Tuneable superbase-catalyzed vinylation of α-hydroxyalkylferrocenes with alkynes

Article abstract of DOI:10.1016/j.tet.2014.06.010

Superbase-catalyzed (KOH/DMSO suspension as a catalyst) vinylation of hydroxymethyl- and hydroxyethylferrocenes with terminal and internal alkynes (acetylene, propyne, phenylacetylene, 3-ethynylpyridine, 1-propyn-1-yl-benzene, diphenylacetylene) affords hitherto unknown vinyl ethers of ferrocene in 30-93% yields depending on the alkyne structure and the tuneable ratio of reactants/KOH/DMSO. The vinylation smoothly proceeds under mild conditions (70-90 °C, 0.25-13 h). With unsubstituted acetylene the process is readily realized under atmospheric pressure (yield of the corresponding vinyl ethers is 81-90%) though under pressure (initial pressure at room temperature is 10-13 atm, maximum pressure is 13-16 atm at the reaction temperature) the yield is close to quantitative (93%). The synthesized compounds were characterized using ¹H and ¹³C NMR, and IR spectroscopy, as well as X-ray diffraction analysis.

Full text of DOI:10.1016/j.tet.2014.06.010

Accepted Manuscript
Tuneable superbase-catalyzed vinylation of α-hydroxyalkylferrocenes with alkynes
Boris A. Trofimov , Ludmila A. Oparina , Olga A. Tarasova , Alexander V. Artem’ev ,
Vladimir B. Kobychev , Yuriy V. Gatilov , Alexander I. Albanov , Nina K. Gusarova
PII:
S0040-4020(14)00856-4
10.1016/j.tet.2014.06.010
TET 25675
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 11 February 2014
Revised Date: 19 May 2014
Accepted Date: 2 June 2014
Please cite this article as: Trofimov BA, Oparina LA, Tarasova OA, Artem’ev AV, Kobychev VB, Gatilov
YV, Albanov AI, Gusarova NK, Tuneable superbase-catalyzed vinylation of α-hydroxyalkylferrocenes
with alkynes, Tetrahedron (2014), doi: 10.1016/j.tet.2014.06.010.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Tuneable superbase-catalyzed vinylation of
Leave this area blank for abstract info.
α-hydroxyalkylferrocenes with alkynes
B. A. Trofimov,* L. A. Oparina, O. A. Tarasova,
A. V. Artem’ev, V. B. Kobychev, Yu. V. Gatilov, A. I. Albanov, N. K. Gusarova

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Tuneable superbase-catalyzed vinylation of α-hydroxyalkylferrocenes with
alkynes
a∗
a
a
a
Boris A. Trofimov, Ludmila A. Oparina, Olga A. Tarasova, Alexander V. Artem’ev, Vladimir B.
Kobychev, Yuriy V. Gatilov, Alexander I. Albanov and Nina K. Gusarova
b
c
a
a
a
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033, Irkutsk, Russian Federation.
Irkutsk State University, 1 K. Marks Str., 664003 Irkutsk, Russian Federation
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 Lavrentiev Ave., 630090, Novosibirsk,
b
c
Russian Federation
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Superbase-catalyzed (KOH/DMSO suspension as a catalyst) vinylation of hydroxymethyl-
and α-hydroxyethylferrocenes with terminal and internal alkynes (acetylene, propyne,
phenylacetylene, 3-ethynylpyridine, 1-propyn-1-yl-benzene, diphenylacetylene) affords
hitherto unknown vinyl ethers of ferrocene in 30-93% yields depending on the alkyne
structure and the tuneable ratio of reactants/KOH/DMSO. The vinylation smoothly
Available online
o
proceeds under mild conditions (70-90 C 0.25-13 h). With unsubstituted acetylene the
Keywords:
Alkynes
Enol Ethers
Ferrocene
Regioselectivity
Superbase systems
process is readily realized under atmospheric pressure (yield of the corresponding vinyl
ethers is 81-90%) though under pressure (initial pressure at room temperature is 10-13 atm,
maximum pressure is 13-16 atm at the reaction temperature) the yield is close to
quantitative (93%). The synthesized compounds were characterized using H and C NMR,
and IR spectroscopy, as well as X-ray diffraction analysis.
1
13
2
009 Elsevier Ltd. All rights reserved.
1
. Introduction
characterized by incomplete description of the IR spectra,
providing no reliable structural proofs.
Meanwhile, the superbase catalytic systems of the type alkali
metal hydroxide (alkoxide) / polar aprotic solvent (DMSO,
HMPA) have allowed substantial improvements in the vinylation
of alcohols, i.e. carrying out the process at much lower
9
Currently, the chemistry of ferrocene compounds continues to
1
progress rapidly. This is due to the fact that ferrocene and its
numerous derivatives are widely used in various fields such as
catalysis, materials science,
organometallic chemistry, medicine, organic synthesis.
Moreover, ferrocene derivatives have been extensively
investigated as reversible redox couples for design of molecular
2
2,3
organometallic and bio-
4
5
6
temperature and under atmospheric pressure (in the case of
8,10
unsubstituted acetylene and propyne).
An advantage of these
catalysts is their tuneability, i.e. the alteration of their basicity
and hence catalytic activity depending on the nature and content
of the alkali metal hydroxide or alkoxide and polar aprotic
7
sensors.
The modification of ferrocene derivatives by diverse reactive,
especially polymerizable functions, considerably increases their
possible for applications in advanced technologies. An attractive
functionalization of the ferrocene scaffold might be introduction
of the enol ether moiety which possesses versatile and rich
solvent passing through true solutions to two-phase systems
10
(
suspensions). The successful adaptation of this methodology to
the vinylation of ferrocene alcohols stays unclear, particularly
having in mind the specific organometallic feature of the
substrates.
Here we report the efficient superbase-catalyzed direct
vinylation of ferrocene alcohols (hydroxymethyl- and α-
hydroxyethylferrocenes) with diverse alkynes (acetylene,
propyne, phenylacetylene, 3-ethynylpyridine, 1-propyn-1-yl-
benzene, diphenylacetylene).
8
reactivity. Surprisingly, until now, vinyl ethers of ferrocene
alcohols remain essentially unknown, except for the single
incomplete
vinyloxymethyl)ferrocene. The latter was claimed to be
synthesized in small yield by the reaction of
hydroxymethylferrocene with acetylene in the presence of KOH
report
on
the
synthesis
of
9
(
o
(28 mol %) at 130-140 C in the absence of solvent or by trans-
vinylation of this ferrocene alcohol with butyl vinyl ether
catalyzed by Hg(OAc) (50-55% yield). The liquid product was
2
—
——
∗
Corresponding author. Tel.: +7-395-251-1431; fax: (+7) 3952419346; e-mail: boris_trofimov@irioch.irk.ru

2
Tetrahedron
2
. Results and Discussion
with pressured acetylene in the KОН/DMSO system (autoclave,
ACCEPTED MANUSCRIPT
о
1
2 atm, 70 С, 2 h) does not lead to the expected vinyl ether
Vinylation with acetylene
(97% of initial alcohol is recovered along with trace amounts of
dehydratation product, i.e. isopropenylferrecene).
Ferrocene alcohols 1a,b react with acetylene in the
KОН/DMSO system under elevated pressure in autoclave (the
initial pressure at room temperature 10-13 atm, maximum
pressure at the reaction temperature 13-16 atm) at 70-80 С to
afford vinyl ethers 2a,b in up to 93% yield (Table 1).
Vinylation with propyne
о
We have found that ferrocene alcohols 1a,b react with
propyne in the KOH/DMSO suspension (80 C, 2 h) under
o
a
atmospheric pressure to give 2-propenyl ethers 2c,d with 100%
regioselectivity, the best yields being 65 and 58%, respectively
Table 1 Vinylation of ferrocenylalkanols 1a,b with acetylene
(Entries 1, 4, Table 2). The exclusive formation of 2-propenyl
ethers is a common feature of nucleophilic vinylation of alcohols
15
with propyne is explained by the destabilization of the
alternative carbanionic center adjacent to the electron-donating
methyl substituent. However, in this case the regioselectivity is
astonishing because it occurs despite obvious steric hindrance
towards the nucleophilic attack of internal acetylenic carbon
atom by voluminous ferrocene alkoxide anions.
Product,
o
Entry Alcohol MOH (mol%) T, C Time, h
b
yield (%)
a
Table 2 Vinylation of ferrocenylalkanols 1a,b with propyne
1
2
3
4
5
6
1a
1a
1a
1a
KOH (100)
KOH (100)
KOH (50)
KOH (10)
KOH (10)
NaOH (10)
80
70-74
70
0.25
2
2a, 58
2a, 65
2a, 70
2a, 81
2b, 93
1
70
1
70
0.75
1
1
1
b
b
[
c]
70
2b, 36
a
Reactions were carried out on 30-mmol scale (0.6 mol/L), with the
mentioned amount of MOH in DMSO (50 mL); initial pressure of acetylene
at ambient temperature was 10-13 atm.
b
Conversion of
Product,
yield
(%)
Isolated yields after chromatographic purification.
Conversion of alcohol 1b being 41%.
KOH
mol%)
T,
C
Time,
h
c
1a,b
Entry Alcohol
o
(
b
(%)
о
The best results were achieved with 10 mol% КОН at 70 С
1
2
1a
1a
100
50
80
90
2
3
84
94
2c, 65
2c, 47
(81% and 93% yields for 2a and 2b, respectively). Noteworthy,
the progressive increase of the KOH content to 100 mol%
decreases the yields of the target products (Entries 1-3 in Table
2
c,
3
1a
50
70
1
ndt
traces
2d, 58
2d, 25
1
), apparently due to the resinification processes (tar formation).
Under similar conditions, the less basic NaОН/DMSO system
allows vinyl ether 2b to be synthesized in 36% yield only,
conversion of the starting alcohol 1b being 41% (Entry 6 in
Table 1).
4
5
1b
1b
100
50
80
90
2
3
74
65
a
Reactions were carried out on 5-mmol scale, with the mentioned amount of
KOH in DMSO (30 mL); propyne flow rate ~ 0.5 L/h).
Isolated yields after chromatographic purification.
It is well-known that for safety reasons and engineering
complications, pressure is a major challenge for the widespread
application of acetylene-based syntheses both in laboratories and
industry. Therefore, we have spent a lot of efforts to accomplish
the vinylation of ferrocene alcohols at atmospheric pressure.
Eventually, we have elaborated the synthetically and
technologically feasible procedure for the synthesis of vinyl
ethers 2a,b in a flow reactor avoiding the neat for pressurized
acetylene. According to this protocol, acetylene is passed through
a suspension of KОН/DMSO containing ferrocenyl alcohol
b
As expected for nucleophilic addition to acetylenes, propyne
displays lower reactivity than unsubstituted acetylene owing to
the electron-donating effect of the methyl group. For example,
under conditions of almost quantitative vinylation of alcohol 1a
o
with acetylene (80 C, 2 h), the reaction with propyne is
incomplete (conversion of the starting alcohol is 84%, Entry 1 in
Table 2). Decreasing the amount of catalyst (from 100 to 50
о
mol%) and carrying out the reaction at 90 С results in a
(
0
1a,b: KOH molar ratio = 1:1, concentration of 1a,b and KOH =
.5 mol/L) at 80 С for 2 h. The yields were 81 and 90% for 2a
substantial drop of the yield (47% for 3 h, Entry 2 in Table 2). At
a lower reaction temperature (70 С, 1 h, Entry 3 in Table 2),
о
о
and 2b, respectively.
ferrocene alcohol 1a reacts with propyne to afford the expected
adduct 2d in trace amounts (the reaction mixture contains mainly
initial reagents).
Similar results have been obtained for the reaction of
ferrocene alcohol 1b with propyne (Entries 4, 5 in Table 2).
However, when the reaction is performed in a closed system (0.3-
It should be underlined that ferrocene alcohols 1a,b (Table 1)
are vinylated at a lower temperature and faster than other
1
1
12
alcohols, e.g. methanol,
prop-2-en-1-ol
and furan-2-
13
ylmethanol. Another interesting feature of the vinylation of
ferrocene alcohols is that normally, secondary alcohols add to
acetylene in the presence of bases much slower than primary
alcohols. In the case of ferrocene alcohols 1a,b the opposite is
true.
o
L Parr-reactor, 70 C, 1 h), ether 2d is formed in 51% isolated
14
yield (conversion of 1b is 63%).
Like the vinylation of ferrocene alcohols 1a,b with acetylene,
their reaction with propyne is accompanied by the formation of
As for vinylation of tertiary ferrocene alcohols, we have
shown that the heating of (1-hydroxy-1-methylethyl)ferrocene

3
considerable amounts of polymers containing
the content of which increases with the reaction temperature.
Other terminal alkyl acetylenes are found to be inactive in the
reaction with the ferrocene alcohols. For example, when alcohol
A
ir
C
on
C
, u
E
p
P
to
T
1
E
2
D
%, MAiso
N
m
U
er
S
r
C
ati
R
o
I
does not noticeably depend on the reactants
P
T
structure, though always being in favor of the Z-isomer. In this
case, violation of the expected Z-selectivity probably results from
steric encumbrance in the Z-isomers, i.e. bears the
thermodynamic character. Indeed, heating of the Z- and E-
1
a is heated with 1-octyne in KOH/DMSO system under close
o
o
conditions (70 C, 4 h), the formation of 1,3H-isomerization
isomers 2e (80 C, 3 h) does not lead to change of their ratio.
product, i.e. 2-octyne, is observed, while alcohol 1a remains
Moreover,
the
theoretical
calculations
[MP2/6-
13
unchanged ( C NMR data). The inertness of the formed 2-octyne
toward alcohol 1a can be explained by lower electrophilicity of
the former in conjunction with its steric hindrance.
311++G(d,p)//B3LYP/6-31G(d,p)] predict that the isomer ratios
for products 2e-g are close to those observable (Table 4).
Table 4 The energy differences between Z- and E-isomers and their ratios for
Vinylation with phenyl- and 3-pyridylacetylenes
a
products 2e-f [MP2/6-311++G(d,p)//B3LYP/6-31G(d,p)]
In the superbase suspension KOH/DMSO, ferrocene alcohols
1
a,b regioselectively add to phenylacetylene and 3-
Product
ꢀG, kcal/mol Z/E ratio
o
ethynylpyridine (70 C, 4 h) to deliver vinyl ethers 2e-h (as
mixtures of E- and Z-isomers) in 42-64% yields (Table 3). Like
in other cases, during the reaction with phenylacetylene and 3-
ethynylpyridine, considerable amounts of brown iron-containing
0
1
.78
.20
80:20
88:12
(2e)
(up to 18 mass% Fe) polymers are formed.
(2f)
Table
arylacetylenes
3 Regioselective vinylation of ferrocenylalkanols 1a,b with
a
0
.51
70:30
(2g)
a
The values are referred to 298 K, 1 atm.
For
evaluation
of
the
relative
reactivity
of
hydroxymethylferrocene (1a) and methanol in their reaction with
Alcohol
(conversion,
phenylacetylene, the alternative reaction method was used. It has
Z/Eb
Yield
(%)
c
Entry
1
Alkyne
Product
o
ratio
been found that heating (70 C, 3 h) of alcohol 1a and methanol
%
)
with phenylacetylene (1:1:1 molar ratio) in KOH(50
1
mol%)/DMSO system gives, according to H NMR spectrum,
adduct 2e (Z/E ratio 60:40) and 1-(2-methoxyethenyl)benzene
1a (85)
1b (80)
68:32
68:32
64
58
(Z/E ratio 55:45) in molar ratio of 59:41. This result clearly
(
2e)
demonstrates that hydroxymethylferrocene (1a), despite the
presence of the bulky ferrocene moiety, appears to be more
reactive then methanol. In order to understanding this issue, we
have calculated the HOMO energies of potassium methoxide and
ferrocenylmethoxide (actual intermediates in vinylation
2
3
(
2f)
17
reactions) as appropriate descriptors of reactivity of the
corresponding alcohols in the reaction with phenylacetylene.
1
7
Following our theoretical model of KOH/DMSO reactive
center, we have considered complexes of potassium alcoholates
with one DMSO molecule within the PCM solvation model. In
the optimized complex of potassium ferrocenylmethoxide with
DMSO (Figure 1), the potassium ion is coordinated to one of
cyclopentadienyl rings. The HOMO energy for this complex is,
1a (90)
1b (68)
57:43
56:44
56
42
(2g)
1
7
4
by 0.24 eV, higher than that for MeOK•DMSO (–9.03 eV).
Consequently, considering this difference in HOMO energy
between these model complexes, we suggest that alcohol 1a
should display increased reactivity with respect to metanol.
(
2h)
a
.
Reaction conditions: alkohol 1a,b (5 mmol), alkyne (5 mmol), KOH 0.5H
2
O
o
(
2.5 mmol) in DMSO (10 mL), 70 C, 4 h.
b
1
Determined by H NMR analysis of the crude reaction mixtures.
Isolated yields after chromatographic purification.
c
The regioselectivity observed can be explained by fact that the
+
Fukui function [calculated by B3LYP/6-31G(d,p)]
f
for
β
α
phenylacetylene C atom (0.1802) is larger than that for C atom
(
0.0599). Similarly, the Fukui functions for triple bonded atoms
+
+
β
α
f
= 0.1597
f
= 0.0475
C
of 3-ethynylpyridine,
C
and
, predicts the
preferred nucleophilic attack at the terminal position of this
alkyne.
Normally, nucleophilic addition to monosubstituted acetylenes
1
6
is a trans-selective process leading to Z-adducts. As stated
above, vinyl ethers 2e-h are formed as the Z/E-mixtures. The

4
Tetrahedron
Fig. 1. Model complex of potassium ferrocenylmethoxide with one DMSO
ACCEPTED MA
O(1)
NU
-C
S
(6
C
) c
R
ha
I
in and Cp ring is 77.50(15)°. The crystal structure
P
T
molecule [B3LYP/6-31G(d,p)].
of 2a displays C-Hꢁꢁꢁπ and C-HꢁꢁꢁO interactions (Figure 2). In
particular, intermolecular C-HꢁꢁꢁCp short contacts between the
cyclopentadienyl hydrogen, C(5)H, and the cyclopentadienyl
carbon C(2), on the one hand, and between the methylene
hydrogen, C(6)H, and the oxygen (O1), on the other, have been
observed. These short interactions contribute to the formation of
supramolecular chains between adjacent molecules along the c
axis.
Vinylation with 1-propyn-1-yl-benzene and diphenylacetylene
To extend the scope of the developed protocol over the
aryl(alkyl)- and diarylacetylenes, we have checked vinylation of
alcohol 1a with 1-propyn-1-yl-benzene and diphenylacetylene
under conditions, optimized for reaction with arylacetylenes (70
o
C, 50 mol% KOH, DMSO). To our surprise, superbase system
KOH/DMSO successfully catalyzes this reaction despite of
sterical hindrance caused by bulky substituents within both
reactants (Table 5). The vinyl ethers 2i,j are isolated as Z/E
isomer mixtures after column chromatography in 30-40% yields
(non-optimized) along with unreacted alcohol 1a (72-75%
conversion).
Table 5 Regioselective vinylation of ferrocenylalkanol 1a with disubstituted
a
alkynes
Fig. 2. Molecular structure of 2a (30% probability thermal ellipsoids)
showing the intermolecular C-HꢁꢁꢁO and C-Hꢁꢁꢁπ interactions. Selected bond
distances (Å) and angles (°): C(7)-C(8) 1.302(6), O(1)-C(6) 1.442(4), O(1)-
C(7) 1.363(5), C(4)-C(6) 1.492(4). The parameters of intermolecular
interactions: C(6)ꢁꢁꢁO(1) 3.506(4), H(6)ꢁꢁꢁO(1) 2.57, C(5)ꢁꢁꢁCg(1) 3.777(4),
H(2)ꢁꢁꢁCg(1) 2.94, C(6)-H(6)ꢁꢁꢁO(1) 159, C(5)-H(2)ꢁꢁꢁCg(1) 149.
Conversion of
alcohol, %
Z/Eb
Yield
(%)
Entry
1
Alkyne
Product
c
ratio
Compound 2c shows a similar structural motif. In this
structure the non-hydrogen atoms of the chain linked to the
ferrocene unit are essentially coplanar. The mean plane formed
by C(7), O(1), C(8), C(9) and C(10) atoms is orthogonal (90°)
with respect to adjacent Cp ring. Interestingly, despite the
presence of hydrogen bond donors and acceptors in 2c, there are
no short contacts within the crystal packing of the latter.
72
75
70:30
52:48
40
30
(2i)
2
(2j)
a
.
Reaction conditions: alkohol 1a (2 mmol), alkyne (2 mmol), KOH 0.5H
2
O
o
(
1 mmol) in DMSO (5 mL), 70 C, 6-13 h.
b
1
Determined by H NMR analysis of the crude reaction mixtures.
c
Isolated yields after chromatographic purification.
To our knowledge, the formation of ethers 2i,j is the first
example of the alcohol addition to internal alkynes under basic
conditions. Now, such synthetic challenge is usually solved by
using of noble metal-based catalysts, which are often too
expensive. Therefore, the result obtained significantly
compliments the existing conceptions on base-catalyzed addition
of alcohols to C≡C bonds.
Fig. 3. Molecular structure of 2c (30% probability thermal ellipsoids). The
atoms C2A, C3A, C5A and C6A were generated by mirror plane x, 0.5-y, z.
Selected bond distances (Å) and angles (°): C(8)-C(9) 1.326(3), C(8)-C(10)
X-ray structure of ferrocenes 2a,c
1
.497(3), O(1)-C(8) 1.369(2), O(1)-C(7) 1.441(2), C(7)-O(1)-C(8) 116.87,
The molecular structures of the (vinyloxymethyl)ferrocene
C(9)-C(8)-C(10) 125.1.
(
2a) and (prop-1-en-2-yloxymethyl)ferrocene (2c) have been
18
determined by X-ray diffraction analysis (Figures 2 and 3). The
Cp (cyclopentadienyl) cycles in the ferrocene moieties are nearly
eclipsed with twist angles of ca. 8.85° (2a) and 0.09° (2c). The
Fe atom is coordinated to the free and substituted Cp rings at an
average CgꢁꢁꢁFe distance of 1.65 Å, with Cg(1)ꢁꢁꢁFeꢁꢁꢁCg(2)
angles of ca. 179°. The lengths of the C-C and C-Fe bonds in the
3
. Conclusion
In summary, a simple, general and efficient synthesis of
vinyloxy group-containing ferrocenes has been developed.
Superbase systems like “alkali metal hydroxide/DMSO” have
been successfully used for direct vinylation of ferrocene-based
alcohols with various terminal and internal acetylenes, both
under elevated and atmospheric pressure. The vinyloxy-
functionalized ferrocenes thus synthesized are prospective
building blocks for organic and organometallic synthesis as well
as promising monomers and co-monomers for the creation of
redox active polymeric materials. The synthesized ferrocenes 2a-
19
ferrocene sandwich fall close to standard values.
Within molecule 2a the vinyloxy fragment, OCH=CH2,
attached to methylene carbon (C6) is almost planar and adopts an
s-cis conformation: the dihedral angle C(6)-O(1)-C(7)-C(8) takes
the value -0.1(6)°. The C(7)-O(1)-C(6)-C(4) side-chain exists in
the s-trans conformation [torsion angle of -179.2(3)°]. Finally,
the dihedral angle between the average plane of the C(8)-C(7)-

5
j are currently being successfully employe
A
d
C
by
C
u
E
s
P
f
T
or
E
t
D
he MAre
N
mo
U
ve
S
a
C
ir.
R
T
I
he autoclave was fed with acetylene again (initial
P
T
o
synthesis of ferrocene-containing phosphines and phosphine
chalcogenides via free-radical addition of diverse P-H addends to
the vinyloxy groups. The detailed results of these investigations
will be published elsewhere.
pressure at ambient temperature was 13 atm) and heated (70 C)
upon stirring for 0.75 or 1 h. The reaction mixture, after cooling
to room temperature, was diluted with an aqueous 1% solution of
NH Cl (50 ml). The aqueous layer was extracted with diethyl
4
ether (20 mL x 6), the extracts were washed with water (15 mL x
4
4
. Experimental section
3
) and dried (Na SO ). Column chromatography (basic Al O ,
2
4
2
3
eluent hexane/diethyl ether with gradient from 1:0 to 1:1) of the
crude residue after removal of the solvent gave the pure adducts
2a,b and unreacted alcohols 1a,b.
.1. General
1
13
The H and C NMR spectra were recorded with a Bruker
o
DPX-400 spectrometer (20-25 C) in CDCl3 solution using
HMDS as an internal standard. The FT-IR spectra were recorded
on a Bruker Vertex 70 spectrometer in the region of 400-4000
cm . The electron ionization mass spectra were obtained by
using Agilent 5975C MSD instrument. Samples were introduced
into the source by means of the gas chromatograph Agilent
Method B. КОН·0.5Н О (3.25 g, 50 mmol) and DMSO (100
2
mL) were placed into a 3-neck flask equipped with a mechanical
stirrer, reflux condenser and a tube for acetylene feeding. The
-
1
о
suspension was vigorously stirred at 120 С for 1 h and cooled to
o
80 C. Then alcohol 1a,b (50 mmol) was added and pure dry
acetylene was fed into the reaction mixture at a rate of ~ 1 L/h for
2 h (the reaction was monitored by TLC). Further treatment was
performed in the same way as described in method A.
6
0
890N through capillary column HP-5MS (30 m x 0.25 mm x
.25 mm), the helium being the gas-carrier. The source
temperature was approximately 190 °C. The elemental analyses
were carried out on a Flash EA 1112 elemental analyzer. The
content of iron in the reaction products was determined by energy
dispersive X-ray analysis (TM 3000 Hitachi microscope
equipped with SDD X-flash 430-m detector). Melting points
4
1
.4.2. General procedure for the reaction of ferrocenylalkanols
a,b with propyne in the KOH/DMSO system
Method A (Table 2, entries 1, 4). Into a glass 50-mL flask
equipped with a stirrer, a reflux condencer, a thermometer, a
bubbler for propyne supply and a gas outlet, alcohol 1a,b (5.0
(uncorrected) were determined on a Kofler micro-hot stage
apparatus. The high-pressure experiments were carried out in a
stainless steel, high-pressure batch reactor (Parr 4572, Parr
Instrument Co.) equipped with an electrical heating jacket, a gas
inlet, a mechanical stirrer and 4848A temperature controller.
TLC analyses were carried out on Silica gel 60 F254 plates.
mmol), КОН·0.5Н О (0.16 g, 2.5 mmol) and DMSO (30 mL)
2
were placed. Propyne was passed on stirring for 2 h through the
o
reaction mixture heated up to 80 C. After cooling to room
temperature the reaction mixture was diluted with an aqueous 1%
solution of NH Cl (50 ml) and extracted with ether (5 x 30 mL),
4
Commercially available KOH·0.5H O, DMSO (with content of
2
the extracts were washed from DMSO by water (2 x 30 mL),
dried over Na SO . Column chromatography (basic Al O , eluent
water up to 0.5%) were used without further purification. The
2
4
2
3
alcohol 1a was prepared from (ferrocenylmethyl)dimethylamine
hexane/diethyl ether with gradient from 1:0 to 3:1) of the crude
residue after removal of the solvent gave the pure adducts 2c,d
and unreacted alcohols 1a,b.
20
according to improved method. The alcohol 1b was synthesized
by acylation of ferrocene (Aldrich) with acetic anhydride in
2
1
presence of BF ·Et O followed by reduction of the resulting
3
2
Method B. A 0.3-L Parr reactor was charged with alcohol 1b
22
acetylferrocene with NaBH4.
(2.30 g, 10 mmol), КОН·0.5Н О (0.16 g, 2.5 mmol), and
2
propyne (2.12 g, 53 mmol) dissolved at room temperature in
DMSO (50 mL). The reaction mixture was heated at 70 C for 1
h. Further treatment was performed in the same way as described
in method A. As a result, 1.37 g (yield 51%) of 2d and 0.86 g of
1b (63% conversion) were isolated.
4
.2. Crystallography
The crystallographic data were obtained on a Bruker Kappa
o
Apex II CCD diffractometer using φ,ω-scans of narrow (0.5°)
frames with MoK radiation (λ = 0.71073 Å) and a graphite
α
monochromator. The structures were solved by direct methods
2
4.4.3. General procedure for the reaction of ferrocenylalkanols
1a,b with phenylacetylene and 3-ethynylpyridine in the
KOH/DMSO system
and refined by full-matrix least-squares method against all F in
23
anisotropic approximation using the SHELX-97 programs set.
The hydrogen atoms positions were calculated with the riding
model.
A mixture of alcohol 1a,b (5 mmol), arylacetylene (5 mmol)
and KOH·0.5H O (0.163 g, 2.5 mmol) in DMSO (10 mL) was
2
4
.3. Theoretical calculations
o
heated (70 C) and stirred for 4 h. The reaction mixture, after
o
All computations were performed using the Gaussian-09
cooling (20-25 C), was diluted with H O (20 mL), neutralized
2
24
package. The equilibrium geometries and Gibbs free energy
corrections were calculated within a density functional theory
with a hybrid Becke's three-parameter exchange functional and
Lee, Yang, and Parr gradient-corrected correlation functional
using the 6-31G(d,p) basis set. The energy of most stable
with aqueous NH Cl and extracted with Et O (10 mL x 6). The
4
2
organic extract was washed with H O (10 mL x 3) and dried
2
25
(Na SO ). Column chromatography (basic Al O , eluent
2
4
2
3
26
hexane/diethyl ether with gradient from 1:0 to 1:1) of the crude
residue after removal of the solvent gave the pure adducts 2e-h
and unreacted alcohols 1a,b.
conformers of Z- and E-isomers was refined using the extended
6
-311++G(d,p) basis set with the correlation effects included in
4
.4.4. General procedure for the reaction of ferrocenylalkanol 1a
the Møller–Plesset second order perturbation theory.
with disubstituted alkynes in the KOH/DMSO system
4
.4. Synthesis
A mixture of alcohol 1a (0.432 g, 2 mmol), 1-propyn-1-yl-
4
.4.1. General procedure for vinylation of ferrocenylalkanols
benzene (0.224 g, 2 mmol) or diphenylacetylene (0.356 g, 2
1
a,b with acetylene
mmol), KOH·0.5H O (0.065 g, 1.0 mmol) in DMSO (5 mL) was
heated (70 C) and stirred for 6 h (in case of 1-propyn-1-yl-
2
o
Method A (Table 1, entries 4, 5). A mixture of alcohol 1a,b
benzene) or 13 h (in case of diphenylacetylene). The reaction
(30 mmol) and КОН·0.5Н О (0.20 g, 3 mmol) in DMSO (50
o
2
mixture, after cooling (20-25 C), was diluted with H O (5 mL),
2
mL) was placed into a 0.3-L Parr reactor. The latter was fed with
acetylene and then decompressed to atmospheric pressure to
neutralized with aqueous NH Cl and extracted with Et O (5 mL x
4
2
6
). The organic extract was washed with H O (5 mL x 3) and
2

6
Tetrahedron
-
1
+
dried (Na SO ). Column chromatography (b
A
asi
C
c
C
Al
E
O , el
3
P
T
E
ue
D
nt MA44
N
5
U
cmSC
.
R
E
I
I-
P
MS: m/z 270 [M ], 100%. Anal. Сalcd for
T
2
4
2
hexane/diethyl ether with gradient from 1:0 to 1:1) of the crude
residue after removal of the solvent gave the pure adducts 2i,j
and unreacted alcohol 1a (0.120 and 0.110 g, conversion 72 and
C H FeO (270.15): С, 66.69; Н, 6.72; Fe, 20.67. Found: C,
1
5
18
66.64; Н, 6. 68; Fe, 20.47.
.5.5. 2-(Phenylethenyl)oxymethylferrocene (2e)
mixture of Z/E isomers in 68:32 ratio (after
chromatographic purification). Yellow powder, mp 45-47
4
7
4
4
5%, respectively).
A
a
.5. Characterization data for compounds 2a-h
o
C
.5.1. Vinyloxymethylferrocene (2a)
(hexane). Yield: 1.02 g (64%). IR (KBr) 3096, 3083, 3049, 3021,
o
2976, 2925, 1650, 1641, 1597, 1492, 1460, 1446, 1419, 1382,
1347, 1322, 1306, 1283, 1240, 1219, 1199, 1162, 1127, 1104,
1078, 1028, 998, 980, 924, 821, 812, 758, 746, 713, 694, 531,
Yellow-orange solid, mp 32 C (hexane). Yield: 5.91 g, 81%
1
(
method A), 9.81 g, 81% (method B). H NMR (400.13 MHz,
CDCl ) δ 6.46 (dd, J = 14.3, J = 6.7 Hz, 1H, CH=), 4.46 (s, 2 H,
CH O), 4.23 (d, J = 14.3 Hz, 1H, CH =), overlapped with 4.22
3
3
3
-1
+
3
511, 481, 412, 403 cm . EI-MS: m/z 318 [M ], two picks
100%). Anal. Сalcd for C H FeO (318.19): С, 71.72; Н, 5.70;
2
2
(
19
18
(
(
br. s, 2 H, 2H in Fc), 4.13-4.12 (m, 7H, 2H in Fc, C H ), 3.99
1
α
β
5
5
3
13
Fe, 17.55. Found: C, 71.64; Н, 5.86; Fe, 17.43. (Z)-2e: H NMR
d, J = 6.7 Hz, 1H, CH =). C NMR (100.62 MHz, CDCl ) δ
2
3
(
2
5
1
400.13 MHz, CDCl ) δ 7.59-7.57 (m, 2 H, H ), 7.27-7.20 (m,
3
o
1
51.6 (CH=), 86.6 (CH =), 82.3 (C in Fc), 68.9 (C in Fc), 68.45
C in Fc), 68.4 (C H ), 66.6 (OCH ). IR (KBr) 3120, 3105,
090, 3031, 2928, 2883, 1660 sh, 1636, 1612, 1408, 1397, 1382,
315, 1242, 1192, 1146, 1105, 1045 sh, 1039, 1027, 998, 984,
53, 928, 867, 828, 813, 749, 509, 500, 482 cm . EI-MS: m/z
3
2
i
β
H, H ), 7.12-6.99 (m, 1H, H ), 6.28 (d, J = 7.1 Hz, 1H, =CHO),
m
p
(
3
3
α
5
5
2
.20 (d, J = 7.1 Hz, 1H, =CHPh), 4.71 (s, 2H, CH ), 4.27 (t, J =
.8 Hz, 2H, H in Fc), 4.16 (t, J = 1.8 Hz, 2H, H in Fc), 4.16 (s,
2
3
1
9
2
3
α
β
13
-
1
5H, C
5
H
5
). C NMR (100.62 MHz, CDCl
3
) δ 146.4 (OCH=),
+
136.1 (C
PhCH=), 83.1 (C in Fc), 71.7 (OCH ), 69.1 (C in Fc), 68.8 (C
β
i
, Ph), 128.3, 128.2 (Co,m, Ph), 125.7 (C , Ph), 105.6
p
42 [M ], 100%. Anal. Сalcd for C H FeO (242.09): С, 64.50;
Н, 5.83; Fe, 23.07. Found: C, 64.74; Н, 5.86; Fe, 23.13.
13
14
(
i
2
α
1
in Fc), 68.6 (C H ). (E)-2e: H NMR (400.13 MHz, CDCl ) δ
5
5
3
4
.5.2. 1-(Vinyloxy)ethylferrocene (2b)
7.59-7.57 (m, 2 H, H
o
), 7.27-7.20 (m, 2H, H
m
), 7.12-6.99 (m, 1H,
3
3
H ), 7.00 (d, J = 12.7 Hz, 1H, =CHO), 5.89 (d, J = 12.7 Hz, 1H,
p
3
Orange syrup. Yield: 7.12 g, 93% (method A), 11.51 g, 90%
=
CHPh), 4.64 (s, 2H, CH ), 4.22 (t, J = 1.8 Hz,, 2H, H in Fc),
2 α
3 13
1
3
(
method B). H NMR (400.13 MHz, CDCl ) δ 6.36 (dd, J = 14.3,
3
3 3
4.16 (t, J = 1.8 Hz,, 2H, H in Fc), 4.16 (s, 5H, C H ). C NMR
β 5 5
3
J = 6.7 Hz, 1H, CH=), 4.71 (q, J = 6.4 Hz, 1H, CH), 4.31 (d, J
14.3 Hz, 1H, CH =), 4.19-4.18 (m, 2 H, 2H in Fc), 4.13-4.12
(100.62 MHz, CDCl ) δ 147.8 (OCH=), 136.5 (C , Ph), 128.6,
3
i
=
2
α
128.2 (Co,m, Ph), 125.1 (C , Ph), 106.4 (PhCH=), 82.3 (C in Fc),
69.1 (C in Fc), 68.8 (C in Fc), 68.7 (C H ), 68.6 (OCH ).
α β 5 5 2
p
i
3
(
m, 7H, 2H in Fc, C H ), 3.98 (d, J = 6.7 Hz, 1H, CH =), 1.53
β 5 5 2
3 13
(d, J = 6.4 Hz, 3H, Me). C NMR (100.62 MHz, CDCl ) δ
3
4
.5.6. 2-(1-[2-Phenylethenyl]oxyethyl)ferrocene (2f)
1
50.7 (CH=), 89.1 (C in Fc), 88.3 (CH =), 74.3 (CH), 68.7
i
2
(
C H ), 68.0, 67.9 (C in Fc), 67.8, 65.9 (C in Fc), 20.4 (Me). IR
5 5 β α
A
mixture of Z/E isomers in 68:32 ratio (after
a
(film) 3096, 2979, 2935, 2891, 2870, 1632, 1611, 1444, 1412,
chromatographic purification). Brown honey-like substance.
Yield 0.96 g (58%). IR (film) 3086, 3056, 3023, 2979, 2930,
2856, 1648, 1599, 1573, 1493, 1448, 1413, 1391, 1373, 1329,
318, 1264, 1241, 1219, 1200, 1152, 1106, 1096, 1062, 1043,
025, 1001, 954, 923, 893, 820, 779, 751, 695, 557, 512, 483,
436, 403 cm . EI-MS: m/z 332 [M ], two picks (100%). Anal.
Сalcd for C H FeO (332.22): С, 72.31; Н, 6.07; Fe, 16.81.
Found: C, 72.44; Н, 5.96; Fe, 17.13. (Z)-2f: H NMR (400.13
MHz, CDCl ) δ 7.64-7.63 (m, 2H, H ), 7.29-7.25 (m, 2H, H ),
7.20-7.18 (m, 1H, H ), 6.34 (d, J = 7.1 Hz, 1H, =CHO), 5.21 (d,
J = 7.1 Hz, 1H, =CHPh), 4.73 (q, J = 6.5 Hz, 1H, MeCH), 4.24
(br. s, 2H, H ), 4.16 (br.s, 7H, H in Fc, C H ), 1.62 (d, J = 6.5
Hz, 3H, Me). C NMR (100.62 MHz, CDCl ) δ 145.7 (OCH=),
1
1
404, 1391, 1371, 1330, 1314, 1240, 1201 sh, 1187, 1153, 1106,
-1
073, 1045, 1027, 1001, 971, 948, 911, 819, 720, 697, 482 cm .
+
EI-MS: m/z 256 [M ], 90%. Anal. Сalcd for C H FeO (256.12):
С, 65.65; Н, 6.30; Fe, 21.80. Found: C, 65.50; Н, 6.18; Fe, 21.89.
14
16
1
1
-
1
+
4
.5.3. 2-(Propenyloxy)methyl]ferrocene (2c)
20
20
o
1
Orange solid, mp 92-94 C (hexane). Yield: 0.88 g, 65%
1
(method A). H NMR (400.13 MHz, CDCl ) δ 4.44 (s, 2H,
3
3
o
m
3
3
OCH ), 4.25 (br. t, J = 1.7 Hz, 2H, H in Fc), 4.14-4.13 (m, 7H,
2
3
2
α
p
3
3
H in Fc, C H ), 3.90 and 3.87 (br. s, each 1H, CH =), 1.81 (s,
β 5 5 2
13
3
H, MeC). C NMR (100.62 MHz, CDCl ) δ 160.0 (OC=), 82.9
3
α
β
5
5
13
(C in Fc), 81.2 (CH =), 69.2 (C in Fc), 68.6 (C H ), 68.5 (C in
i 2 α 5 5 β
3
Fc), 65.8 (OCH ), 21.2 (MeC). IR (film) 3114, 3101, 3083, 2991,
2
136.4 (C , Ph), 128.2, 128.2 (C , Ph), 125.6 (C , Ph), 105.3
PhCH=), 89.9 (C in Fc), 77.8 (OCH), 68.8 (C H ), 68.0 (C in
Fc), 67.4, 66.0 (C in Fc), 21.6 (Me). (E)-2f: H NMR (400.13
MHz, CDCl ) δ 7.22-7.20 (m, 2H, H ), 7.12-7.09 (m, 3H, Hm,p),
i
o,m
p
2
1
9
956, 2922, 2850, 1655, 1648 sh, 1595, 1482, 1462, 1449, 1430,
406, 1398, 1376, 1357, 1277, 1240, 1106, 1055, 1041, 1024,
(
i
5
5
β
1
α
-
1
92, 952, 931, 879, 841, 827, 798, 732, 514, 497, 485, 449 cm .
3
o
+
3
3
EI-MS: m/z 256 [M ], 100%. Anal. Сalcd for C H FeO
14
16
6.94 (d, J = 12.7 Hz, 1H, =CHO), 5.93 (d, J = 12.7 Hz, 1H,
3
(256.12): С, 65.65; Н, 6.30; Fe, 21.80. Found: C, 65.27; Н, 6.69;
=
CHPh), 4.81 (q, J = 6.5 Hz, 1H, MeCH), 4.21 (br. s, 2H, H in
α
3
Fe, 21.36.
Fc), 4.15 (br. s, 7H, H in Fc, C H ), 1.60 (d, J = 6.5 Hz, 3H,
β
5
5
1
3
Me). C NMR (100.62 MHz, CDCl ) δ 146.9 (OCH=), 136.7
3
4
.5.4. 2-[1-(Propenyloxy)ethyl]ferrocene (2d)
(
C , Ph), 128.6, 125.6 (C , Ph), 125.1 (Co,m, Ph), 107.8 (PhCH=),
i
p
o
Yellow solid, mp 83-84 C (hexane). Yield: 0.79 g, 58%
88.9 (C in Fc), 76.1 (OCH), 68.8 (C H ), 68.3, 68.2 (C in Fc),
68.0, 66.0 (C in Fc), 20.8 (Me).
i
5
5
β
1
(method A), 1.37 g, 51% (method B). H NMR (400.13 MHz,
α
3
CDCl ) δ 4.92 (q, J = 6.2 Hz, 1H, CHMe), 4.21-4.20 (m, 2H, H
in Fc), 4.13 (s, 5H, C H ), 4.11-4.10 (m, 2H, H in Fc), 3.92 (s,
3
α
4
.5.7. 3-{2-[(Ferrocenyl)methoxy]ethenyl}pyridine (2g)
5
5
β
3
2
H, CH =), 1.80 (s, 3H, MeC), 1.51 (d, J = 6.2 Hz, 3H, MeCH).
2
A
mixture of Z/E isomers in 57:43 ratio (after
a
13
C NMR (100.62 MHz, CDCl ) δ 158.6 (OC=), 90.4 (C in Fc),
3
i
chromatographic purification). Reddish-brown oil, yield 0.89 g
(56%). IR (film) 3091, 3040, 3031, 3022, 2987, 2933, 2873,
858, 1649, 1633, 1586, 1566, 1480, 1457, 1425, 1413, 1382,
353, 1348, 1332, 1286, 1239, 1196, 1146, 1124, 1104, 1077,
040, 1023, 1001, 986 sh, 945, 932, 876, 831, 816, 800 sh, 776,
8
6
3
1
1
1.6 (CH =), 68.5 (C H ), 70.4 (C in Fc), 67.8, 67.6 (C in Fc),
2 5 5 α β
6.3 (OCHMe), 21.8 (MeCH), 19.4 (MeC). IR (film) 3113, 3102,
090, 2989, 2981, 2941, 2922, 1649, 1584, 1478, 1443, 1430,
408, 1373, 1318, 1274, 1241, 1207, 1105, 1098, 1069, 1046,
027, 1002, 979, 916, 893, 832, 816, 794, 712, 545, 506, 482,
2
1
1
7
-
1
+
51, 710, 511, 500, 491, 484, 438 cm . EI-MS: m/z 320 [M ],

7
two picks (80%). Anal. Сalcd for C H Fe
A
NOCC(3
E
19
P
.1
T
8)
E
:
D
С, MA(1
N
00
U
.62
S
M
C
H
R
z
I
,
P
C
T
DCl ) δ 155.8 (OC=), 137.9 (C , Ph), 128.7,
3 i
18
17
6
1
8
7.73; Н, 5.37; Fe, 17.50; N, 4.39. Found: C, 67.70; Н, 5.46; Fe,
128.2 (C , Ph), 125.1 (C , Ph), 100.1 (PhCH=), 82.8 (C in Fc),
69.2 (C in Fc), 68.6 (C H ), 68.5 (C in Fc), 65.6 (OCH ), 18.2
(Me). (E)-2i: H NMR (400.13 MHz, CDCl ) δ 7.58-7.08 (m,
5H, Ph), 5.33 (s, 1H, =CHPh), 4.72 (s, 2H, CH ), 4.27 (br.s, 2H,
H in Fc), 4.16 (br.s, 2H, H in Fc), 4.14 (s, 5H, C H ), 2.07 (s,
3H, Me). C NMR (100.62 MHz, CDCl ) δ 152.7 (OC=), 136.7
o,m
p
i
1
7.13; N, 4.20. (Z)-2g: H NMR (400.13 MHz, CDCl ): δ 8.68-
3
α
5
5
β
2
3
4
1
.67 (m, 1H, H-2, Py), 8.32 (dd, J = 4.7, J = 1.8 Hz, 1H, H-6,
3
3
4
4
Py), 7.97 (dt, J = 7.6, J ≈ J = 1.8, Hz, 1H, H-4, Py), 7.17 (dd,
2
3
3
3
J = 7.6, J = 5.0 Hz, 1H, H-5, Py), 6.40 (d, J = 6.9 Hz, 1H,
α
β
5
5
3
13
=
CHO), 5.18 (d, J = 6.9 Hz, 1H, =CHPy), 4.75 (s, 2H, OCH ),
2
3
4
5
1
1
6
.27 (br. s, 2H, H in Fc), 4.20-4.19 (m, 2H, H in Fc), 4.16 (br. s,
(C , Ph), 128.0 (C , Ph), 125.2 (C , Ph), 107.6 (PhCH=), 83.7
α
β
i
o,m
p
13
H, C H ). C NMR (100.62 MHz, CDCl ) δ 149.4 (C-2, Py),
(C in Fc), 68.6 (C H ), 68.5 (C in Fc), 68.3 (C in Fc), 66.2
5
5
3
i
5
5
β
α
48.1 (C-6, Py), 146.4 (OCH=), 134.8 (C-4, Py), 132.1 (C-3, Py),
(OCH ), 19.6 (Me).
2
23.1 (C-5, Py), 102.0 (PyCH=), 101.7 (C in Fc), 72.0 (OCH ),
i
2
1
4.5.10. 1-{[(1,2-diphenylethenyl)oxy]methyl}ferrocene (2j)
mixture of Z/E isomers in 52:48 ratio (after
8.9 (C in Fc), 68.6 (C H ), 68.5 (C in Fc). (E)-2g: H NMR
β
5
5
α
3
(400.13 MHz, CDCl ) δ 8.46-4.44 (m, 1H, H-2, Py), 8.34 (dd, J
A
a
3
4
3
o
=
4
=
5.0, J = 1.7 Hz, 1H, H-6, Py), 7.50 (br. d, J = 7.0 Hz, 1H, H-
, Py), 7.15 (dd, J = 7.08, J = 5.0 Hz, 1H, H-5, Py), 7.03 (d, J
12.7 Hz, 1H, =CHO), 5.83 (d, J = 12.7 Hz, 1 H, =CHPy), 4.67
chromatographic purification). Yellow powder, mp 68-81 C
3
3
3
(hexane). Yield: 0.235 g (30%). IR (KBr) 3109, 3080, 3060,
3018, 2997, 2925, 2877, 2857, 1668, 1633, 1623, 1596, 1570,
1492, 1446, 1410, 1392, 1378, 1330, 1317, 1277, 1242, 1224,
1201, 1181, 1103, 1098, 1073, 1042, 1024, 1000, 969, 952, 934,
920, 910, 889, 863, 842, 828, 815, 773, 750, 728, 695, 646, 574,
3
(s, 2H, OCH ), 4.27 (br. s, 2H, H in Fc), 4.20-4.19 (m, 2H, H in
2
α
β
13
Fc), 4.16 (br. s, 5H, C H ). C NMR (100.62 MHz, CDCl ) δ
1
1
5
5
3
49.0 (C-2, Py), 147.0 (C-6, Py), 146.8 (OCH=), 132.4 (C-3, Py),
-
1
+
31.5 (C-4, Py), 123.4 (C-5, Py), 102.8 (PyCH=), 101.7 (C in
503, 480 cm . EI-MS: m/z 394 [M ], two picks (90%). Anal.
i
Fc), 69.2 (C in Fc), 69.0 (OCH ), 68.8 (C H ), 68.3 (C in Fc).
Сalcd for C H FeO (394.29): С, 76.15; Н, 5.62; Fe, 14.16.
β
2
5
5
α
25 22
1
Found: С, 76.04; Н, 5.55; Fe, 13.89. (Z)-2j: H NMR (400.13
4
.5.8. 3-{2-[1-(2-Ferrocenyl)ethoxy]ethenyl}pyridine (2h)
MHz, CDCl ) δ 7.71-7.16 (m, 10 H, Ph), 6.10 (s, 1H, =CHPh),
3
A
mixture of Z/E isomers in 82:18 ratio (after
a
4.73 (s, 2H, CH
2
), 4.30 (br. s, 2H, H
α
in Fc), 4.13 (br.s, 2H, H
β
in
13
Fc), 4.12 (s, 5H, C H ). C NMR (100.62 MHz, CDCl ) δ 156.6
(OC=), 137.2, 136.1 (C
128.3, 128.1 (Co,m, Ph), 113.9 (PhCH=), 83.08 (C
chromatographic purification). Reddish-brown oil, yield 0.70 g
42%). IR (film) 3094, 3036, 2979, 2935, 2896, 2869, 1647,
586, 1564, 1477, 1428, 1404, 1375, 1330, 1315, 1276, 1241,
221, 1198, 1153, 1126, 1106, 1098, 1069, 1042, 1024, 1002,
47, 923, 893, 816, 710, 751, 629, 511, 483, 436 cm . EI-MS:
m/z 333 [M ], two picks (100%). Anal. Сalcd for C H FeNO
333.20): С, 68.49; Н, 5.75; Fe, 16.76; N, 4.20. Found: C, 68.30;
Н, 5.59; Fe, 16.62; N, 4.12. (Z)-2h: H NMR (400.13 MHz,
CDCl ): δ 8.73 (br. s, 1H, H-2, Py), 8.32 (br. d, J = 4.7 Hz, 1H,
H-6, Py), 8.00 (br. d, J = 7.9 Hz, 1H, H-4), 7.18 (dd, J = 7.9,
5
5
3
(
i
, Ph), 128.4, 126.7 (C
p
, Ph), 129.0, 128.4,
1
1
9
i
in Fc), 69.2
(
C in Fc), 68.8 (C H , OCH ), 68.6 (C in Fc), 65.6 (OCH ). (E)-
α
5
5
2
β
2
-
1
1
2j: H NMR (400.13 MHz, CDCl
5.91 (s, 1H, =CHPh), 4.55 (s, 2H, CH
4
) δ 7.33-6.96 (m, 10 H, Ph),
), 4.20 (br.s, 2H, H in Fc),
.15 (br. s, 2H, H in Fc), 4.04 (s, 5H, C H ). C NMR (100.62
3
+
19
19
2
α
13
(
β
5
5
1
MHz, CDCl
) δ 155.1 (OC=), 137.1, 136.3 (C
128.7, 126.8 (Co,m, Ph), 128.7, 125.4 (C , Ph), 103.3 (PhCH=),
p
, Ph), 129.6, 128.9,
3
i
3
3
3
3
8
2.8 (C in Fc), 69.5 (C in Fc), 68.9 (C in Fc), 68.6 (C H ), 67.0
i
α
β
5
5
5-4
3
3
J5-6 = 4.7 Hz, 1H, H-5, Py), 6.46 (d, J = 6.3 Hz, 1H, =CHO),
.17 (d, J = 6.9 Hz, 1H, =CHPy), 4.79 (q, J = 6.3 Hz, 1H,
MeCH), 4.21 and 4.23 (br. s, each 1H, H in Fc), 4.17 (br. s, 2H,
H in Fc), 4.15 (s, 5H, C H ), 1.64 (d, J = 6.3 Hz, 3H, Me).
(OCH
2
).
3
3
5
Acknowledgments
α
3
13
C
β
5
5
NMR (100.62 MHz, CDCl ) δ 149.4 (C-2, Py), 147.4 (C-6, Py),
This work was supported by the President of the Russian
Federation (program for the support of leading scientific schools,
grant NSh-156.2014.3).
3
1
1
46.4 (OCH=), 134.7 (C-4, Py), 131.5 (C-3, Py), 123.1 (C-5, Py),
01.7 (PyCH=), 89.2 (C in Fc), 78.3 (OCH), 68.8 (C H ), 68.2
i
5
5
1
(
C in Fc), 67.5, 66.0 (C in Fc), 21.5 (Me). (E)-2h: H NMR
β α
3
(400.13 MHz, CDCl ) δ 8.44 (br. s, 1H, H-2, Py), 8.32 (d, J =
Supplementary Material
3
3
4
.9 Hz, 1H, H-6, Py), 7.47 (br. d, J = 7.8 Hz, 1H, H-4, Py), 7.13
3
3
3
(dd, J = 7.8, J = 4.9, Hz, 1H, H-5, Py), 6.97 (d, J = 12.7 Hz,
Copies of NMR spectra for compounds 2a-j; crystallographic
data for compounds 2a,c; structural and thermochemical data for
compounds 2e-g from DFT and MP2 calculations can be found in
the online version, at … .
3
3
1
H, =CHO), 5.85 (d, J = 12.7 Hz, 1H, =CHPy), 4.85 (q, J = 6.3
Hz, 1H, MeCH), 4.21 and 4.23 (br. s, each 1H, H in Fc), 4.17
α
3
(
br. s, 2H, H in Fc), 4.15 (s, 5H, C H ), 1.62 (d, J = 6.3 Hz, 3H,
β 5 5
13
Me). C NMR (100.62 MHz, CDCl ) δ 148.10 (C-2, Py), 146.8
3
(
(
(
OCH=), 146.7 (C-6, Py), 132.5 (C-3, Py), 132.3 (C-4, Py), 123.4
References and notes
C-5, Py), 104.1 (PyCH=), 88.5 (C in Fc), 76.6 (OCH), 68.8
i
C H ), 68.4, 68.3 (C in Fc), 68.0, 66.0 (C in Fc), 20.7 (Me).
5
5
β
α
1. (a) Togni, A.; Halterman, R. L. Metallocenes, Wiley: Weinheim, 1998;
(
b) Phillips, E. S. Ferrocenes: Compounds, Properties and
4
.5.9. 1-{[(1-methyl-2-phenylethenyl)oxy]methyl}ferrocene (2i)
Applications, Nova Science Publishers, Incorporated, 2011.
(a) Stepnicka, P. Ferrocenes: Ligands, Materials and Biomolecules,
Wiley: Chichester, 2008; (b) Dai, L.-X.; Hou, X.-L. Chiral Ferrocenes
in Asymmetric Catalysis: Synthesis and Applications, Wiley: Weinheim,
2009.
2
.
A
mixture of Z/E isomers in 70:30 ratio (after
a
o
chromatographic purification). Yellow powder, mp 44-59
C
(hexane). Yield: 0.26 g (40%). IR (KBr) 3086, 3055, 3021, 2996,
2
1
1
5
950, 2919, 2872, 1649, 1598, 1573, 1493, 1463, 1438, 1411,
391, 1380, 1352, 1339, 1313, 1289, 1271, 1240, 1179, 1157,
106, 1075, 1046, 1025, 1001, 963, 913, 818, 752, 736, 698, 639,
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-
1
+
23, 504, 486 cm . EI-MS: m/z 332 [M ], two picks (100%).
4
272; (b) Butler, I. S.; Kengne-Momo, R. P.; Vessières, A.; Policar, G.
Anal. Сalcd for C H FeO (322.22): С, 72.31; Н, 6.07; Fe,
1
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2
0
20
1
6.81. Found: C, 71.41; Н, 5.99; Fe, 16.20. (Z)-2i: H NMR
(400.13 MHz, CDCl ) δ 7.58-7.08 (m, 5 H, Ph), 5.67 (s, 1H,
3
(a) Biot, C. Curr. Med. Chem.: Anti-Infective Agents 2004, 3, 135-147;
=
2
CHPh), 4.59 (s, 2H, CH ), 4.29 (br. s, 2H, H in Fc), 4.17 (br. s,
2 α
13
(b) van Staveren, D. R.; Metzler-Nolte, N. Chem. Rev. 2004, 104, 5931–
H, H in Fc), 4.16 (s, 5H, C H ), 2.00 (s, 3 H, Me). C NMR
β
5
5

8
Tetrahedron
5
986; (c) Wu, X.; Go, M. L. in: Metallotherapeutic Drugs and Metal-Based
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Bioorganometallics: Biomolecules, Labeling, Medicine, Wiley:
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886; (b) Correia-Ledo, D.; Arnold, A. A.; Mauzeroll, J. J. Am. Chem.
Soc., 2010, 132, 15120–15123; (c) Matas, I.; Whittell, G. R.; Partridge,
B. M.; Holland, J. P.; Haddow, M. F.; Green, J. C.; Manners, I. J. Am.
Chem. Soc., 2010, 132, 13279–13289; (d) Gao, D.-W.; Shi, Y.-C.; Gu,
Q.; Zhao, Z.-L.; You, S.-L. J. Am. Chem. Soc., 2013, 135, 86–89.
(a) Zhou, M.; Sun, Z.; Shen, C.; Li, Z.; Zhang, Y.; Yang, M. Biosens.
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Thakur, A.; Ponniah, J.; Ghosh, S. RSC Adv. 2013, 3, 18614-18625; (c)
Uahengo, V.; Xionga, B.; Zhao, P.; Zhang, Y.; Cai, P.; Hu, K.; Cheng,
G. Sensor. Actuat. B-Chem. 2014, 190, 937–945.
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Trofimov, B. A. in: Modern Problems of Organic Chemistry (Eds.:
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University Press, St. Petersburg, 2004, Issue 14, pp. 121-163.
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0. Trofimov, B. A.; Gusarova, N. K. Russ. Chem. Rev. 2007, 76, 507–527.
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ACCEPTED MANUSCRIPT
Supporting Information
Table of Contents
Page
S2
Crystallographic data for compounds 2a,c
1
13
Copies of H and C NMR spectra of the synthesized products
S3-S12
Structural and thermochemical data for compounds 2e-g from DFT and MP2
calculations
S13-S18
S1

ACCEPTED MANUSCRIPT
Crystallographic data for compounds 2a,c
Compound
2a
2c
Empirical formula
C H FeO
C HFeO
14
1
3
14
Formula weight
242.09
241.00
Temperature/K
223(2)
200(2)
Crystal system
Space group
monoclinic
orthorhombic
Pnma
P2 /c
1
a/Å
b/Å
c/Å
α/°
β/°
γ/°
Volume/Å
Z
13.976(3)
9.967(2)
8.0699(14)
90.00
93.419(7)
90.00
1122.1(4)
4
1.433
1.312
504.0
0.16 × 0.14 × 0.02
MoKα (λ = 0.71073)
11.4876(3)
8.2377(2)
12.4947(3)
90.00
90.00
90.00
1182.39(5)
4
1.354
1.246
476.0
3
3
ρ mg/mm
calc
-1
m/mm
F(000)
Crystal size/mm
Radiation
3
0.58 × 0.35 × 0.07
MoKα (λ = 0.71073)
4.82 to 60.12°
26802
2
Θ range for data collection 2.92 to 54.98°
Reflections collected
11203
Independent reflections
2576 [R = 0.0519, R
= 0.0478]1847 [R = 0.0426, R
= 0.0157]
sigma
int
sigma
int
Data/restraints/parameters 2576/0/136
1847/7/94
1.149
2
Goodness-of-fit on F
1.033
Final R indexes [I>=2σ (I)] R = 0.0378, wR = 0.1209
R = 0.0267, wR = 0.0880
1
2
1
2
Final R indexes [all data]
Largest diff. peak/hole / e Å 0.54/-0.49
R = 0.0650, wR = 0.1517
R = 0.0289, wR = 0.0905
0.61/-0.60
1
2
1
2
-3
S2

ACCEPTED MANUSCRIPT
1
13
Copies of H and C NMR spectra of the synthesized products
Vinyloxymethylferrocene (2a).
O
Fe
S3

ACCEPTED MANUSCRIPT
1-(Vinyloxy)ethylferrocene (2b).
O
Fe
Me
S4

ACCEPTED MANUSCRIPT
2-(Propenyloxy)methyl]ferrocene (2c).
O
Fe
Me
S5

ACCEPTED MANUSCRIPT
2
-[1-(Propenyloxy)ethyl]ferrocene (2d)
O
Fe
Me Me
S6

ACCEPTED MANUSCRIPT
2
-(Phenylethenyl)oxymethylferrocene (2e).
O
Ph
Fe
S7

ACCEPTED MANUSCRIPT
2
-(1-[2-Phenylethenyl]oxyethyl)ferrocene (2f).
O
Ph
Fe
Me
S8

ACCEPTED MANUSCRIPT
3
-{2-[(ferrocenyl)methoxy]ethenyl}pyridine (2g)
O
Fe
N
S9

ACCEPTED MANUSCRIPT
3
-{2-[1-(2-ferrocenyl)ethoxy]ethenyl}pyridine (2h)
O
Fe
Me
N
S10

ACCEPTED MANUSCRIPT
1
-{[(1-methyl-2-phenylethenyl)oxy]methyl}ferrocene (2i)
H
O
Fe
Me
Ph
S11

ACCEPTED MANUSCRIPT
1
-{[(1,2-diphenylethenyl)oxy]methyl}ferrocene (2j)
H
O
Fe
Ph
Ph
Structural and thermochemical data for compounds 2e-g from DFT and MP2 calculations
S12

ACCEPTED MANUSCRIPT
The B3LYP/6-31G(d,p) optimized structures, the MP2/6-311++G(d,p)//B3LYP/6-31G(d,p) energies
EMP2) and the B3LYP/6-31G(d,p) corrections to Gibbs free energy (G ) of 2e – g
(
corr
C
C
C
C
C
C
C
C
O
C
C
C
C
C
C
Fe
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
0.082704
0.240303
1.528883
2.616637
2.445361
1.170657
-0.865972
-2.056099
-3.119472
-3.018943
-4.322682
-4.468480
-5.860780
-6.580474
-5.633893
-5.431511
-6.047061
-4.638726
-4.415350
-5.686000
-6.694704
-7.656468
-5.859371
-3.659101
-5.854872
-7.761891
-6.536413
-3.876018
-3.452325
-6.292912
-2.211005
-2.289169
-0.663557
-0.902588
1.020204
3.290421
3.599898
1.675083
-2.757009
-0.021953
-0.128534
-0.407075
-0.552874
-0.425673
-0.160810
0.025737
0.584341
0.751651
0.220617
0.393620
0.631204
0.628565
0.390102
0.237652
2.081758
3.499483
3.591639
3.848915
3.914788
3.699249
0.348681
0.063203
0.793879
4.088514
3.681118
3.296793
3.449871
3.963352
0.795578
0.727045
0.992678
-0.322079
0.151867
-0.074340
-0.540168
-0.765613
-0.502417
-0.845981
-0.069911
1.325579
1.817074
0.958574
-0.420161
-0.927147
2.280373
1.996976
2.823791
4.148555
4.861499
6.266475
6.578023
5.368806
4.312441
5.194390
3.842062
4.050971
5.437075
6.084838
5.098208
5.267451
3.269778
6.966217
7.138954
5.273528
2.899149
3.298617
5.916069
7.555202
4.694149
1.018609
3.288657
-0.492019
-1.999699
-1.092319
1.368793
2.890200
4.079465
EMP2 = – 2070.4468811 a.u.
Gcorr = 0.268319 a.u.
S13

ACCEPTED MANUSCRIPT
C
C
C
C
C
C
C
C
O
C
C
C
C
C
C
Fe
C
C
C
C
C
H
H
H
H
H
H
H
0.137643
0.061986
1.081924
2.120319
2.175311
1.176390
-1.062260
-1.421345
-0.747367
-1.383050
-0.464415
0.955071
1.407637
0.271004
-0.884274
0.438534
-0.571561
0.276876
1.618662
1.597527
0.244472
2.435688
1.572559
-1.902553
-0.041379
2.495563
2.455457
-0.101147
-1.646524
0.282878
-2.317125
-2.304329
-1.719476
1.056967
2.896011
2.987348
1.206521
-0.635565
-1.640744
0.318899
0.186350
-0.542052
-1.113899
-0.977372
-0.254581
0.814403
0.759746
0.068697
0.035827
-0.567720
-0.414910
-1.061048
-1.605278
-1.303258
-2.405232
-3.958372
-4.446507
-4.077838
-3.362106
-3.287852
-1.139422
0.083064
-1.586355
-4.990756
-4.292863
-2.936762
-2.784765
-4.069550
-2.165241
-0.539262
1.294699
1.417411
-0.647720
-1.670063
-1.426434
-0.136523
0.880057
1.065444
0.113291
1.513967
2.160828
1.428550
0.039904
-0.614760
2.209975
3.504457
4.464791
5.749447
6.762764
6.840644
8.029126
8.698587
7.917973
6.816571
5.928627
6.967922
6.649865
5.415175
4.968827
8.355879
6.106537
8.150698
7.846786
7.245450
4.912562
4.076869
5.882412
9.623721
5.689925
3.851141
1.588851
3.237810
1.948192
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6.042101
EMP2 = –2070.4486162 a.u.
Gcorr = 0.268813a.u.
H
H
H
H
H
H
H
H
H
H
H
S14

ACCEPTED MANUSCRIPT
C
C
C
C
C
Fe
C
C
C
C
C
C
C
O
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
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-8.518595
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EMP2 = –2109.6507017 a.u.
Gcorr = 0.294375 a.u.
S15

ACCEPTED MANUSCRIPT
C
C
C
C
C
Fe
C
C
C
C
C
C
O
C
H
H
H
H
H
H
H
H
H
H
H
H
H
C
C
H
H
C
C
C
C
C
C
H
H
H
H
H
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EMP2 = – 2109.6523318 a.u.
Gcorr = 0.294094 a.u.
S16

ACCEPTED MANUSCRIPT
C
C
C
C
C
Fe
C
C
C
C
C
C
O
C
C
C
C
C
C
N
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
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EMP2 = – 2086.47317741 a.u.
Gcorr = 0.255562 a.u.
S17

ACCEPTED MANUSCRIPT
C
C
C
N
C
C
C
C
O
C
H
C
C
C
C
C
Fe
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
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EMP2 = – 2086.476448 a.u
Gcorr = 0.258022 a.u.
S18