One-pot synthesis of substituted styrenes from vicinal dibromoalkanes and arylboronic acids

Article abstract of DOI:10.1007/s11172-007-0020-5

Dehydrobromination of vicinal dibromoalkanes in systems comprising 1,2-dimethoxy-ethane, N-butyl-N′-methylimidazolium tetrafluoroborate (or tetrabutylammonium bromide), and a base with subsequent palladium-catalyzed cross-coupling of the thus formed bromoalkenes with arylboronic acids furnished substituted styrenes. Springer Science+Business Media, Inc. 2007.

Full text of DOI:10.1007/s11172-007-0020-5

Russian Chemical Bulletin, International Edition, Vol. 56, No. 1, pp. 122—129, January, 2007
122
Oneꢀpot synthesis of substituted styrenes from vicinal dibromoalkanes
and arylboronic acids
А. А. Tikhonov,a А. А. Vasil´ev,bꢀ М. V. Chirskaya,c М. I. Struchkova,b N. L. Merkulova,c and S. G. Zlotinb
аMoscow Chemical Lyceum 1303,
4 Tamozhennyi pr., 111033 Moscow, Russian Federation
bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 5328. Eꢀmail: vasiliev@ioc.ac.ru
cChemBridge Corp.,
1 ul. Malaya Pirogovskaya, 119435 Moscow, Russian Federation.
Fax: +7 (495) 956 4948
Dehydrobromination of vicinal dibromoalkanes in systems comprising 1,2ꢀdimethoxyꢀ
ethane, NꢀbutylꢀN´ꢀmethylimidazolium tetrafluoroborate (or tetrabutylammonium bromide),
and a base with subsequent palladiumꢀcatalyzed crossꢀcoupling of the thus formed bromoalkenes
with arylboronic acids furnished substituted styrenes.
Key words: styrenes, bromoalkenes, boronic acids, crossꢀcoupling, the Suzuki reaction,
bromination, dehydrobromination, ionic liquids.
Among numerous methods for the synthesis of styꢀ
ever, for some dibromides the selective formation of one
of them is possible.6 Recently, we have found7 that
dehydrobromination of 1ꢀ(2,3ꢀdibromopropyl)cycloꢀ
hexanol with K2CO3 in an ionic liquid, NꢀbutylꢀN´ꢀ
methylimidazolium tetrafluoroborate ([bmim][BF4]), proꢀ
ceeded regioꢀ and stereoselectively with the formation of
(Е)ꢀ1ꢀ(3ꢀbromopropꢀ2ꢀenꢀ1ꢀyl)cyclohexanol.
In order to investigate the factor of 1,2ꢀdibromoalkane
structure and reaction conditions, we studied the deꢀ
hydrobromination of model 1,2ꢀdibromohexane (1а),
1,2ꢀdibromoꢀ1ꢀcyclohexylethane (1b), and 1,2ꢀdibromoꢀ
1ꢀphenylethane (1c) in several systems, including ionic
liquids (Scheme 1, Table 1).
renes, reactions catalyzed by transition metal complexes
(the Suzuki,1 Heck,2 and Stille3 reactions) are of particuꢀ
lar interest. From the preparative point of view, the first of
them is the most convenient due to its lower substrate
dependence, as well as to the fact that boronꢀcontaining
secondary products formed in the course of the process
can be easily separated from the crossꢀcoupling products.
One of the versions of the Suzuki reaction consists of the
coupling of alkenyl halides with arylboron derivatives.
For the synthesis of starting alkenyl halides,4 it is conveꢀ
nient to make use of dehydrobromination of available
vicinal dibromoalkanes with bases.
In the present work, we studied the possibility of synꢀ
thesis of various styrenes using a oneꢀpot sequence of two
reactions, viz., dehydrobromination of vicinal dibromoꢀ
alkanes and the Suzuki crossꢀcoupling of the thus formed
bromoalkenes. This approach, when the same base is used
in both stages of the process, makes it possible to avoid
the bromoalkene isolation step, which considerably simꢀ
plifies the procedure and in number of cases ensures the
higher yields of the products. It should be taken into
account that the media used for dehydrobromination must
be compatible with the conditions of the second stage of
crossꢀcoupling.
Scheme 1
Obviously, the selectivity of dehydrobromination of
vicinal dibromoalkanes is a crucial factor that determines
the preparative value of the method. Usually, a mixture of
regioꢀ and stereoisomers is formed in this reaction,5 howꢀ
R = Bu (a), cycloꢀC6H11 (b), Ph (c)
It turned out that dehydrobromination of compounds
1a,b with potassium carbonate or potassium phosphate in
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 116—123, January, 2007.
1066ꢀ5285/07/5601ꢀ0122 © 2007 Springer Science+Business Media, Inc.

Styrenes from 1,2ꢀdibromoalkanes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 1, January, 2007
123
Table 1. Dehydrobromination of vicinal dibromides 1a—с up to 100% conversion under various
conditions
Entry Dibroꢀ
mide
Base*
Solvent
(catalyst**)
T/°С
t/h Product composition (mol.%)
2
Zꢀ3 + Eꢀ3
1
2
3
4
5
6
7
8
1a
K2CO3
K2CO3
K3PO4
K3PO4
K2CO3
K3PO4
K3PO4
K3PO4
KOH
K2CO3
K2CO3
K3PO4
K3PO4
DMSO
DMSO
DMF
DMA
[bmim]BF4
[bmim]BF4
DME ([bmim]BF4)
DME (Bu4NBr)
DME ([bmim]BF4)
DMSO
20
55
100
110
20
20
20
70
20
20
20
70
70
24
168
2
4.5
48
24
48
4
—
—
39
44
49
59
69
65
53
73
—
29 + 32
28 + 28
26 + 25
18 + 23
13 + 18
18 + 17
25 + 22
13 + 14
—
9
3
10
11
12
13
1b
1c
24
72
4
[bmim]BF4
DME ([bmim]Cl)
DME ([bmim]BF4)
98
71
100
2
8 + 21
—
3
* 4 equiv.
** ~30 mol.%.
Scheme 2
polar aprotic solvents, such as DMSO, DMF, and diꢀ
methylacetamide (DMA), proceeded effectively only at
the temperatures ~100 °С (see Table 1, entries 1—4). The
use of potassium carbonate in [bmim]BF4 enabled us to
remarkably increase the rate of the reaction and to lower
its temperature (see Table 1, entries 5 and 11; cf. Ref. 7).
High yields of the products were obtained by carrying
out the reaction in 1,2ꢀdimethoxyethane (DME) in the
presence of ~30 mol.% of imidazolium ([bmim]BF4,
[bmim]Cl) or tetraalkylammonium (Bu4NBr) salts (see
Table 1, entries 7—9, 12, 13). These additives apparently
serve as phase transfer catalysts, since without them the
process does not take place. The catalytic version of the
reaction seems more preferable, since it allows one to
diminish the consumption of expensive organic salts. The
rate of dehydrobromination increases on moving from
K2CO3 or K3PO4 to more basic potassium hydroxide (see
Table 1, entry 9).
R1 = H, R2 = C6H13 (1d—3d, 4a); R1 + R2 = (CH2)5 (1e—3e, 4b);
1 + R2 = (CH2)4 (1f—3f, 4c)
The usual products of the reaction under considerꢀ
ation are mixtures of isomers 2, Zꢀ3 and Еꢀ3. The content
of isomer 2 increases in the series of starting dibromides
1a < 1b < 1c so that in the latter case αꢀbromostyrene 2с
becomes the only dehydrobromination product (see
Table 1, entry 13).
R
of Pd(OAc)2 and powdered solid inorganic bases9,10
were described. It is known that imidazolium salts, formꢀ
Table 2. Dehydrobromination of hydroxylꢀcontaining dibromo
derivatives 1d—f in [bmim]BF4 (4 equiv. K2CO3, 20 °C, converꢀ
sion 100%)
The fraction of type 3 bromoalkenes grows higher for
the dehydrobromination of 1,2ꢀdibromoalkanes 1d—f
bearing hydroxyl group in position 4 (Scheme 2, Table 2).
The process, however, is accompanied by cyclization into
3ꢀbromotetrahydrofuran derivatives 4 (cf. Ref. 7).
The dehydrobromination media can, in principle, be
used for the further crossꢀcoupling of bromoalkenes
thus formed with arylboronic acids. For example, the
crossꢀcoupling in Na2CO3—DME—H2O in the presence
Entry
Comꢀ
pound
R1, R2
t/h Product composition (mol.%)
2
Zꢀ3
Eꢀ3
4
1
2
3
1d
1e
1f
H, C6H13
(CH2)5
(CH2)4
4
4
1
7
5
7
07
11
09
16
56
59
70
28
25
8
of Pd(PPh3)4 as well as in DMF in the presence

124
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 1, January, 2007
Tikhonov et al.
ing catalytically active complexes with palladium comꢀ
pounds,11 have a beneficial effect on the process of crossꢀ
coupling. In fact, addition of arylboronic acids together
with palladium catalyst into in situ formed mixture of
dehydrobromination products 2, Zꢀ3 and Eꢀ3 effected the
crossꢀcoupling reaction leading to styrenes 5 and 6
(Scheme 3).
The isomeric composition of products 5 and 6 correꢀ
sponds to the isomeric composition of dehydrobrominaꢀ
tion products 2 and 3 (see Table 1). From dibromide 1с,
individual 1,1ꢀdisubstituted alkenes 5e,f were obtained.
The reactions in DME—[bmim]BF4 (see Experimental,
method А) proceeded chemoselectively with the formation
of crossꢀcoupling products, whereas in DMF (method B,
see Ref. 10), according to chromatoꢀmass spectrometry
data, the formation of considerable amount of biaryls
(due to homodimerization of arylboronic acids) and dienes
(due to homodimerization of alkenyl bromides) was obꢀ
served. The preparative experiments were carried out acꢀ
cording to method А, the main reaction products were
identified by GCꢀMS and 1H and 13C NMR spectra.
The described sequence of reactions of symmetrical
mesoꢀ4,5ꢀdibromooctane (mesoꢀ1h), obtained by bromiꢀ
nation of transꢀoctꢀ4ꢀene, leads to individual bromoalkene
Eꢀ2h and, correspondingly, to styrene Eꢀ7 with cisꢀorienꢀ
tation of propyl groups at the double bond in 67% yield
(Scheme 4; for the stereochemistry of brominaꢀ
tion—dehydrobromination of cisꢀ and transꢀalkenes see
Ref. 12). For dlꢀ4,5ꢀdibromooctane (dlꢀ1h), obtained
from cisꢀoctꢀ4ꢀene, dehydrobromination to bromoalꢀ
kene Zꢀ2h proceeds quite effectively (GLC data). Howꢀ
ever, subsequent crossꢀcoupling of this compound with
4ꢀmethoxyphenylboronic acid gives the styrene derivative
Zꢀ7 in 5% yield only. This apparently occurs due to the
steric hindrance, created by propyl group cis to the broꢀ
mine atom. The configurations of compounds 7 were
unambiguously proved by 13С NMR data: the allylic
C(3) atom in Eꢀ7 isomer resonates at δ 32.2, whereas the
analogous signal for isomer Zꢀ7 is observed at δ 41.5 (the
effect of steric compression).
Scheme 3
1—3: R = Bu (a), cycloꢀC6H11 (b), Ph (c), Pri (g)
5, 6
R
Ar
Yield (%)
a
b
c
d
e
f
Bu
Bu
Ph
63 (5 + 6)
75 (5 + 6)
69 (5 + 6)
64 (5 + 6)
54 (5)
4ꢀMeOC6H4
4ꢀMeOC6H4
4ꢀMeOC6H4
4ꢀMeOC6H4
Ph
cycloꢀC6H11
Pri
Ph
Ph
51 (5)
By analogy, transꢀ1,2ꢀdibromocyclooctane (1i) was
transformed into individual cisꢀ1ꢀphenylcyclooctꢀ1ꢀene
(8) in 65% yield (Scheme 5). It is known that intermeꢀ
Reagents and conditions: a. Br2, CH2Cl2. b. K3PO4, [bmim]BF4,
DME, 55 °C, 3 h. c. ArB(OH)2, Pd(PPh3)4.
Scheme 4
Reagents and conditions: a. Br2, CH2Cl2. b. K3PO4, [bmim]BF4, DME, 55 °C, 3 h. c. 4ꢀMeOC6H4B(OH)2, Pd(PPh3)4.

Styrenes from 1,2ꢀdibromoalkanes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 1, January, 2007
125
diate 1ꢀbromocyclooctꢀ1ꢀene (2i), resulted from the deꢀ
hydrobromination of compound 1i, has cisꢀconfiguration,
since the transꢀelimination of HBr would have led to the
strained transꢀ1ꢀbromocyclooctene (cf. Ref. 13). Bromiꢀ
nation of a mixture of cisꢀ and transꢀcyclododecenes
leads to a diastereomeric mixture of 1,2ꢀdibromocycloꢀ
dodecanes (1j), dehydrobromination of which gives a mixꢀ
ture of cisꢀ and transꢀ1ꢀbromocyclododecꢀ1ꢀenes (2j). It
so happened that only cisꢀisomer with more sterically
accessible bromine atom reacts with the phenylboronic
acid. The configuration of product 9 has been ascertained
by comparison of 1Н NMR characteristic signals with
those of the authentic sample, prepared by dehydration
of 1ꢀphenylcyclododecanol.14 Dehydrobromination of
transꢀ1,2ꢀdibromocyclohexane under investigated condiꢀ
tions actually does not occur (cf. Refs 13, 15).
In the conclusion, we have studied the scope of oneꢀ
pot procedure for the synthesis of substituted styrenes,
which includes the sequence of dehydrobromination of
vicinal dibromoalkanes and crossꢀcoupling of bromoꢀ
alkenes thus formed with arylboronic acids. In a number
of cases, this approach makes easier the preparative synꢀ
thesis of different styrenes. It should be noted that earlier
the similar approach has been described only for the
1,2ꢀdibromoꢀ3,3,3ꢀtrifluoropropane17 and 1,2ꢀdibromoꢀ
ethane,18 which form individual dehydrobromination
products.
Experimental
NMR spectra were recorded on a Bruker AMꢀ300 specꢀ
trometer (300.13 (1H) and 75.47 (13С) MHz) in CDCl3.
Chromatoꢀmass spectra were taken with Agilent Technologies
85973 Network instrument (EI, 70 eV), connected with Agilent
Technologies 6890 chromatograph (HPꢀ5MS 30000×0.25 mm
capillary column, the temperature of injector and flameꢀionizaꢀ
tion detector of 280 °С, temperature programming: 60→300 °С
(5 min), then 10 deg min–1, helium as the carrier gas,
2 mL min–1). During the analysis the total ionic current and the
signals of the flameꢀionization detector were recorded. The
GLCꢀanalysis was performed with Chromꢀ5 instrument (2×2500
mm column, SEꢀ30 on Chromaton NꢀAWꢀDMCS, the thermoꢀ
stat temperature (depending on the nature of the analyzed comꢀ
pound) varied in the range of 130—180 °С, the injector and
detector temperature — 250 °С).
Scheme 5
NꢀButylꢀN´ꢀmethylimidazolium chloride ([bmim]Cl)19
and
NꢀbutylꢀN´ꢀmethylimidazolium
tetrafluoroborate
([bmim]BF4)20 were obtained by known procedures and before
use were preꢀdried for 8—10 h at 50 °С (~1 Torr). Potassium
carbonate was calcined in air. Solvents were dried by standard
methods. Potassium phosphate, 4ꢀmethoxyphenylboronic acid,
and transꢀoctꢀ4ꢀene were purchased from Aldrich, phenylboronic
acid and cyclododecene, from Acros, vinylcyclohexane, from
Fluka, and were used without further purification. Hexꢀ1ꢀene
and styrene (Reakhim) were redistilled before use. cisꢀOctꢀ4ꢀene
was obtained by partial hydrogenation of octꢀ4ꢀyne (1 atm H2,
Raney Ni, 5% pyridine in EtOH). Column chromatography was
performed on Silica gel (Merck).
Decꢀ1ꢀenꢀ4ꢀol, 1ꢀallylcyclohexanol, and 1ꢀallylcyclopentanol
were obtained by modified procedure.21 To a flask with 50 mmol
of carbonyl compound, 50 mL of THF, 5 g (77 mmol) of zinc
dust, and ~1 mL of allyl bromide, 1—2 drops of acetic acid were
added with stirring to initiate the reaction. After the exothermic
stage was over, the rest allyl bromide was added (total of 9.1 g,
6.5 mL, 75 mmol). The mixture was stirred for 2—3 h until
complete conversion of the carbonyl compound (GLCꢀconꢀ
trol). The mixture was quenched with 5% H2SO4, light petroꢀ
leum was added, and this was filtered through a glass filter. The
organic layer was separated and washed several times with satuꢀ
rated NaHCO3 solution until the aqueous layers became clear.
The organic layer was dried with MgSO4, concentrated and the
residue was distilled in vacuo. The physical and chemical data of
compounds obtained corresponded to those reported in the litꢀ
erature.21,22
n = 3 (1i, 2i, 8), 7 (1j, 2j, 9)
Reagents and conditions: a. Br2, CH2Cl2. b. K3PO4, [bmim]BF4,
DME, 55 °C, 3 h. c. PhB(OH)2, Pd(PPh3)4.
Attempted oneꢀpot sequence of dehydrobromination
and crossꢀcoupling starting from 4ꢀhydroxyꢀ1,2ꢀdibromoꢀ
alkanes 1d—f leads to the formation, along with the target
styrenes, a considerable amount of byproducts (1Н NMR
data), which are difficult to separate by column chroꢀ
matography. In this case, it is reasonable to make phenylꢀ
boronic acid react with the preliminarily purified bromoꢀ
alkene, for example, Eꢀ3е. As a result, styrene derivative
10 was obtained in 47% yield (Scheme 6). It should be
noted that the alternative synthesis of alcohols of type 10
by reaction of carbonyl compounds with organoelement
cinnamyl derivatives is accompanied as a rule by allylic
rearrangement of the nucleophilic component.16
Scheme 6
Decꢀ1ꢀenꢀ4ꢀol. The yield was 3.78 g (48%), b.p. 105 °С
(15 Torr).

126
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 1, January, 2007
Tikhonov et al.
1ꢀAllylcyclohexanol. The yield was 4.48 g (64%), b.p. 80 °С
(10 Torr).
1ꢀAllylcyclopentanol. The yield was 5.4 g (43%), b.p.
70—80 °С (15 Torr).
Bromodecꢀ1ꢀenꢀ4ꢀols 2d, 3d. Oil. Found (%): C, 51.46;
H, 7.97. C10H19BrO. Calculated (%): C, 51.08; H, 8.14.
1H NMR spectrum of the mixture consisted of the following
groups of overlapped signals of the three isomers, δ: 0.89 (m,
3 H, Me); 1.26—1.74 (m, 11 H, CH2, OH). 2ꢀBromodecꢀ1ꢀenꢀ
4ꢀol (2d). 1Н NMR, characteristic signals, δ: 2.51 (dd, 1 H,
=C—CH2, J = 14.4 Hz, J = 8.3 Hz); 2.57 (dd, 1 H, =C—CH2,
J = 14.4 Hz, J = 3.9 Hz); 3.93 (m, 1 H, OCH); 5.53, 5.69
(both s, 1 H each, =CH2). 13C NMR, δ: 14.0 (Me); 22.6, 25.5,
29.2, 31.8, 36.4 (all СН2); 49.4 (=C—CH2); 69.1 (OCH); 119.5
(=CH2); 130.9 (=CBr). (Z )ꢀ1ꢀBromodecꢀ1ꢀenꢀ4ꢀol (Zꢀ3d).
1Н NMR, characteristic signals, δ: 2.06—2.40 (m, 2 H,
=C—CH2); 3.76 (m, 1 H, OCH); 6.18—6.27 (m, 2 H, CH=CH).
(Е)ꢀ1ꢀBromodecꢀ1ꢀenꢀ4ꢀol (Eꢀ3d). 1Н NMR, characteristic sigꢀ
nals, δ: 2.06—2.40 (m, 2 H, =C—CH2); 3.67 (m, 1 H, OCH);
6.14 (d, 1 H, =CH, J = 13.5 Hz); 6.23 (dt, 1 H, =CH, J =
13.5 Hz, J = 7.3 Hz). 13С NMR, δ: 14.0 (Me); 22.7, 25.5, 29.7,
31.9, 36.8 (all CH2); 40.7 (=C—CH2); 70.5 (OCH); 106.7
(=CHBr); 134.3 (=CH).
Vicinal dibromides 1a—j (general procedure). To a solution
of an olefin (1 mmol) in CH2Cl2 (3 mL), bromine (192 mg,
0.062 mL, 1.2 mmol) in CH2Cl2 (2 mL) was added at 0—5 °C
under stirring until the color persisted. An aqueous solution of
Na2S2O3 and NaHCO3 was added to the mixture, which was
stirred for another 15—20 min. The organic layer was separated,
the aqueous layer was extracted with CH2Cl2, the extracts were
dried with CaCl2 or Na2SO4 and concentrated in vacuo. The
residue was used in the next stage without additional purifiꢀ
cation.
Dehydrobromination of vicinal dibromides 1a—j (general proꢀ
cedure). To a mixture of vicinal dibromide 1 (1 mmol) and
[bmim]BF4 (1 g), freshly powdered K2CO3 (552 mg, 4 mmol)
was added under stirring and the mixture was stirred at the
temperature indicated in Tables 1 and 2. Periodically, aliquots
were withdrawn, which were suspended in water, extracted with
hexane, and the extracts were analyzed by GLC to monitor the
conversion of starting dibromide 1 and the isomeric composiꢀ
tion of the products formed. Reaction with the use of other
solvents and bases were carried out similarly. The duration and
temperatures of the reactions as well as the isomeric composiꢀ
tions of the products formed are given in Tables 1 and 2. After
complete conversion of dibromide 1, the mixture was diluted
with water, extracted with hexane, the extract was dried and
concentrated in vacuo. The residue was analyzed by 1Н NMR
and, if needed, purified by distillation and/or by column chroꢀ
matography.
3ꢀBromoꢀ5ꢀhexyltetrahydrofuran (4a). Mixture of two diaꢀ
stereomers (3 : 1), oil, b.p. 95 °С (1 Torr). Found (%): C, 51.06;
H, 8.21; Br, 33.66. C10H19BrO. Calculated (%): C, 51.08;
H, 8.14; Br, 33.98. 1H NMR spectrum of the mixture consisted
of the following groups of overlapped signals of both diastereoꢀ
mers, δ: 0.88 (t, Me, J = 6.9 Hz); 1.22—1.78 (m, 10 H, CH2).
Major diastereomer. 1Н NMR, characteristic signals, δ: 2.00
(ddd, 1 H, CH2, J = 13.7 Hz, J = 9.1 Hz, J = 6.6 Hz); 2.33 (ddd,
1 H, CH2, J = 13.7 Hz, J = 5.9 Hz, J = 2.4 Hz); 4.01 (dd, 1 H,
OCH2, J = 10.5 Hz, J = 3.7 Hz); 4.19 (m, 1 H, CHBr); 4.30 (dd,
1 H, OCH2, J = 10.5 Hz, J = 5.1 Hz); 4.44 (m, 1 H, OCH).
13С NMR, δ: 14.0 (Me); 22.5, 26.1, 29.3, 31.7, 35.0, 43.0
(all СН2); 47.1 (CHBr); 76.1 (OCH2); 78.5 (OCH). Minor
Bromohexenes 2а and 3а. 2ꢀBromohexꢀ1ꢀene (2а). 1Н NMR,
characteristic signals, δ: 2.44 (t, 2 H, =C—CH2, J = 7.4 Hz);
5.39, 5.55 (both s, 1 H each, =CH2). (Z)ꢀ1ꢀ Bromohexꢀ1ꢀene
(Zꢀ3a). 1Н NMR, characteristic signals, δ: 2.21 (br.q, 2 H,
=C—CH2, J = 7.4 Hz). (E)ꢀ1ꢀBromohexꢀ1ꢀene (Eꢀ3a).
1Н NMR, characteristic signals, δ: 2.06 (br.q, 2 H, =C—CH2,
J = 7.4 Hz). The spectral characteristics are in agreement with
those described in the literature.5a
1
diastereomer. Н NMR, characteristic signals, δ: 1.95 (m, 1 H,
CH2); 2.63 (dt, 1 H, CH2, J = 13.7 Hz, J = 6.9 Hz); 3.88
(quint, 1 H, CHBr, J = 6.9 Hz); 3.98—4.06 (m, 2 H, OCH2);
4.35 (m, 1 H, OCH). 13С NMR, δ: 14.0 (Me); 22.5, 26.0,
29.2, 31.7, 35.8, 42.7 (all СН2); 44.9 (CHBr); 75.5 (OCH2);
79.6 (OCH).
Dehydrobromination of 1ꢀ(2,3ꢀdibromopropyl)cyclohexanol
(1e) gave products 2e, 3e, and 4b, the spectral characteristics of
which agreed with those described earlier.7
Dehydrobromination of 1ꢀ(2,3ꢀdibromopropyl)cyclopentanol
(1f) gave products 2f, 3f, and 4c. After column chromatography
tetrahydrofuran 4c and mixture of alcohols 2f and 3f were obꢀ
tained.
Bromo cyclohexyl ethylenes 2b and 3b. Mixture of isomers,
b.p. 80—82 °С (15 Torr). Found (%): С, 50.60; H, 7.04. C8H13Br.
Calculated (%): C, 50.81; H, 6.93. 1ꢀBromoꢀ1ꢀcyclohexylꢀ
1
ethylene (2b). Н NMR, characteristic signals, δ: 2.18 (m, 1 H,
=C—CH); 5.38, 5.56 (both s, 1 H each, =CH2). 13С NMR, δ:
25.7 (С(4)cycloꢀC H ); 25.9 (С(3)cycloꢀC H , С(5)cycloꢀC H );
6
11
6
6
11
32.1 (С(2)cycloꢀC H , С(6)cycloꢀC H ); 48.151 (С(1)cycloꢀC H );
1ꢀ(Bromopropenyl)cyclopentanols 2f and 3f. Found (%):
C, 46.70; H, 6.33. C8H13BrO. Calculated (%): C, 46.85; H, 6.39.
1H NMR spectrum of the mixture consisted of the following
groups of overlapped signals of the three isomers, δ: 1.53—1.88
(m, CH2 of cyclopentane). 1ꢀ(2ꢀBromopropꢀ2ꢀenꢀ1ꢀyl)cycloꢀ
6
11
6
11
11
114.0 (=CH2); 141.2 (=С). (Z)ꢀ1ꢀBromoꢀ2ꢀcyclohexyleth6ylene
(Zꢀ3b). 1Н NMR, characteristic signals, δ: 2.53 (m, 1 H,
=C—CH); 5.93 (t, 1 H, =CH, J = 7.4 Hz); 6.05 (d, 1 H, =CH,
J = 7.4 Hz). (Е)ꢀ1ꢀBromoꢀ2ꢀcyclohexylethylene (Eꢀ3b).
1Н NMR, characteristic signals, δ: 2.02 (m, 1 H, =C—CH);
6.00 (d, =CH, J = 13.6 Hz); 6.15 (dd, =CH, J = 13.6 Hz, J =
7.3 Hz). (E,Z)ꢀIsomers 3b. 13C NMR, characteristic signals withꢀ
out assignment, δ: 25.5, 31.6, 32.2, 38.8, 41.7, 103.0, 105.4,
140.1, 143.6.
1
pentanol (2f). Н NMR, characteristic signals, δ: 2.79 (s, 2 H);
5.60, 5.70 (both s, 1 H each). 13С NMR, characteristic signals,
δ: 23.5, 39.6, 51.8 (all CH2); 120.7 (=CH2); 129.1 (=C).
(Z )ꢀ1ꢀ(3ꢀBromopropꢀ2ꢀenꢀ1ꢀyl)cyclopentanol
(Zꢀ3f).
1Н NMR, characteristic signals, δ: 2.53 (d, 2 H, J = 5.6 Hz).
13C NMR, characteristic signals, δ: 39.7, 41.4 (both СН2); 109.8
(=CHBr); 131.2 (=CH). (E)ꢀ1ꢀ(3ꢀBromopropꢀ2ꢀenꢀ1ꢀyl)cycloꢀ
pentanol (Eꢀ3f). 1Н NMR, characteristic signals, δ: 2.33 (d,
2 H, J = 7.6 Hz); 6.14 (d, 1 H, J = 13.6 Hz); 6.29 (dt, 1 H, J =
13.6 Hz, J = 7.6 Hz). 13С NMR, δ: 23.7, 39.4, 44.6 (all CH2);
81.3 (COH); 106.9 (=CHBr); 134.1 (=CH).
Dehydrobromination of 1,2ꢀdibromodecanꢀ4ꢀol (1d). Using
K2CO3 in [bmim]BF4 gave a mixture of 3ꢀbromoꢀ5ꢀhexylꢀ
tetrahydrofuran (4a) and bromodecꢀ1ꢀenꢀ4ꢀols 2d and 3d (7 : 3).
After workup and column chromatography 110 mg (47%) of
tetrahydrofuran 4a and 45 mg (19%) of mixture of alcohols 2d
and 3d were obtained.

Styrenes from 1,2ꢀdibromoalkanes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 1, January, 2007
127
3ꢀBromoꢀ1ꢀoxaspiro[4.4]nonane (4c). Oil, b.p. 101—103 °С
(15 Torr). Found (%): C, 46.91; H, 6.46; Br, 38.82. C8H13BrO.
Calculated (%): C, 46.85; H, 6.39; Br, 38.96. 1Н NMR, δ:
1.46—1.81 (m, 7 H); 1.99 (m, 1 H); 2.25 (dd, 1 H, J = 13.9 Hz,
J = 4.9 Hz); 2.47 (dd, 1 H, J = 13.9 Hz, J = 7.3 Hz); 3.93 (dd,
1 H, J = 10.0 Hz, J = 5.1 Hz); 4.14 (dd, 1 H, J = 10.0 Hz, J =
5.6 Hz); 4.37 (m, 1 H). 13С NMR, δ: 23.6, 24.0, 38.6, 38.7
(all CH2); 45.5 (CHBr); 46.7 (CH2); 74.7 (OCH2); 91.4 (OC).
Oneꢀpot synthesis of styrenes from vicinal dibromides (genꢀ
eral procedure). A. To a solution of 1.5 mmol of vicinal dibromide
in 4.5 mL of DME, [bmim]BF4 (100 mg, 0.44 mmol) (or equimoꢀ
lar amount of the other phase transfer catalyst) and 1.274 g
(6 mmol) of K3PO4 were added. The mixture was refluxed with
stirring for 1—2 h until complete conversion of starting dibromide
(GLC control). Oxygen was removed from the mixture by
several cycles of evacuation (before vigorous boiling of the
solvent started) and filling with argon. After addition of
Pd(PPh3)4 (40 mg, 2.3 mol.%) the reaction mixture was stirred
for 30—40 min and then 1.5 mmol of the corresponding
arylboronic acid and 3 mL of water were added, and the mixture
was refluxed for 4—6 h under argon. The mixture was cooled,
diluted with water, and the organic components were extracted
with benzene. The extracts were dried with Na2SO4 and conꢀ
centrated in vacuo. Column chromatography of the residue
(1—3% of ethyl acetate in hexane as the eluent) gave the mixꢀ
tures of corresponding isomeric styrenes, which we were not
able to separate by this method. The yields were 50—75%.
B. A mixture of dibromide 1 (1 mmol) and K3PO4 (848 mg,
4 mmol) in DMF (2 mL) was heated to ~100 °C and stirred until
complete conversion of starting compound 1 (2—4 h). The mixꢀ
ture was cooled and deoxygenated by triple sequential evacuaꢀ
tion and filling with argon, then Pd(OAc)2 (10 mg, 4.5 mol.%)
and 1.2 mmol of the corresponding arylboronic acid were added.
The reaction mixture was stirred for 4—5 h at ~90 °C, diluted
with water, and the organic components were extracted with
benzene. The extract was dried, filtered through a short pad of
silica and analyzed by chromatoꢀmass spectrometry.
Phenylhexenes 5а and 6а. Total yield was 151 mg (63%).
1H NMR spectrum of the mixture consisted of the following
groups of overlapped signals of the three isomers, δ: 0.97 (t, 3 H,
Me, J = 6.6 Hz); 1.35—1.57 (m, 4 H, CH2); 7.21—7.53 (m, 5 H,
Ph). 2ꢀPhenylhexꢀ1ꢀene (5а). 1Н NMR, characteristic signals,
δ: 2.58 (t, 2 H, =C—CH2, J = 7.9 Hz); 5.13, 5.33 (both s,
1 H each, =CH2). MS, m/z: 160 [M]+. (Z)ꢀ1ꢀPhenylhexꢀ1ꢀene
(Zꢀ6a). 1Н NMR, characteristic signals, δ: 2.41 (br.q, 2 H,
=C—CH2, J = 7.2 Hz); 5.74 (dt, 1 H, =CH, J = 11.8 Hz, J =
7.2 Hz); 6.48 (d, 1 H, =CH, J = 11.2 Hz). MS, m/z: 160 [M]+.
(Е)ꢀ1ꢀPhenylhexꢀ1ꢀene (Eꢀ6a). 1Н NMR, characteristic sigꢀ
nals, δ: 2.27 (br.q, 2 H, =C—CH2, J = 7.2 Hz); 6.29 (dt, 1 H,
=CH, J = 15.8 Hz, J = 6.6 Hz); 6.46 (d, 1 H, =CH, J =
15.8 Hz). MS, m/z: 160 [M]+. The spectral characteristics of the
compounds obtained were in agreement with those described in
the literature.23
14.0 (q); 22.5, 30.6, 35.2 (all t); 55.3 (q); 110.5 (t); 113.7,
127.2 (both d); 134.0, 148.1, 159.0 (all s). MS, m/z: 190 [M]+.
1
(Z)ꢀ1ꢀ(4ꢀMethoxyphenyl)hexꢀ1ꢀene (Zꢀ6b). Н NMR, characꢀ
teristic signals, δ: 2.35 (br.q, 2 H, =C—CH2, J = 6.6 Hz); 5.60
(dt, 1 H, =CH, J = 11.8 Hz, J = 7.4 Hz); 6.36 (d, 1 H, =CH, J =
11.8 Hz); 7.25 (d, 2 H, H arom., J = 8.8 Hz). 13С NMR, δ:
14.0 (q); 22.5, 28.5, 32.3 (all t); 55.3 (q); 113.7, 128.2,
130.0, 131.7 (all d); 130.5, 158.1 (both s). MS, m/z: 190 [M]+.
(Е)ꢀ1ꢀ(4ꢀMethoxyphenyl)hexꢀ1ꢀene (Eꢀ6b). 1Н NMR, characꢀ
teristic signals, δ: 2.22 (br.q, 2 H, =C—CH2, J = 6.6 Hz); 6.11
(dt, 1 H, =CH, J = 15.4 Hz, J = 7.4 Hz); 6.35 (d, 1 H, =CH, J =
15.4 Hz). MS, m/z: 190 [M]+. The spectral characteristics of the
compounds obtained were in agreement with those described in
the literature.23
Cyclohexyl 4ꢀmethoxyphenyl ethylenes 5c and 6c. Total yield
1
was 224 mg (69%). H NMR spectrum of the mixture consisted
of the following groups of overlapped signals of the three isoꢀ
mers, δ: 1.10—1.44, 1.64—1.92 (both m, 5 H each, CH2); 3.82
(s, 3 H, OMe); 6.87, 7.29 (both d, 2 H each, H arom., J =
8.6 Hz). 1ꢀCyclohexylꢀ1ꢀ(4ꢀmethoxyphenyl)ethylene (5c).
1Н NMR, characteristic signals, δ: 2.44 (m, 1 H, =C—CH);
4.96, 5.10 (both s, 1 H each, =CH2). 13C NMR, δ: 26.6, 27.0,
32.9 (all CH2); 42.6 (CH); 55.3 (OMe); 109.1 (=CH2); 113.5,
127.6 (both =CH arom.); 135.3 (=C arom.); 154.3 (=C olefin);
158.8 (=С—О). MS, m/z: 216 [M]+. (Z)ꢀ2ꢀCyclohexylꢀ1ꢀ
(4ꢀmethoxyphenyl)ethylene (Zꢀ6c). 1Н NMR, characteristic sigꢀ
nals, δ: 2.58 (m, 1 H, =C—CH); 5.42 (dd, 1 H, =CH, J =
11.8 Hz, J = 9.6 Hz); 6.26 (d, 1 H, =CH, J = 11.8 Hz). MS,
m/z: 216 [M]+. (Е)ꢀ2ꢀCyclohexylꢀ1ꢀ(4ꢀmethoxyphenyl)ethylene
(Eꢀ6c). 1Н NMR, characteristic signals, δ: 2.12 (m, 1 H,
=C—CH); 6.05 (dd, 1 H, =CH, J = 16.2 Hz, J = 6.6 Hz); 6.31
(d, 1 H, =CH, J = 16.2 Hz). MS, m/z: 216 [M]+. The spectral
characteristics of the compounds obtained were in agreement
with those described in the literature.24
(4ꢀMethoxyphenyl)ꢀ3ꢀmethylbutꢀ1ꢀenes 5d and 6d. Total
yield was 169 mg (64%). 1H NMR spectrum of the mixture
consisted of the following groups of overlapped signals of the
three isomers, δ: 1.14 (d, 6 H, gemꢀMe, J = 6.6 Hz); 3.84 (s, 3 H,
OMe); 6.89, 7.33 (both d, 2 H each, H arom., J = 8.6 Hz).
2ꢀ(4ꢀMethoxyphenyl)ꢀ3ꢀmethylbutꢀ1ꢀene (5d). 1Н NMR, charꢀ
acteristic signals, δ: 2.84 (sept, 1 H, =C—CH, J = 6.6 Hz); 5.00,
5.14 (both s, 1 H each, =CH2). 13C NMR, δ: 22.2 (gemꢀMe);
32.4 (CH); 55.3 (OMe); 108.8 (=CH2); 113.6, 127.7
(both =CH arom.); 136.0 (=C arom.); 155.2 (=C olefin); 158.9
(=С—О). MS, m/z: 176 [M]+. (Z)ꢀ1ꢀ(4ꢀMethoxyphenyl)ꢀ3ꢀ
methylbutꢀ1ꢀene (Zꢀ6d). 1Н NMR, characteristic signals, δ: 5.42
(t, 1 H, =CH, J = 11.0 Hz); 6.27 (d, 1 H, =CH, J = 11.0 Hz).
MS, m/z: 176 [M]+. (Е)ꢀ1ꢀ(4ꢀMethoxyphenyl)ꢀ3ꢀmethylbutꢀ1ꢀ
ene (Eꢀ6d). 1Н NMR, characteristic signals, δ: 6.09 (dd, 1 H,
=CH, J = 16.2 Hz, J = 6.6 Hz); 6.32 (d, 1 H, =CH, J =
16.1 Hz). MS, m/z: 176 [M]+. The spectral characteristics of the
compounds obtained were in agreement with those described in
the literature.24,25
(4ꢀMethoxyphenyl)hexenes 5b and 6b. Total yield was 214 mg
(75%). 1H NMR spectrum of the mixture consisted of the folꢀ
lowing groups of overlapped signals of the three isomers, δ: 0.93
(t, 3 H, Me, J = 7.4 Hz); 1.30—1.52 (m, 4 H, CH2); 3.83 (s, 3 H,
OMe); 6.89 (d, 2 Н, Н arom., J = 8.8 Hz). 2ꢀ(4ꢀMethoxyꢀ
phenyl)hexꢀ1ꢀene (5b). Н NMR, characteristic signals, δ: 2.50
(t, 2 Н, =C—CH2, J = 7.4 Hz); 5.00, 5.22 (both s, 1 H each,
=CH2); 7.38 (d, 2 H, H arom., J = 8.8 Hz). 13С NMR, δ:
1ꢀ(4ꢀMethoxyphenyl)ꢀ1ꢀphenylethylene (5e). The yield was
170 mg (54%). 1H NMR, δ: 3.85 (s, 3 H); 5.40, 5.42 (both s,
1 H each); 6.89, 7.31 (both d, 2 H each, J = 8.8 Hz); 3.37
(m, 5 H). 13C NMR, δ: 55.3 (OMe); 112.8 (=CH2); 113.6,
127.6, 128.1, 128.3, 129.3 (all =CH); 134.1, 141.9, 149.6
(all =С); 159.4 (=С—О). The spectral characteristics of the
compounds obtained were in agreement with those described in
the literature.18,26
1

128
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 1, January, 2007
Tikhonov et al.
1,1ꢀDiphenylethylene (5f). The yield was 138 mg (51%).
due (1→5% gradient of ethyl acetate in hexane as the eluent)
gave 170 mg (47%) of compound 10 as a viscous solidifying oil.
1H NMR, δ: 1.20—1.80 (m, 11 H); 2.39 (d, 2 H, J = 7.4 Hz);
6.31 (dt, 1 H, J = 15.4 Hz, J = 7.4 Hz); 6.48 (d, 1 H, J =
15.4 Hz); 7.18—7.43 (m, 5 H). 13C NMR, δ: 22.1, 25.7, 37.4,
45.9 (all CH2); 71.5 (OC); 125.3, 126.1, 127.1, 128.4, 133.5
(all =CH); 137.3 (=C). The spectral characteristics were in
agreement with those described in the literature.31
1H NMR, δ: 5.57 (s, 2 H); 7.38—7.50 (m, 10 H). 13C NMR, δ:
114.2 (=CH2); 127.6, 128.1 (CH arom.); 141.4 (C arom.);
150.0 (=C). The spectral characteristics were in agreement with
those described in the literature.27
(Е)ꢀ4ꢀ(4ꢀMethoxyphenyl)octꢀ4ꢀene (Eꢀ7). The yield was
220 mg (67%). 1H NMR, δ: 0.96, 1.04 (both t, 3 H each, J =
7.4 Hz); 1.44, 1.54 (both sext, 2 H each, J = 7.4 Hz); 2.24 (q,
2 H, J = 7.4 Hz); 2.53 (t, 2 H, J = 7.4 Hz); 3.85 (s, 3 H); 5.67 (t,
1 H, J = 6.6 Hz); 6.91, 7.35 (both d, 2 H each, J = 8.8 Hz).
13C NMR, δ: 13.9 (2 Me); 21.8, 23.1, 30.6 (all СН2); 32.2
(C(3)H2); 55.1 (OMe); 113.4, 127.3, 127.8 (all =CH); 136.0,
139.3 (both =C); 158.3 (=С—О). MS, m/z: 218 [M]+. The
spectral characteristics were in agreement with those described
in the literature.28
(Z )ꢀ4ꢀ(4ꢀMethoxyphenyl)octꢀ4ꢀene (Zꢀ7). The yield was
16 mg (5%). 1H NMR, δ: 0.86, 0.88 (both t, 3 H each, J =
7.4 Hz); 1.27—1.42 (m, 4 H); 1.94 (q, 2 H, J = 7.4 Hz); 2.30 (t,
2 H, J = 7.4 Hz); 3.83 (s, 3 H); 5.42 (t, 1 H, J = 7.4 Hz); 6.88,
7.07 (both d, 2 H each, J = 8.8 Hz). 13C NMR, δ: 13.5, 13.8
(both Me); 21.2, 23.3, 30.9 (all СН2); 41.5 (C(3)H2); 55.1
(OMe); 113.3, 127.1, 129.4 (all =CH); 133.8, 140.2 (both =С);
158.0 (=С—О). The spectral characteristics were in agreement
with those described in the literature.29
This work was financially supported by the Russian
Federation President Council for Grants (Program for
Support of the Leading Scientific Schools of the Russian
Federation, Grant No. NShꢀ1802.2003.3), the Presidium
of the Russian Academy of Sciences (Program for Basic
Research), and the Russian Foundation for Basic Reꢀ
search (Project No. 06ꢀ03ꢀ32603).
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(Е)ꢀ1ꢀPhenylcyclooctene (8). The yield was 181 mg (65%).
1H NMR, δ: 1.41—1.84 (m, 8 H); 2.33, 2.67 (both m, 2 H each);
6.06 (t, 1 H, J = 8.3 Hz); 7.18—7.52 (m, 5 H). 13C NMR, δ:
26.1, 26.9, 27.4, 28.5, 29.4, 30.0 (all СН2); 125.7, 126.4, 127.9,
128.2 (all =CH); 140.2, 143.2 (both =C). MS, m/z: 186 [M]+.
The spectral characteristics were in agreement with those deꢀ
scribed in the literature.30
(Е)ꢀ1ꢀPhenylcyclododecene (9). The chromatoꢀmass specꢀ
trometry data showed the following composition of the reaction
product: cyclododecene ([M]+ 166) 12%, Zꢀ2j ([M]+ 244
for 79Br) 38%, Eꢀ2j ([M]+ 244) 8%, 9 ([M]+ 242) 41%. For
identification of the target component of the mixture, an indeꢀ
pendent synthesis14 of (Е,Z)ꢀ1ꢀphenylcyclododecenes (9 : 1)
1
was performed. (Е)ꢀIsomer. H NMR, δ: 1.26—1.38 (m, 2 H);
1.42—1.62 (m, 12 H); 1.62—1.74 (m, 2 H); 2.38 (q, 2 H, C(3)H2,
J = 7.4 Hz); 2.70 (t, 2 H, C(12)H2, J = 7.4 Hz); 5.69 (t, 1 H,
C(2)H, J = 8.1 Hz); 7.30 (m, 1 H, H arom.); 7.35 (m, 4 H,
H arom.). 13C NMR, δ: 22.4, 22.5, 24.3, 24.4, 24.8, 24.9, 25.3,
25.4, 25.6 (all CH2); 27.4 (C(12)H2); 126.3, 126.7, 128.0
(all CH arom.); 130.2 (C(2)H); 140.4 (C arom.); 143.4 (C(1)).
(Z)ꢀIsomer. 1Н NMR, characteristic signals, δ: 2.14 (m, 2 H,
C(3)H2); 2.56 (m, 2 H, C(12)H2); 5.86 (t, 1 H, C(2)H, J =
8.1 Hz). 13C NMR, δ: 23.2, 23.8, 24.0, 24.3, 26.1, 26.3, 27.2,
27.6, 29.1 (all CH2); 37.0 (C(12)H2); 126.2, 127.9, 128.3
(all CH); 138.4, 140.8 (both C).
1ꢀ[(2E)ꢀ3ꢀPhenylpropꢀ2ꢀenꢀ1ꢀyl]cyclohexanol (10). A mixꢀ
ture of 1ꢀ[(2E)ꢀ(3ꢀbromopropꢀ2ꢀenꢀ1ꢀyl)]cyclohexanol (Eꢀ3e)
(365 mg, 1.67 mmol) and Pd(PPh3)4 (40 mg, ~2 mol.%) in
DME (2 mL) was stirred for 40 min under argon (during this
time, the dark yellow precipitate formed). Then phenylboronic
acid (244 mg, 2.0 mmol) was added in one portion under argon
followed by a degassed solution of Na2CO3 (0.54 g) in water
(2.1 mL). The mixture was refluxed with stirring for 6 h while
precipitation of palladium black was observed. The mixture was
cooled, diluted with water, and the organic components were
extracted with benzene. The extracts were dried with Na2SO4
and concentrated in vacuo. Column chromatography of the resiꢀ

Styrenes from 1,2ꢀdibromoalkanes
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Received March 28, 2006;
in revised form November 24, 2006