CH2), 3.85 s (3H,
OCH3), 3.86 s (3H, OCH3), 6.67‒6.73 m (2H, Harom),
5-{(4-2H1)-2-[(2H1)Methyl]butyl}-2-propoxy-
3
6.78 d (1H, Harom, J = 8.8 Hz). 13C NMR spectrum
1
(O-2H)phenol (10). H NMR spectrum (CDCl3), δ,
(CDCl3), δC, ppm: 35.3 (C3), 37.9 (C5), 41.3 (C2),
55.86 (OCH3), 55.91 (OCH3), 61.0 (C4), 65.5 (C1),
111.2 (C10), 112.3 (C7), 121.1 (C11), 132.9 (C6), 147.3
(C9), 148.8 (C8). Found, %: C 65.01; H 8.4. C13H20O4.
Calculated, %: C 64.98; H 8.39.
ppm: 0.77‒0.85 m (2H, CHCH2D), 0.88‒0.97 m (2H,
CH2CH2D), 1.04‒1.12 m (3H, CH3), 1.53‒1.68 m (1H,
CH), 1.78‒1.93 m (2H, CH3CH2CH2), 2.22‒2.38 m
and 2.49‒2.65 m (1H each, 5-CH2), 3.92‒4.08 m (2H,
CH2O), 6.64‒6.70 m (1H, Harom), 6.65‒6.69 m (1H,
2-[(3-Hydroxy-4-methoxyphenyl)methyl]butane-
H
arom), 6.83‒6.89 m (1H, Harom). 13C NMR spectrum
1
1,4-diol (12c). Yield 233 mg (63%). H NMR spec-
(CDCl3), δC, ppm: 10.5 (CH3), 11.3 t (C4, JCD
=
trum (CDCl3), δ, ppm: 1.56‒1.68 m and 1.69‒1.80 m
(1H each, OCH2CH2), 1.93‒2.03 m (1H, CH), 2.51 d.d
18.9 Hz), 18.8 t (C1, JCD = 19.0 Hz), 22.5 (CH3CH2),
36.8 (C2), 43.1 (C5), 70.3 (OCH2); 113.9, 112.6, 121.7,
133.6, 143.7, 145.7 (Carom). Mass spectrum, m/z
(Irel, %): 224 (16) [M]+, 182 (3), 181 (1), 165 (32), 123
(100), 77 (9), 43 (14), 42 (6), 41 (12).
3
3
(2J = 14.0, J = 6.8 Hz) and 2.63 d.d (2J = 14.0, J =
7.6 Hz) (1H each, PhCH2), 3.53 d.d (1H, OCH2CH,
3
2J = 11.2, J = 7.2 Hz), 3.52‒3.64 m (2H, OCH2CH,
OCH2CH2), 3.77‒3.86 m (1H, OCH2CH2), 3.90 s (3H,
4-{(4-2H1)-2-[(2H1)Methyl]butyl}-2-propoxy-
3
OCH3), 6.68 d (1H, Harom, J = 7.8 Hz), 6.70 s (1H,
1
(O-2H)phenol (11). H NMR spectrum (CDCl3), δ,
Harom), 6.85 d (1H, Harom, 3J = 7.8 Hz). 13C NMR spec-
trum (CDCl3), δC, ppm: 35.2 (C3), 38.0 (C5), 41.4 (C2),
55.9 (OCH3), 61.2 (C4), 65.6 (C1), 111.5 (C7), 114.2
(C10), 121.7 (C11), 132.1 (C6), 143.9 (C8), 146.4 (C9).
Found, %: C 63.64; H 7.98. C12H18O4. Calculated, %:
C 63.70; H 8.02.
ppm: 0.77‒0.85 m (2H, CHCH2D), 0.88‒0.97 m (2H,
CH2CH2D), 1.04‒1.12 m (2H, CH3), 1.53‒1.68 m (1H,
CH), 1.78‒1.93 m (2H, CH3CH2CH2), 2.22‒2.38 m
and 2.49‒2.65 m (1H each, 4-CH2), 3.92‒4.08 m (2H,
CH2O), 6.58‒6.69 m (1H, Harom), 6.74‒6.81 m (1H,
H
arom), 6.75‒6.82 m (1H, Harom). 13C NMR spectrum
2-[(3,4,5-Trimethoxyphenyl)methyl]butane-1,4-
(CDCl3), δC, ppm: 10.5 (CH3), 11.3 t (C4, JCD
=
1
diol (12d). Yield 296 mg (60%). H NMR spectrum
18.9 Hz), 18.8 t (C1, JCD = 19.0 Hz), 22.6 (CH3CH2),
36.6 (C2), 42.7 (C5), 70.5 (OCH2); 111.3, 115.3, 120.5,
135.1, 144.0, 145.5 (Carom). Mass spectrum, m/z
(Irel, %): 224 (13.6) [M]+, 182 (7), 181 (6), 165 (11),
123 (100), 77 (7), 41 (9).
(CDCl3), δ, ppm: 1.57‒1.70 m and 1.71‒1.83 m
(1H each, OCH2CH2), 1.95‒2.08 m (1H, CH), 2.53 d.d
3
3
(2J = 10.6, J = 7.6 Hz) and 2.65 d.d (2J = 10.6, J =
7.4 Hz) (1H each, PhCH2, 3.55 d.d (2J = 10.6, J =
3
4.8 Hz) and 3.66‒3.73 m (1H each, OCH2CH), 3.66‒
3.75 m and 3.79‒3.82 m (1H each, OCH2CH2), 3.87 s
(6H, OCH3), 3.85 s (3H, OCH3), 6.41 s (2H, Harom).
2-[(4-Methoxyphenyl)methyl]butane-1,4-diol
1
(12a). Yield 210 mg (64%). H NMR spectrum
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 12 2016

CYCLOALUMINATION OF ALLYLBENZENES WITH TRIETHYLALUMINUM
1755
13C NMR spectrum (CDCl3), δC, ppm: 35.3 (C3), 38.7
(C5), 41.2 (C2), 56.1 (OCH3), 60.9 (C4), 61.2 (OCH3),
65.6 (C1), 106.0 (C7), 136.1 (C9), 153.1 (C8).
Found, %: C 62.22; H 8.13. C14H22O5. Calculated, %:
C 62.20; H 8.20.
7. Pan, J., Chen, S., Yang, M., Wu, J., Sinkkonen, J., and
Zou, K., Nat. Prod. Rep., 2009, vol. 26, p. 1251.
8. Teponno, R.B., Kusari, S., and Spiteller, M., Nat. Prod.
Rep., 2016, vol. 33, p. 1044.
9. Dzhemilev, U.M. and Ibragimov, A.G., Russ. Chem.
Rev., 2000, vol. 69, p. 121.
10. D’yakonov, V.A., Dzhemilev Reaction in Organic and
Organometallic Synthesis (Chemistry Research and
Applications), New York: Nova Science, 2010.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 12-03-00363-a, 15-03-03227a).
11. Parfenova, L.V., Berestova, T.V., Kovyazin, P.V.,
Yakupov, A.R., Mesheryakova, E.S., Khalilov, L.M.,
and Dzhemilev, U.M., J. Organomet. Chem., 2014,
vols. 772–773, p. 292.
12. Tyumkina, T.V., Islamov, D.N., Parfenova, L.V.,
Khalilov, L.M., and Dzhemilev, U.M., Magn. Reson.
Chem., 2016, vol. 54, p. 62.
13. Dzhemilev, U.M., Ibragimov, A.G., Zolotarev, A.P.,
Muslukhov, R.R., and Tolstikov, G.A., Izv. Akad. Nauk
SSSR, Ser. Khim., 1990, p. 2831.
14. Parfenova, L.V., Kovyazin, P.V., Tyumkina, T.V., Mak-
rushina, A.V., Khalilov, L.M., and Dzhemilev, U.M.,
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