Palladium-catalyzed reaction of 2-iodoferrocenyl alcohols with internal alkynes: Synthesis of functionally 1,2-disubstituted ferrocenes and ferroceno-pyrans

Article abstract of DOI:10.1016/j.jorganchem.2012.01.007

The reaction of racemic (2-iodoferrocenyl)methanol with internal alkynes in the presence of (dppf)PdCl₂ and i-Pr₂NH produces alkenyl-substituted ferrocene carboxaldehydes in moderate yields. All reactions are carried out at 100 or 120 °C for different reaction times (between 6 and 26 h) in a screw-cap Pyrex bottle. The scope and limitations of this reaction are studied by employing variously substituted 11 internal alkynes. The reactions are regioselective with alkynes having a sterically crowded substituent such as t-butyl and trimethylsilyl groups. Moreover, racemic 1-(2-iodoferrocenyl)ethanol derivatives are synthesized as two diastereomers. Both diastereomers are reacted with internal alkynes in the presence of (dppf)PdCl₂ and i-Pr₂NH at 120 °C to afford alkenyl-substituted acetylferrocenes and ferroceno-pyrans in moderate to good yields. According to the alkyne employed, different reaction times (between 6 and 55 h) are necessary to drive the reactions to completion. Mechanisms are also suggested for the formation of observed products.

Full text of DOI:10.1016/j.jorganchem.2012.01.007

Journal of Organometallic Chemistry 704 (2012) 49e64
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Journal of Organometallic Chemistry
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Palladium-catalyzed reaction of 2-iodoferrocenyl alcohols with internal alkynes:
Synthesis of functionally 1,2-disubstituted ferrocenes and ferroceno-pyrans
*
Baris Yucel , Bahar Sanli, Huseyin Soylemez, Huseyin Akbulut
Istanbul Technical University, Department of Chemistry, 34469 Maslak, Istanbul, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of racemic (2-iodoferrocenyl)methanol with internal alkynes in the presence of (dppf)PdCl2
and i-Pr2NH produces alkenyl-substituted ferrocene carboxaldehydes in moderate yields. All reactions
are carried out at 100 or 120 ꢀC for different reaction times (between 6 and 26 h) in a screw-cap Pyrex
bottle. The scope and limitations of this reaction are studied by employing variously substituted 11
internal alkynes. The reactions are regioselective with alkynes having a sterically crowded substituent
such as t-butyl and trimethylsilyl groups. Moreover, racemic 1-(2-iodoferrocenyl)ethanol derivatives are
synthesized as two diastereomers. Both diastereomers are reacted with internal alkynes in the presence
of (dppf)PdCl2 and i-Pr2NH at 120 ꢀC to afford alkenyl-substituted acetylferrocenes and ferroceno-pyrans
in moderate to good yields. According to the alkyne employed, different reaction times (between 6 and
55 h) are necessary to drive the reactions to completion. Mechanisms are also suggested for the
formation of observed products.
Received 26 October 2011
Received in revised form
5 January 2012
Accepted 10 January 2012
Keywords:
1,2-Disubstituted ferrocene
Ferrocene carboxaldehyde
Ferroceno-pyran ferrocenyl alcohol
Ferrocenyl alkene
Ó 2012 Elsevier B.V. All rights reserved.
1. Introduction
diseases, for example, malaria [39e42]. Generally, enhanced bio-
logical activities have been achieved by replacement of an organic
In last two decades, ferrocene has emerged as a most remark-
able organometallic compound in various research areas because of
its intrinsic physical and chemical properties [1,2]. In materials
science, as an electron donor and redox active unit having thermal
and photochemical stability, ferrocene moieties are components of
electron transfer systems with electron acceptors as well as redox
active species [3e28]. Indispensable contributions to organic
synthesis have been provided by both achiral and chiral ferrocene-
containing ligands [1,2,29e32]. In numerous metal-catalyzed
organic transformations, achiral ferrocenyl phosphine ligands,
such as bidentate 1,10-bis(diphenylphosphino)ferrocene (dppf), are
extensively used [33]. Ferrocenyl phosphines involving central and
planer chirality have been successfully applied for catalytic enan-
tioselective processes in academia, and also in industry [1,2,29e32].
Moreover, ferrocene and its derivatives have been widely employed
in biorganometallic chemistry [34e36]. Their low acute mammal
toxicity, high resistance in aqueous aerobic conditions and biode-
gradability fulfill basic requirements for medicinal applications. As
a potential source of iron, ferrocene derivatives are promising drug
candidates for iron-related disorders [37,38] and infectious
moiety, mostly aryl derivatives, with ferrocene in already existing
biologically active compounds including antitumor agents [43e47],
antibiotics [48e50] and insecticides [51,52]. The well-defined
electrochemical properties of ferrocene play a pivotal role in
biological applications. The cytotoxic efficacy of ferrocene-
substituted hydroxytamoxifen analogs, hydroxyferrocifens, have
been explained via a proton-coupled electron transfer mechanism
involving the redox states (Fe2þ/Fe3þ) of the iron atom [53]. In
addition, numerous ferrocene-containing biomolecules such as
amino acids [35,54e57], peptides [35,58e62] proteins [63e66],
nucleobases [35,67], steroids [68,69] and lipids [70e72] have been
prepared and these bioconjugates of ferrocene were generally
used as electrochemical sensors in biological applications. There-
fore, the synthesis of new functionalized ferrocenes and ferrocenyl-
substituted carbo- and heterocyclic structures are currently
receiving considerable attention.
Most ferrocene-containing structures are prepared starting from
ferrocene derivatives having one or more functional substituents.
For example, ferrocifens [43e46] and ferrocenyl flavones [73] are
easily available from ferrocenyl ketones and aldehydes, respectively.
Ferrocenyl amines are building blocks for antimalarial agents fer-
rochloroquine [39] and ferrocenyl analogs of atovaquone [42].
Moreover, ferrocenyl alkynes and ferrocenyl alkenes are desired
structural motifs for ferrocene-based opto-electronic materials [4].
* Corresponding author. Tel.: þ90 212 2857021; fax: þ90 212 2856386.
E-mail address: yucelbar@itu.edu.tr (B. Yucel).
0022-328X/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2012.01.007

50
B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
Preparation of these simple, functionalized ferrocenes relies on
usual methodologies including VilsmeiereHaack formylation,
FriedeleCrafts acylation, and transmetallation [74e78]. Further-
more, syntheses of numerous ferrocene-containing structures have
been recently achieved by well-established methods based on
valuable building blocks; for instance, group 6 Fischer carbene
complexes and cyclobutenediones [27,79e82]. Application of these
methods with ferrocenyl-substituted starting materials has resulted
in formation of unexpected and desired ferrocene-containing
compounds together. The formation of the unexpected products
can be attributed to the non-benzenoic aromaticity and the
reversible oxidation states of ferrocene.
N(CH3)2
I
N(CH3)2
1) t-BuLi, THF
0 oC, 15 min.
Fe
Fe
2) I(CH2)I, THF
0 oC, 5 min
then,
3
4 (67%)
20 oC, 15 min
AcOH
Ac2O
Toluene
95 oC, 16 h
Recently, the palladium-catalyzed reactions of ortho-function-
alized aromatic halides with internal alkynes have been proven to
be one the most powerful method for the synthesis of heterocycles
such as indoles, indenones, benzofurans, isocoumarins and iso-
quinolines [83e86]. Surprisingly, this method has not been previ-
ously applied for readily accessible ortho-functionalized ferrocenyl
halides and internal alkynes. Thus, we anticipated that an extension
of the methodology in this manner would provide functionally
substituted and scarcely available heteroannulated ferrocenes.
Inspired by the pioneering studies of Larock and co-workers [87,88],
we investigated the palladium-catalyzed reactions of racemic
2-iodoferrocenyl alcohols 1 and 2 with internal alkynes, which
afforded ferrocenyl aldehydes and ketones containing differently
substituted alkenyl side chains and ferroceno-pyrans (Scheme 1). To
the best of our knowledge, difunctional ferrocene derivatives and
ferroceno-pyrans described here have not been reported before in
literature. Herein we present the full details of this study.
O
CH3
O
I
OH
I
NaOH (aq)
Fe
Fe
CH3OH, THF
65 oC, 2 h
1 (88%)
5 (84%)
Scheme 2. Three-step synthesis of racemic (2-iodoferrocenyl)methanol (1).
chosen as the model to explore the “optimal” reaction conditions.
Initially, we tested the conditions applied previously for the
palladium-catalyzed annulation of internal alkynes by various aryl
halides bearing a nucleophilic group in their ortho positions
[87,88,91,92]. It was reported that these annulation reactions
proceed in a regioselective manner and afford the heterocycles in
high yields under the catalytic conditions containing, in general,
Pd(OAc)2 or Pd(dba)2, solid ionic bases and chloride sources such as
LiCl and n-Bu4NCl. The most of the described annulation reactions
were carried out in DMF at temperatures of 80e120 ꢀC
[87,88,91,92]. The literature protocols also imply that the pres-
ence of a phosphine ligand in the catalytic cocktail was not always
essential for success [87,88,91,92]. We have employed analogous
conditions in our model reaction. In all attempts, Pd(OAc)2 (5 mol%)
was used with an excess amount of solid base (2.5 equivalents) such
as Na2CO3, K2CO3, NaOAc and KOAc in the presence of LiCl
(1.0 equivalent) or n-Bu4NCl (1.0 equivalent). Reactions were
carried out in DMF at different temperatures (80, 100, 120 and
140 ꢀC) for different reaction times (between 12 and 100 h) in
a screw-cap Pyrex bottle. The effect of the ligand (PPh3, 10 mol%)
was also tested. However, none of the tested conditions furnished
any products. We partially recovered diphenylacetylene (6a) used
in excess (3.0 equivalents) from the reaction mixtures. In all reac-
tions, ferrocenyl alcohol 1 slowly decomposed and the formation of
Pd black was observed. However, from several reactions, we iso-
lated a red oily mixture in very small quantities by a column
chromatography, and thus the substances in the mixture could not
be characterized.
2. Results and discussion
The synthesis of racemic (2-iodoferrocenyl)methanol (1) was
accomplished from N,N-dimethylaminomethylferrocene (3) in
three steps according to known or modified literature procedures
(Scheme 2) [89,90]. The key compound 2-(N,N-dimethylamino-
methyl)-iodoferrocene (4) was prepared by ortho-lithiation of 3
with t-BuLi and then addition of 1,2-diiodoethane [I(CH2)2I] in THF
via a “cannula” into the solution of initially formed lithiated
ferrocene. Under the same conditions, iodination with diiodo-
methane (CH2I2) and iodine (I2) gave lower yields (36% and 38%,
respectively). Iodoferrocene 4 was then heated in the mixture of
acetic anhydride, acetic acid and toluene to afford ferrocenyl
acetate 5 in 84% yield. In the third step, (2-iodoferrocenyl)methanol
(1) was obtained in 88% yield by alkaline hydrolysis of acetate 5.
We next investigated palladium-catalyzed reactions of racemic
2-iodoferrocenyl alcohol (1) with internal alkynes. The reaction
between diphenylacetylene (6a) and ferrocenyl alcohol 1 was
O
H
cat. Pd (0)
OH
R2
i-Pr2NH
I
We turned then our attention to the palladium-catalyzed reac-
tions of functionally substituted iodoferrocene derivatives in the
literature [93e95]. For example, inspired by the successful Sono-
gashira coupling reaction of 2-(N,N-dimethylaminomethyl)iodo-
ferrocene with terminal alkynes [96], we reasoned that similar
catalytic conditions might also be applicable for our purpose.
Therefore, 2-iodoferrocenyl alcohol 1 (1.00 mmol) and diphenyla-
cetylene (6a) (2.00 mmol) in diisopropylamine (7.00 mL) were
treated with (Ph3P)2PdCl2 (0.01 mmol) at 100 ꢀC for 24 h (Table 1,
entry 1). The reaction afforded ferrocenyl aldehyde 7a in 24% yield
R1
R1
R2
Fe
Fe
1
O
H3C
H3C
Fe
CH3
R1
cat. Pd (0)
i-Pr2NH
O
OH
I
R2
R2
+
R1
R1
R2
Fe
Fe
2
together with the unreacted 2-iodoferrocenyl alcohol
1 and
Scheme 1. Palladium-catalyzed reactions of racemic 2-iodoferrocenyl alcohols 1 and 2.
diphenylacetylene (6a). We also proved the configuration of

B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
51
Table 1
Palladium-catalyzed reaction of ferrocenyl alcohol 1 with diphenylacetylene (6a).
O
H
OH
Pd catalyst
Ph
i-Pr2NH
I
Fe
Fe
Ph
Ph
Ph
6a
1
7a
Entry
Pd catalyst
Time (h)
Temp. (ꢀC)
Yield of 7a (%)a
1
2
3
(Ph3P)2PdCl2 [0.01]
(Ph3P)2PdCl2 [0.01]
(Ph3P)2PdCl2 [0.01]
(Ph3P)2PdCl2 [0.01]
(Ph3P)2PdCl2 [0.01]
(Ph3P)2PdCl2 [0.03]
(Ph3P)2PdCl2 [0.03]
(Ph3P)2PdCl2 [0.03]
(Ph3P)2PdCl2 [0.03]
(Ph3P)2PdCl2 [0.05]
(dppf)PdCl2 [0.03]
(dppf)PdCl2 [0.03]
PdCl2 [0.05]
24
48
72
96
48
24
64
12
6
12
6
3
8
8
100
100
100
100
80
100
100
100
100
100
100
100
100
100
100
100
24
41
28
31
18
66
55
69
35
70
81
71
76
23
e
4
5b
6
7
8
9
10
11
12
13
14
15
16
Fig. 1. Structure of ferrocenyl aldehyde 7a in the crystal. The displacement ellipsoids
are drawn at 35% probability level [28]. C25H20FeO (392.26); crystal dimensions
0.12 ꢁ 0.48 ꢁ 0.60 mm3, wavelength ¼ 0.71073 Å, triclinic, a ¼ 8.2594 (5) Å, b ¼ 10.1119
(8) Å, c ¼ 12.1263 (17) Å,
a
¼ 100.246 (9)ꢀ,
b
¼ 102.421 (8)ꢀ,
g
¼ 98.185 (6)ꢀ, V ¼ 955.94
(16) nm3, space group ¼ Pꢂ1, Temp. ¼ 293 (2) K, absorption coefficient ¼ 0.8 mmꢂ1
, q
Pd(OAc)2 [0.05]
Pd(dba)2 [0.03]
Pd(PPh3)4 [0.05]
range for data collection ¼ 2.42e26.29ꢀ, reflection collected ¼ 3904, reflection used in
6
6
refinement
¼
3726, number of refined parameters
¼
248, absorption
e
correction ¼ semi-empirical, refinement method ¼ full matrix, R/Rw values ¼ 0.0536/
a
Isolated yields.
Triethylamine (Et3N) was used as base and solvent.
0.1466, Goodness-of-fit (F2) ¼ 0.963, final shift ¼ 0.0001, (Δ
r)
¼ 0.411 e Åꢂ3
,
min
b
(Δ
r)
¼ ꢂ0.354 e Åꢂ3
.
max
ferrocenyl aldehyde 7a by an X-ray crystal structure analysis (Fig. 1)
[97]. We next decided to increase the reaction time to obtain fer-
rocenyl aldehyde 7a in a higher yield. After 48 h, the reaction
produced ferrocenyl aldehyde 7a in 41% yield (Table 1, entry 2), but
the prolonged reaction times (72 h and 96 h) gave the product in
lower yields (Table 1, entries 3 and 4). When triethylamine (Et3N)
was used as base and solvent at 80 ꢀC for 48 h, ferrocenyl aldehyde
7a was isolated, albeit in only 18% yield (Table 1, entry 5). When we
increased the amount of (Ph3P)2PdCl2 to 0.03 mmol, the reaction
afforded the product (7a) in 66% yield in 24 h at 100 ꢀC (Table 1,
Table 2
The palladium-catalyzed reaction of 2-iodoferrocenyl alcohol 1 with internal alkynes (6ael).
O
O
H
H
OH
I
(dppf)PdCl2
i-PrN2H
R1
R2
+
R2
R1
Fe
Fe
Fe
R1
R2
6b–l
7b2–l2
1
7b1–l1
(B)
(A)
Entry
Alkyne 6bel
R1
R2
Time (h)
Temp. (ꢀC)
Product
Yield (%)a
A:Bb
1c
2
3
6b
6b
6c
6c
6d
6e
6f
CH(OC2H5)2
CH(OC2H5)2
Ph
Ph
CH3
CH3
CH3
CH3
C(CH3)]CH2
C(CH3)]CH2
CH3
CO2C2H5
HCO
Ph
Ph
Si(CH3)3
Si(CH3)3
Ph
Si(CH3)3
C(CH3)3
C(CH3)3
C2H5
C2H5
C2H5
Ph
Ph
6
6
6
6
6
22
22
22
26
7.5
6
7.5
3
3
100
100
100
120
120
100
100
120
100
120
100
120
120
120
7b1 þ 7b2
32
46
30
34
23
30
16
31
32
48
e
1:1
1.9:1
e
7b1 þ 7b2
7c1
7c1
7d1
7e1
7f1
7f1
4
e
5d
6
e
e
7
8
9
10
11
12
13
14
e
6f
e
6g
6g
6h
6i
6k
6l
7g1 þ 7g2
1:5
1:3.5
e
7g1 þ 7g2
e
e
e
e
e
e
e
e
CH2OH
CH3
e
e
a
Isolated yields.
The ratio of regioisomers according to the isolated yields.
2.0 mmol 6b was used.
This reaction gave also ferrocenyl aldehyde 8d (16%) (See Scheme 3).
b
c
d

52
B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
ferrocenyl aldehyde 7a in 81% yield only in 6 h and ferrocenyl alcohol
Ph
O
O
1 had been completely consumed at the end of the reaction (Table 1,
entry 11). The shorter reaction time (3 h) was not enough for the total
conversion of ferrocenyl alcohol 1 (Table 1, entry 12). PdCl2 was also
an effective palladium catalyst, yet the reaction mixture had to be
heated for 8 h to drive the reaction to completion (Table 1, entry 13).
When the reaction was carried out in the presence of Pd(OAc)2,
ferrocenyl aldehyde 7a was obtained in only 23% yield and we did
not detected ferrocenyl alcohol 1 after a 8 h reaction time (Table 1,
entry 14). On the other hand, Pd(dba)2 and Pd(PPh3)4 were
completely ineffective in this reaction (Table 1, entries 15 and 16).
We next studied the scope and limitations of this methodology
by allowing a variety of internal alkynes (6bel) to react with fer-
rocenyl alcohol 1 under the optimized reaction conditions. The
results are summarized in Table 2.
The use of 2.0 equivalents (2.0 mmol) of unsymmetrical alkyne
(phenylpropargyl aldehyde diethyl acetal, 6b) produced two
regioisomeric ferrocenyl aldehyde derivatives 7b1 and 7b2 in a 1:1
ratio in 32% yield at 100 ꢀC for 6 h (Table 2, entry 1). The
regioisomers 7b1 and 7b2 are separated by a column chromatog-
raphy and easily identified by comparison of their 1H NMR spectra.
However, using the same conditions, the use of 4.0 equivalents
CH3
CH3
H
H
OH
I
(dppf)PdCl2
i-Pr2NH
120 oC, 6 h
Ph
+
Fe
Fe
Fe
Ph
CH3
H3C
Ph
1
6d
7d1 (23%)
8d (16%)
Scheme 3. Palladium-catalyzed reaction of ferrocenyl alcohol 1 with 1-phenyl-1-
propyne (6d).
entry 6). The same catalytic system was allowed to react at the
same temperature for 64 h, the yield of ferrocenyl aldehyde 7a
decreased to 55% (Table 1, entry 7). When the same reaction was
carried out at 100 ꢀC for 12 h, ferrocenyl aldehyde 7a was obtained
in 69% yield (Table 1, entry 8). On the other hand, the shorter
reaction time (6 h) dramatically lowered the yield to 35% (Table 1,
entry 9). Further addition of (Ph3P)2PdCl2 (0.05 mmol) did not have
a strong effect on the reaction yield (Table 1, entry 10).
We next examined the effect of different palladium catalysts on
the model reaction. The use of (dppf)PdCl2 (0.03 mmol) furnished
Ph
Pd
O
CH3
CH3
Ph
HPd
Ph
O
CH3
CH3
H
Fe
14d
O
Ph
HI
CH3
CH3
H
Fe
Ph
Fe
Ph
15d
Ph
IPd
8d
HO
CH3
CH3
Pd(0)
OH
I
Fe
Ph
Fe
13d
O
1
OH
PdI
H
OH
Fe
Ph
PdI
H3C
Ph
Pd(0)
Fe
7d1
CH3
6d
9
CH3
Fe
Ph
10d2
H3C
OH
Ph
H
6d
O
PdH
Ph
PdI
Ph
Fe
CH3
Fe
10d1
CH3
12d1
O
Pd
Ph
Fe
11d1
CH3
HI
Scheme 4. Proposed catalytic cycles for the formation of 7d1 and 8d.

B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
53
(4.0 mmol) of alkyne 6b increased the reaction yield to 46% and 7b1
was isolated as a major regioisomer (Table 2, entry 2). Thus, for
further reactions of ferrocenyl alcohol 1, 4.0 equivalents of internal
alkynes (6cel) were employed.
When we employed 1-phenyl-2-trimethylsilylacetylene (6c),
only one regioisomer (7c1) was isolated in 30% yield (Table 2,
entry 3). The regiochemistry of product 7c1 was assigned by a 2-D
NOESY experiment. The NOESY spectrum of 7c1 exhibited interac-
tions between phenyl hydrogens and the hydrogens of both
cyclopentadiene rings in the ferrocenyl moiety. On the other hand,
an interaction between trimethylsilyl group and ferrocenyl hydro-
gens was not observed. When the same reaction was carried out at
120 ꢀC for 6 h, product 7c1 was achieved in slightly higher (34%)
yield (Table 2, entry 4).
The reaction carried out with 1-phenyl-1-propyne (6d) afforded
two products. The major product ferrocenyl aldehyde derivative
7d1 was isolated in 23% yield and its configuration was easily
described by 1H NMR spectroscopy (Table 2, entry 5). The minor
product 8d (16% yield) formed via two subsequent insertions of
1-phenyl-1-propyne (6d) was quite unstable (Scheme 3) [98].
Although we isolated compound 8d in 16% yield, we were not
able to fully characterize it. For the characterization of 8d, we used
only 1H NMR, IR and high-resolution MS spectra. Unfortunately,
a good-quality 13C NMR spectrum of 8d could not be achieved
O
H3C
Fe
H3C
H3C
CH3
O
OH
O
Ac2O
LiAlH4
Et2O
0 oC, 3 h
DMAP, NEt3
Fe
Fe
20 oC, 17 h
18 (93%)
HN(CH3)2
16
17 (97%)
CH3OH
20 oC, 19 h
O
H3C
Fe
H3C
H3C
CH3
1) sec-BuLi
O
I
N(CH3)2
I
N(CH3)2
Et2O
Ac2O
DMAP, NEt3
0 oC, 3 h
Fe
Fe
19 (93%)
40 oC, 48 h
2) I2, Et2O
0 oC, 15 min.
then,
20 (62%)
21-I (76%)
20 oC, 1 h
Ac2O, AcOH
NaOH (aq)
Toluene
THF, MeOH
80 oC, 5 h
20 oC, 5 h
O
H3C
H3C
Fe
CH3
OH
I
O
I
Fe
2-
21-
I
(52%) + 21-II (34%)
I
(95%)
O
H3C
H3C
OH
CH3
O
I
NaOH (aq)
I
THF, MeOH
20 oC, 5 h
Fe
Fe
21-II
2-II (90%)
Scheme 5. Synthesis of 1-(2-iodoferrocenyl)ethanol derivatives (2-I and 2-II) as two separable diastereomers.

54
B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
reaction mixture by TLC. Thus, the reaction had to be carried out at
O
H3C
Fe
120 ꢀC for 22 h to drive it to completion (Table 2, entry 8).
The reaction carried out with 2-methyl-1-hexen-3-yne (6g)
produced two regioisomers 7g1 and 7g2 in a 1:5 ratio and in 32%
yield at 100 ꢀC for 26 h (Table 2, entry 9). The stereochemistry of
regioisomers 7g1 and 7g2 was easily determined by comparison of
CH3
Ph
OH
I
(dppf)PdCl2
i-Pr2NH
100 oC, 6 h
Ph
Ph
Fe
Ph
Ph
6a
2-I
1
their H NMR spectra. When the same reaction was run at 120 ꢀC
22a (88%)
for 7.5 h, the regioisomers were isolated in 48% yield, but in a 1:3.5
ratio (Table 2, entry 10).
O
H3C
H3C
Fe
CH3
The reaction of unhindered 2-pentyne (6h) gave a highly
complex mixture at 100 ꢀC for 6 h (Table 2, entry 11). According to
the 1H NMR spectrum, the mixture contains two ferrocenyl alde-
hyde derivatives formed most likely by multi-insertion of alkyne
6h. However, these two products could not be separated from each
other and isolated in a pure form.
(dppf)PdCl2
i-Pr2NH
120 oC, 6 h
O
OH
I
Ph
+
Fe
Fe
22a (27%)
Ph
Ph
Ph
Ph
6a
23a (43%)
2-II
Furthermore, the use of ethyl phenylpropiolate (6i) afforded an
inseparable mixture of two products (Table 2, entry 12). One of the
products was assigned as a ferrocenyl aldehyde derivative (7i1 or
7i2) by 1H NMR spectrum of the isolated mixture. The spectrum
shows clearly the aldehyde and the methine hydrogens as singlet at
9.64 and 6.46 ppm, respectively. Methyl hydrogens appear at
1.09 ppm as triplet and methylene hydrogens at 4.00 ppm as quartet.
Moreover, the peaks of phenyl group are observed in the aromatic
region. Unfortunately, all attempts to isolate ferrocenyl aldehyde
(7i1 or 7i2) in a pure form by column chromatography were not
successful. Thus, the full spectral characterization and the stereo-
chemistry of ferrocenyl aldehyde (7i1 or 7i2) could not be achieved.
The reactions of 2-iodoferrocenyl alcohol 1 with phenyl-
propargyl aldehyde (6k) and 2-butyn-1-ol (6l) failed to give any
product (Table 2, entry 13 and 14). At the end of the reactions,
ferrocenyl alcohol 1 was not present in the reaction mixtures. The
isolated fractions from the crude mixtures could not be identified,
and in none of the fractions the desired ferrocenyl aldehyde
derivatives could be detected by NMR spectroscopy.
Scheme 6. Palladium-catalyzed reactions of ferrocenyl alcohols 2-I and 2-II with
diphenylacetylene (6a).
because of rapid decomposition of the compound. However, the 1H
NMR spectrum of the compound clearly shows hydrogens of
methyl groups as two singlets at 1.68 and 1.77 ppm and the
methine proton as a singlet at 6.15 ppm [99]. Ferrocenyl hydrogens
appear as four singlets at 3.76 (for the unsubstituted ring), 4.47,
4.62 and 4.80 ppm. Moreover, two phenyl groups appear as broad
multiplets between 6.98 and 7.53 ppm and the aldehyde proton is
clearly observed at 10.07 ppm. The suggested mechanism for the
formation of this compound (8d) will be discussed later.
Similarly, the reaction between ferrocenyl alcohol 1 and 1-(tri-
methylsilyl)propyne (6e) furnished two products, yet only the
major one (7e1) could be isolated in pure form (Table 2, entry 6).
The unstable minor product was most likely the double insertion
product of the alkyne 6e according to 1H NMR spectrum of the
crude sample. In this case, the reaction was rather slow, reaching
completion within 22 h.
Therefore, these results imply that the palladium-catalyzed
reactions of racemic 2-iodoferrocenyl alcohol 1 with a wide
variety of alkynes (6ael) produce ferrocenyl aldehydes (7a, 7b1eg1
and 7b2, 7g2) bearing an alkenyl side chain in moderate yields. The
reactions are regioselective when, particularly, one of the
The reaction of ferrocenyl alcohol 1 with 4,4-dimethyl-2-
pentyne (6f) was completely regioselective and gave ferrocenyl
aldehyde derivative 7f1, albeit in 16% yield (Table 2, entry 7). At the
end of the reaction time (22 h), we detected starting alcohol 1 in the
Table 3
Palladium-catalyzed reactions of ferrocenyl alcohols 2-I and 2-II with internal alkynes 6b,c, 6eef.
O
O
H3C
Fe
H3C
Fe
CH3
R2
CH3
R1
O
OH
I
(dppf)PdCl2
i-Pr2NH
R1
R2
R2
+
R1
Fe
Fe
R1
R2
6b–c,
6e–f
2-
I
22b1–c1
22e1–f1
(A)
,
22b2
23c, f
or
2-II
(C)
(B)
Entry
Alcohol
Alkyne
R1
R2
Time (h)
Temp. (ꢀC)
Product
Yield (%)a
A:B:Cb
1
2-I
2-I
2-I
2-I
2-II
2-II
6b
6c
6e
6f
6c
6f
CH(OC2H5)2
Ph
CH3
CH3
Ph
Ph
6
46
24
6
55
6
120
120
120
120
120
120
22b1 þ 22b2
22c1
50
42
13
65
70
74
(A:B) 3:1
e
2
Si(CH3)3
Si(CH3)3
C(CH3)3
Si(CH3)3
C(CH3)3
3c
4
22e1
e
22f1 þ 23fId
(A:C) 2.2:1
(A:C) 1:1.6
(A:C) 1:2.4
5
6
22c1 D 23c
22f1 þ 23fII
d
CH3
a
Isolated yields.
The ratio of products according to the isolated yields.
This reaction gave also compounds 24e (13%) and 25e (7%) (See Scheme 7).
Ferroceno-pyrans 23fI and 23fII are diastereomers.
b
c
d

B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
55
H3C
Fe
(dppf)PdCl2
i-Pr2NH
120 oC, 24 h
OH
I
(H3C)3Si
CH3
2-
I
6e
CH3
O
H3C
Fe
O
CH3
OH
CH3
CH3
Si(CH3)3
Si(CH3)3
Si(CH3)3
Si(CH3)3
Fe
+
Fe
+
CH3
CH3
22e1 (13%)
24e (13%)
25e (7%)
Scheme 7. Palladium-catalyzed reaction of 2-I and 6e.
substituents of the alkyne is sterically highly encumbered, for
example the alkynes with t-butyl and trimethylsilyl substituents.
Based on the results presented here and previously reported
studies [83e88], we proposed a mechanism for the palladium-
catalyzed reaction of racemic 2-iodoferrocenyl alcohol (1) with
internal alkynes such as 1-phenyl-1-propyne (6d). A possible
mechanism for the formation of products 7d1 and 8d is depicted in
Scheme 4. First, oxidative addition of 2-iodoferrocenyl alcohol 1 to
the actual catalyst Pd(0) formed by reduction of the pre-catalyst
[(dppf)PdCl2] gives a ferrocenylpalladium complex 9. We believe
that the syn-insertion of 1-phenyl-1-propyne (6d) into the ferro-
cenylpalladium bond does not proceed regioselectively, and thus
two regioisomeric vinylic palladium intermediates (10d1 and 10d2)
are formed. Intramolecular nucleophilic attack on the palladium
center by the hydroxyl group in 10d1 produces a seven-membered
diastereomer in 76% yield. In the second procedure, iodoamine 20
was heated in a mixture of acetic anhydride, acetic acid and toluene
at 80 ꢀC for 5 h, yet the reaction produced a mixture of diastereo-
mers 21-I and 21-II in 52% and 34% isolated yields, respectively.
Finally, each diastereomer (21-I and 21-II) was hydrolyzed under
the same conditions to obtain 1-(2-iodoferrocenyl)ethanol as two
diastereomers 2-I and 2-II in high yields.
These two 2-iodoferrocenyl alcohols (2-I and 2-II) were reacted
with diphenylacetylene (6a) under the already optimized reaction
conditions (Scheme 6). The reaction of the major diastereomer 2-I
produced only ferrocenyl ketone derivative 22a in 88% yield. On the
other hand, the reaction of diastereomer 2-II gave ferrocenyl
ketone 22a and ferroceno-pyran 23a derivatives in 10% and 30%
isolated yields, respectively. When the same reaction was carried
out at 120 ꢀC for 6 h, the yields of ferrocenyl ketone 22a and
ferroceno-pyran 23a increased to 27% and 43% respectively. The
formation of ferrocenyl pyran 23a can be attributed to a reductive
elimination process which occurs in a seven-membered pallada-
cycle of type 11d1 (see Scheme 4).
To extend the scope of this method even further, we studied the
reaction of ferrocenyl alcohols 2-I and 2-II with different internal
alkynes under the optimized reaction conditions (Table 3). The
reaction of ferrocenyl alcohol 2-I with phenylpropargyl aldehyde
diethyl acetal (6b), gave acetylferrocene derivatives 22b1 and 22b2
as two regioisomers in 50% yield at 120 ꢀC for 6 h (Table 3, entry 1).
These regioisomers (22b1 and 22b2) could be separated by
a column chromatography and easily identified by comparison of
their 1H NMR spectra. The use of sterically hindered 1-phenyl-2-
trimethylsilylacetylene (6c) produced only one product 22c1 in
42% yield at 120 ꢀC, yet the prolonged reaction time (46 h) was
necessary (Table 3, entry 2).
palladacycle 11d1. Next, the palladacyle undergoes a b-hydrogen
elimination to yield a palladium hydride complex 12d1, which
affords product 7d1 and regenerates Pd(0) by reductive elimination.
On the other hand, the vinylic palladium intermediate 10d2 gives
complex 13d via the second insertion of alkyne 6d. Then, the
displacement of the iodide by the nucleophilic attack of the hydroxyl
moiety produces nine-membered cyclopalladated complex 14d.
(Previously, ferrocene-containing nine-membered palladacycles
were reported [98,100e103]). After a b-hydrogen elimination in the
palladacycle 14d, complex 15d undergoes reductive elimination to
furnish ferrocenyl aldehyde derivative 8d as a second product of the
reaction and regenerates the Pd(0) catalyst.
We next synthesized racemic 1-(2-iodoferrocenyl)ethanol
derivatives as two separable diastereomers 2-I and 2-II starting
from acetylferrocene (16) [104] in six steps according to known or
modified literature procedures (Scheme 5) [104e108]. Firstly, ace-
tylferrocene (16) was reduced to ferrocenylethanol 17 by LiAlH4,
and then the esterification of alcohol 17 with acetic anhydride
produced acetate 18 quantitatively. The reaction of acetate 18 with
dimethylamine in methanol at room temperature for 19 h gave N,N-
dimethylaminoethylferrocene (19) in 93% yield. The key compound
2-(N,N-dimethylaminoethyl)iodoferrocene (20) was obtained as an
only diastereomer in 62% yield by ortho-lithiation of 19 with sec-
BuLi followed by iodination. Iodoamine 20 was converted to
acetates 21-I and 21-II via two different procedures. In the first
procedure, iodoamine 20 was reacted with acetic anhydride in the
presence of triethylamine and DMAP (4-dimethylaminopyridine) at
40 ꢀC for 48 h and the reaction furnished acetate 21-I as a single
The reaction of diastereomer 2-I with 1-(trimethylsilyl)propyne
(6e) afforded a mixture of three products 22e1, 24e and 25e
H3C
OH
H3C
OH
PdI
Si(CH3)3
Si(CH3)3
HI
Fe
Fe
26e
−PdI2
CH3
CH3
25e
Scheme 8. The formation of compound 25e by protonation.

56
B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
O
H3C
Fe
CH3
H3C
CH3
OH
I
OH
I
I
MnO2
CH3MgBr
(eq.1)
(eq.2)
Fe
Fe
Benzene
50 oC, 24 h
THF
0 oC, 3 h
27 (63%)
28 (39%)
2-
I
CH3
H3C
CH3
CH3
O
H3C
H3C
OH
(dppf)PdCl2
i-PrN2H
120 oC, 6 h
OH
I
Ph
Ph
+
Fe
Fe
Fe
29a (44%)
Ph
Ph
Ph
Ph
6a
28
30a (26%)
Scheme 9. Synthesis of ferrocenyl alcohol 28 (Eq. (1)) and the palladium-catalyzed reaction of alcohol 28 with diphenylacetylene (6a) (Eq. (2)).
(Table 3, entry 3). These products were separated by a column
chromatography and identified by NMR, IR and high-resolution MS
spectroscopies (Scheme 7).
alcohol 2-I and 4,4-dimethyl-2-pentyne (6f) (Table 3, entry 4),
ferroceno-pyran 23fII was isolated as a major product in this
reaction. 1H NMR and 13C NMR spectra of both ferroceno-pyran
derivatives (23fI and 23fII) clearly show that these two
compounds are diastereomers.
The acetylferrocene derivative 22e1 was isolated in 13% yield
and its configuration was easily assigned by its 1H NMR spectrum.
The second product (24e) formed by two subsequent insertion of 1-
(trimethylsilyl)propyne (6e) was rather unstable. We observed that
compound 24e undergoes desilylation process and then decom-
poses to unidentified fragments when it was stored even under N2
atmosphere in the freezer. However, it could be isolated in 13% yield
and then characterized by 1H NMR and high-resolution MS spectra.
The third product (25e) of the reaction was most probably formed
by protonation of the intermediate complex 26e by HI and isolated
in 7% yield (Scheme 8) [109,110].
The reaction carried out with ferrocenyl alcohol 2-I and
4,4-dimethyl-2-pentyne (6f) gave a mixture of acetylferrocene 22f1
and ferroceno-pyran 23fI derivatives in a 2.2:1 ratio and 65% iso-
lated yield at 120 ꢀC for 6 h (Table 3, entry 4). Although, in the
reaction mixture, we have also determined a protonation product
similar to the compound 25e, we could not isolate it in a pure form,
and thus the compound could not be fully characterized.
The reaction accomplished by the second diastereomer of the
ferrocenyl alcohol 2-II and1-phenyl-2-trimethylsilylacetylene (6c)
produced a 1:1.6 mixture of acetylferrocene derivative 22c1 and
ferroceno-pyran 23c in 70% yield (Table 3, entry 5). The reaction
was very slow and the catalytic mixture had to be heated at 120 ꢀC
for 55 h to drive the reaction to completion.
Furthermore, the reaction of ferrocenyl alcohol 2-II and
4,4-dimethyl-2-pentyne (6f) produce a mixture of acetylferrocene
22f1 and ferroceno-pyran 23fII derivatives in 74% total yield at
120 ꢀC for 6 h (Table 3, entry 6). Unlike the reaction of ferrocenyl
We next prepared ferrocenyl alcohol 28 in hopes that the
reactions of this alcohol with internal alkynes would give only
corresponding ferroceno-pyran derivatives. The ferrocenyl alcohol
(28) was synthesized in two steps starting from ferrocenyl alcohol
2-I (Scheme 9, Eq. (1)). Firstly, the alcohol 2-I was oxidized by MnO2
in benzene at 50 ꢀC to the racemic o-iodo acetylferrocene (27) in
63% yield. In the second step, acetylferrocene 27 was reacted with
MeMgBr in THF at 0 ꢀC for 3 h to afford desired ferrocenyl alcohol 28
in 39% yield. The reaction of ferrocenyl alcohol 28 with dipheny-
lacetylene (6a) under the optimized reaction conditions produced
a mixture of alkenyl substituted ferrocenyl alcohol 29a and
ferroceno-pyran 30a in 44 and 26% isolated yields respectively
(Scheme 9, Eq. (2)).
Finally, to add another dimension to this study, we attempted
the reaction of racemic 2-iodoferrocenyl alcohol 1 and dipheny-
lacetylene (6a) in the presence of CO under our standard condi-
tions (Scheme 10) [111,112]. We used 2.0 equivalents of Mo(CO)6 as
a CO source and the reaction was carried out in a screw-cap Pyrex
bottle at 100 ꢀC for 6 h. At the end of the reaction, only five-
membered ferrocenyl lactone 31 was isolated in 80% yield. The
other possible product, seven-membered ferrocenyl lactone 32,
was not determined in the reaction mixture. Therefore, this result
implies that the insertion of CO into the carbonepalladium bond in
the complex 9 (see Scheme 4) is faster than that of diphenylace-
tylene (6a) into the same bond. Interestingly, we also noticed that
diphenylacetylene (6a) is essential for the success of the reaction.
When the same reaction was attempted without diphenylacety-
lene (6a), the five-membered lactone 31 was obtained in only 17%
yield.
O
O
O
(dppf)PdCl2
i-Pr2NH
Mo(CO)6
OH
I
O
Ph
+
3. Conclusions
Fe
Fe
32 (0%)
Fe
31 (80%)
Ph
100 oC, 6 h
We have investigated the palladium-catalyzed reactions of
racemic 2-iodoferrocenyl alcohols with various internal alkynes,
producing functionally 1,2-disubstituted ferrocenes and ferroceno-
pyrans in moderate to good yields. The reactions are regiose-
lective when sterically hindered alkynes are employed. Moreover,
1
Ph
Ph
6a
Scheme 10. Palladium-catalyzed reaction of ferrocenyl alcohol 1 with diphenylace-
tylene (6a) in the presence of Mo(CO)6.

B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
57
methyl-substituted internal alkynes are prone to undergo two
subsequent insertion processes, affording highly unstable ferrocenyl
dienes. In a few reactions, alkenyl-substituted ferrocenyl alcohols
have been formed via protonation of intermediate alkenyl palla-
dium complexes. Altogether these results imply that under the
appropriate conditions the palladium-catalyzed reaction of
2-iodoferrocenyl alcohols with internal alkynes is valuable synthetic
approach to functionally substituted ferrocenes and hardly acces-
sible ferroceno-pyrans.
4.2.2. 2-Acetoxymethyl-1-iodoferrocene (5)
To a solution of 2-(N,N-dimethylaminomethyl)-1-iodoferrocene
(4, 2.71 g, 7.34 mmol) in toluene (8 mL) at room temperature, acetic
anhydride (16 mL) and acetic acid (8 mL) were added. The resulting
solution was stirred at 95 ꢀC for 16 h. Then, the solution was
concentrated in a rotary evaporator and the remaining reddish-
brown oil residue was subjected to the chromatography on silica
gel using 1:1 (ethyl acetate:hexane) as eluent to yield 5 (2.38 g, 84%,
orange oil). The physical and spectroscopic data are in agreement
with those reported previously for this compound [107,113].
4. Experimental
4.2.3. (2-Iodoferrocenyl)methanol (1)
4.1. General
To a methanol (65 mL)-THF (135 mL) solution of 2-
acetoxymethyl-1-iodoferrocene (5, 4.73 g, 12.3 mmol), NaOH
(2.83 g) and H2O (135 mL) were added. The resulting solution was
stirred at 65 ꢀC for 2 h. After then, the solution was cooled to room
temperature and diluted with ether (200 mL) and the organic layer
was separated. The aqueous layer was extracted with ether
(2 ꢁ 100 mL). The combined organic layers were dried over Na2SO4
and filtered. The solution concentrated in a rotary evaporator and
the remaining orange residue was subjected to the chromatography
on silica gel using 1:1 (ethyl acetate:hexane) as eluent to yield 1
(3.70 g, 88%, yellow solid). Mp 84e85 ꢀC, Rf ¼ 0.33 (4:1, hex-
All reagents were used as purchased from commercial suppliers
without further purification unless otherwise indicated. Diethyl
ether and THF were freshly distilled from sodium/benzophenone
ketyl. Solvents for column chromatography, ethyl acetate and
hexane, were distilled in a rotary evaporator. Chromatographic
separations were performed with Merck Silica 60 (200e400 or
70e230 mesh). TLC was performed with Merck TLC Silicagel60 F254
plates, detection was under UV light at 254 nm. NMR spectra were
recorded with a Bruker AM 250 (250 MHz for 1H and 62.9 MHz for
13C NMR),
(400 MHz for 1H and 100.59 MHz for 13C NMR) instruments.
Chemical shifts were given in ppm relative to residual peaks of
a
Bruker Spectrospin Avance DPX400 Ultrashield
ane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
d
¼ 1.64 (bs, 1H, OH),
4.17 (s, 5H, Fc), 4.24 (t, J ¼ 2.3 Hz,1H, Fc), 4.32 (bs, 1H, Fc), 4.35e4.53
d
(AB system, dA ¼ 4.51, dB ¼ 4.31, JAB ¼ 13.0 Hz, 2H, CH2), 4.48 (bs, 1H,
deuterated solvents and coupling constants, J, were given in Hertz.
The following abbreviations are used to describe spin multiplicities
in 1H NMR spectra: s ¼ singlet; bs ¼ broad singlet; d ¼ doublet;
t ¼ triplet; q ¼ quartet; dd ¼ doublet of doublets; m ¼ multiplets.
Multiplicities in 13C NMR spectra were determined by DEPT (Dis-
tortionless Enhancement by Polarization Transfer) or APT (Attached
Proton Test) measurements and were given as (Cquat, CH, CH2, CH3).
IR spectra were recorded on a NICOLET 6700 FT IR spectrometer.
Band intensities were reported relative to the most intense band
and were listed as: br (broad), vs (very strong), s (strong), m
(medium), w (weak), vw (very weak). Low resolution mass spectra
(APIeES, 70 eV, and APCI) were obtained on an Agilent 1100 LC-MS
instrument equipped with a diode array UVevisible range detector
and Thermo LCQ Deca Ion Trap Mass Spectrometer (Thermo Fin-
nigan). High-resolution mass spectra (HRMS) were obtained on
a Waters Synapt Q-TOF-MS spectrometer.
Fc); 13C NMR (62.9 MHz CDCl3, DEPT)
67.70 (CH, Fc), 69.03 (CH, Fc), 71.32 (5ꢁ CH, Fc), 75.06 (CH, Fc), 88.26
(Cquat). The physical and spectroscopic data are in agreement with
also those reported previously for this compound [107,113].
d
¼ 43.74 (Cquat), 61.31 (CH2),
4.2.4. 2-[(E)-1,2-Diphenylvinyl]ferrocenecarboxaldehyde (7a)
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(1,1.00 mmol, 342 mg), diphenylacetylene (6a, 2.00 mmol, 357 mg),
(dppf)PdCl2(0.03 mmol, 24.48 mg) and i-Pr2NH (7 mL). Nitrogen
was bubbled through the mixture for 2 min and the bottle was
tightly closed. The mixture was stirred at 100 ꢀC for 6 h. After
cooling to room temperature, the mixture was concentrated in
a rotary evaporator and the remaining residue was subjected to the
chromatography on silica gel using 4:1 (hexane:ethyl acetate) as
eluent to yield 7a (316 mg, 81%, red solid). Mp 84e85 ꢀC, Rf ¼ 0.33
(4:1, hexane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
d
¼ 4.23
(s, 5H, Fc), 4.57 (s, 1H, Fc), 4.67 (s, 1H, Fc), 4.99 (s, 1H, Fc), 6.98e7.36
4.2. Procedures
(m, 11H, Ph, CH); 9.94 (s, 1H, Ald.) 13C NMR (62.9 MHz, CDCl3, DEPT)
d
¼ 68.44 (CH, Fc), 71.03 (5ꢁ CH, Fc), 71.90 (CH, Fc), 74.79 (CH, Fc),
4.2.1. 2-(N,N-Dimethylaminomethyl)-1-iodoferrocene (4)
76.87 (Cquat, Fc), 95.35 (Cquat, Fc), 126.88 (CH), 127.59 (CH), 128.00
(2ꢁ CH, Ph), 128.66 (2ꢁ CH, Ph), 129.20 (4ꢁ CH, Ph), 130.70 (CH),
136.50 (Cquat), 137.49 (Cquat), 140.57 (Cquat), 192.44 (CH, Ald.); IR
To
a solution of dimethylaminomethylferrocene (3.00 g,
12.33 mmol, 1.18 equivalents) in THF (20 mL) at 0 ꢀC under
a nitrogen atmosphere, t-BuLi (6.15 mL of a 1.7 M of pentane
solution, 10.45 mmol, 1.0 equivalents) was added dropwise via
a syringe over 10 min. The resulting red solution was stirred at 0 ꢀC
for 15 min and a THF (10 mL) solution of 1,2-diiodoethane (I(CH2)2I,
4.35 g, 11.0 mmol, 1.05 equivalents) was added via cannula. After
stirring firstly at 0 ꢀC for 5 min and then at room temperature for
additional 15 min, the resulting solution was quenched by addition
of 10% Na2S2O3 (50 mL) solution. The mixture was extracted with
ether (100 mL) and the organic layer was separated. The aqueous
layer was washed with ether (2 ꢁ 50 mL). The combined organic
layers were dried over Na2SO4 and filtered. The solution was
concentrated in a rotary evaporator and the remaining reddish-
brown oil residue was subjected to the chromatography on silica
gel using 10:10:1 (ethyl acetate:hexane:triethylamine) as eluent to
yield 4 (2.60 g, 67%, dark red oil). The physical and spectroscopic
data are in agreement with those reported previously for this
compound [90,96].
(ATR):
n
¼ 3080.5, 3016.1, 2956.8, 2922.5, 2847.2, 1725.3, 1654.5,
1596.5, 1489.7, 1427.2, 1262.9, 1213.0, 1105.3, 1037.1, 1026.4, 937.5,
838.2, 772.4, 713.2, 693.7; MS (APCI), m/z (%): 393.20 (100)
[Mþ þ H], 375.33 (23), 365.20 (10), 255.47 (24). HRMS [TOF MS
ESþ]: m/z [Mþ þ Na] calc. For C25H20FeONa 415.0761, found
415.0757 (ꢂ1.0 ppm).
4.2.5. 2-[(Z)-3,3-Diethoxy-1-phenylprop-1-en-2-yl]ferrocenecar-
boxaldehyde (7b1) and 2-[(E)-3,3-diethoxy-1-phenylprop-1-en-1-
yl]ferrocenecarboxaldehyde (7b2)
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(1, 1.00 mmol, 342 mg), phenylpropiolaldehyde diethyl acetal
(6b, 4.00 mmol, 817 mg), (dppf)PdCl2 (0.03 mmol, 24.48 mg) and
i-Pr2NH (7 mL). Nitrogen was bubbled through the mixture for
2 min and the bottle was tightly closed. The mixture was stirred at
100 ꢀC for 6 h. After cooling to room temperature, the mixture was
concentrated in a rotary evaporator and the remaining residue was

58
B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
subjected to the chromatography on silica gel using 4:1 (hex-
ane:ethyl acetate) as eluent to yield 7b1 (126 mg, 30%, orange solid)
and 7b2 (66 mg, 16%, orange solid). Compound (7b1): Mp 56e57 ꢀC,
Rf ¼ 0.41 (4:1, hexane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
was tightly closed. The mixture was stirred at 120 ꢀC for 6 h. After
cooling to room temperature, the mixture concentrated in a rotary
evaporator and the remaining residue was subjected to the chro-
matography on silica gel using 4:1 (hexane:ethyl acetate) as eluent
to yield 7d1 (76 mg, 23%, orange solid) and 8d (71 mg, 16%, orange
oil). Compound (7d1): Mp 74e75 ꢀC, Rf ¼ 0.44 (4:1, hexane:ethyl
d
¼ 1.10 (t, 3H, J ¼ 7.04 Hz, CH3), 1.17 (t, 3H, J ¼ 7.04 Hz, CH3),
3.29e3.63 (m, 4H, CH2), 4.31 (s, 5H, Fc), 4.65 (s, 1H, Fc), 4.85 (s, 1H,
Fc), 4.95 (s, 1H, Fc), 5.15 (s, 1H, CH), 7.31e7.43 (m, 6H, Ph, CH), 10.17
acetate); 1H NMR (250 MHz, CDCl3)
d
¼ 2.34 (s, 3H, CH3), 4.30 (s, 5H,
(s, 1H, Ald.) 13C NMR (62.9 MHz, CDCl3, DEPT)
d
¼ 14.93 (CH3), 15.07
Fc), 4.68 (d, 1H, J ¼ 2.13 Hz, Fc), 4.70 (s, 1H, Fc), 4.99 (s, 1H, Fc), 6.58
(CH3), 62.27 (CH2), 62.76 (CH2), 67.17 (CH, Fc), 70.84 (5ꢁ CH, Fc),
71.41 (CH, Fc), 75.54 (CH, Fc), 78.10 (Cquat, Fc), 91.15 (Cquat, Fc),
100.06 (CH), 127.42 (CH, Ph),128.16 (2ꢁ CH, Ph),128.86 (2ꢁ CH, Ph),
134.98 (Cquat), 135.57 (CH), 136.02 (Cquat), 193.85 (CH, Ald.). IR
(s, 1H, CH), 7.27e7.40 (m, 5H, Ph), 10.26 (s, 1H, Ald.) 13C NMR
(62.9 MHz, CDCl3)
72.07 (CH, Fc), 72.63 (CH, Fc), 97.14 (Cquat, Fc), 126.75 (CH), 128.31
d
¼ 19.46 (CH3), 68.43 (CH, Fc), 70.68 (5ꢁ CH, Fc),
(2ꢁ CH, Ph), 129.01 (2ꢁ CH, Ph), 130.17 (CH), 131.83 (Cquat), 137.53
(ATR):
n
¼ 2973.7 (m), 2927.8 (w), 2863.6 (m), 1668.7 (vs), 1442.4
(Cquat), 192.49 (CH, Ald.); IR (ATR):
n
¼ 3083.9 (w), 2920.6 (w),
(w), 1379.8 (w), 1349.7 (w), 1274.0 (w), 1106.8 (vs), 1059.9 (vs),
1025.5 (s), 1002.7 (s), 927.3 (w), 819.2 (m), 782.8 (m), 757.6 (m); MS
(APCI), m/z (%): 373.07 (100) [Mþ ꢂ OCH2CH3]; HRMS [TOF MS
ESþ]: m/z [Mþ þ Na] calc. For C24H26FeO3Na 441.1129, found
441.1122 (ꢂ1.6 ppm). Compound (7b2): Mp 87e88 ꢀC, Rf ¼ 0.35 (4:1,
2850.4 (w), 1664.9 (vs), 1491.6 (w), 1425.8 (m), 1272.2 (w), 1220.5
(w), 1106.8 (w), 1002.0 (w), 821.7 (m), 782.3 (m), 702.8. (m); MS
(APIeES, 70 eV), m/z (%): 331 (100) [Mþ þ H], 313 (26), 258 (6), 230
(9), 193 (7); HRMS [TOF MS ESþ]: m/z [Mþ þ Na] calc. For
C20H18FeONa 353.0605, found 353.0612 (2.0 ppm). Compound
hexane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
d
¼ 1.20
(8d): 1H NMR (250 MHz, CDCl3)
CH3), 3.76 (s, 5H, Fc), 4.47 (s, 1H, Fc), 4.62 (s, 1H, Fc), 4.80 (s, 1H, Fc),
d
¼ 1.68 (s, 3H, CH3), 1.77 (s, 3H,
(q, J ¼ 6.96 Hz, 6H, 2ꢁ CH3), 3.41e3.67 (m, 4H, 2ꢁ CH2), 4.18 (s, 5H,
Fc), 4.62 (s, 2H, Fc), 4.80 (d, 1H, J ¼ 7.74 Hz, CH), 4.92 (s, 1H, Fc), 6.23
(d, 1H, J ¼ 7.74 Hz, CH), 7.24e7.38 (m, 5H, Ph), 9.76 (s, 1H, Ald.) 13C
6.15 (s, 1H, CH), 6.98e7.53 (m, 10H, Ph), 10.07 (s, 1H, Ald.); IR (ATR):
n
¼ 2958.3 (w), 2910.8 (w), 2853.48(w), 1672.6 (vs), 1260.1 (m),
NMR (100.6 MHz, CDCl3)
d
¼ 15.23 (CH3), 15.26 (CH3), 60.72 (CH2),
1107.0 (m), 1022.4 (m), 818.2 (m), 798.8 (m), 701.3. (s); MS (APCI),
m/z (%): 447 (100) [Mþ þ H], 429 (100); HRMS [TOF MS ESþ]: m/z
[Mþ] calc. For C29H26FeO 446.1333, found 446.1342 (2.0 ppm).
61.11 (CH2), 68.39 (CH, Fc), 70.97 (5ꢁ CH, Fc), 71.75 (CH, Fc), 75.11
(CH, Fc), 76.86 (Cquat, Fc), 92.94 (Cquat), 99.00 (CH), 127.74 (CH, Ph),
128.06 (2ꢁ CH, Ph), 128.72 (2ꢁ CH, Ph), 129.05 (CH), 139.47 (Cquat),
140.15 (Cquat), 192.33 (CH, Ald.); IR (ATR):
n
¼ 2972.7 (m), 2870.7
4.2.8. 2-[(E)-1-(Trimethylsilyl)prop-1-en-2-yl]ferrocenecarboxal-
dehyde (7e1)
(m), 1663.7 (vs), 1427.5 (m), 1370.8 (w), 1330.8 (w), 1263.6 (w),
1135.4(s), 1106.8 (vs), 1050.5 (vs), 1000.4 (s), 822.9 (m), 778.4 (m),
703.0 (m); MS (APCI), m/z (%): 373.07 (100) [Mþ ꢂ OCH2CH3], 345
(23); HRMS [TOF MS ESþ]: m/z [Mþ þ Na] calc. For C24H26FeO3Na
441.1129, found 441.1129 (0.0 ppm).
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(1, 1.00 mmol, 342 mg), 1-trimethylsilyl-1-propyne (6e, 4.00 mmol,
452 mg), (dppf)PdCl2 (0.03 mmol, 24.48 mg) and i-Pr2NH (7 mL).
Nitrogen was bubbled through the mixture for 2 min and the bottle
was tightly closed. The mixture was stirred at 100 ꢀC for 22 h. After
cooling to room temperature, the mixture was concentrated in
a rotary evaporator and the remaining residue was subjected to the
chromatography on silica gel using 4:1 (hexane:ethyl acetate) as
eluent to yield 7e1 (98 mg, 30%, orange oil). Rf ¼ 0.56 (4:1, hex-
4.2.6. 2-[(E)-2-Trimethylsily-1-phenylvinyl]ferrocenecarboxalde -
hyde (7c1)
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(1, 1.00 mmol, 342 mg), 1-phenyl-2-(trimethylsilyl)acetylene
(6c, 4.00 mmol, 697 mg), (dppf)PdCl2 (0.03 mmol, 24.48 mg) and
i-Pr2NH (7 mL). Nitrogen was bubbled through the mixture for
2 min and the bottle was tightly closed. The mixture was stirred at
120 ꢀC for 6 h. After cooling to room temperature, the mixture was
concentrated in a rotary evaporator and the remaining residue was
subjected to the chromatography on silica gel using 4:1 (hex-
ane:ethyl acetate) as eluent to yield 7c1 (132 mg, 34%, orange solid).
Mp 71e72 ꢀC, Rf ¼ 0.53 (4:1, hexane:ethyl acetate); 1H NMR
ane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
d
¼ 0.16 (s, 9H,
SiMe3), 2.22 (s, 3H, CH3), 4.25 (s, 5H, Fc), 4.62 (s, 2H, Fc), 4.94 (s, 1H,
Fc), 5.61 (s, 1H, CH), 10.13 (s, 1H, Ald.) 13C NMR (62.9 MHz, CDCl3)
d
¼ ꢂ0.02 (SiMe3), 22.2 (CH3), 68.15 (CH, Fc), 70.64 (5ꢁ CH, Fc),
71.75 (CH, Fc), 72.58 (CH, Fc), 76.83 (Cquat, Fc), 97.92 (Cquat, Fc),
131.85 (CH), 146.53 (Cquat), 192.67 (CH, Ald.) IR (ATR)
n
¼ 3097.2 (w),
2952.8 (w), 2855.8 (w), 1667.3 (vs), 1592.0 (m), 1421.3 (m), 1381.3
(w), 1349.7 (w), 1246.6 (s), 1205.8 (w), 1117.1 (s), 1107.1 (s), 1036.3
(w), 1001.7 (w), 830.6 (vs), 771.5. (s), 749.9 (m), 710.7 (m); MS
(APIeES, 70 eV), m/z (%): 327 (100) [Mþ þ H], 117 (16); HRMS [TOF
MS ESþ]: m/z [Mþ þ H] calc. For C17H23FeOSi 327.0868, found
327.0874 (1.8 ppm).
(250 MHz, CDCl3)
(s, 1H, Fc), 4.60 (s, 1H, Fc), 4.94 (s, 1H, Fc), 6.14 (s, 1H, CH), 7.25e7.36
(m, 5H, Ph), 9.94 (s, 1H, Ald.) 13C NMR (62.9 MHz, CDCl3)
d
¼ ꢂ0.16 (s, 9H, SiMe3), 4.13 (s, 5H, Fc), 4.49
d
¼ ꢂ0.15
(SiMe3), 68.38 (CH, Fc), 70.97 (5ꢁ CH, Fc), 71.80 (CH, Fc), 74.37
(CH, Fc), 76.73 (Cquat, Fc), 95.51 (Cquat), 127.49 (CH), 127.82 (2ꢁ CH,
Ph), 128.74 (2ꢁ CH, Ph), 134.14 (CH), 142.71 (Cquat), 152.58 (Cquat),
4.2.9. 2-((E)-4,4-Dimethylpent-2-en-2-yl)ferrocenecarboxaldehyde
(7f1)
192.52 (CH, Ald.); IR (ATR):
n
¼ 2973.8 (m), 2858.7 (m), 1670.1 (vs),
1490.7 (m), 1420.9 (w),1381.2 (w),1349.6 (w),1246.6 (s),1151.0 (w),
1116.4 (vs), 1074.6 (m), 1042.2 (w), 846.1 (vs), 831.6 (vs), 775.5. (s),
758.8 (s), 702.6 (vs); MS (APIeES, 70 eV), m/z (%): 389 (100)
[Mþ þ H], 179 (11); HRMS [TOF MS ESþ]: m/z [Mþ þ Na] calc. For
C22H24FeOSiNa 411.0844, found 411.0847 (0.7 ppm).
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(1, 1.00 mmol, 342 mg), 4,4-dimethyl-2-pentyne (6f, 4.00 mmol,
385 mg), (dppf)PdCl2 (0.03 mmol, 24.48 mg) and i-Pr2NH (7 mL).
Nitrogen was bubbled through the mixture for 2 min and the bottle
was tightly closed. The mixture was stirred at 100 ꢀC for 22 h. After
cooling to room temperature, the mixture was concentrated in
a rotary evaporator and the remaining residue was subjected to the
chromatography on silica gel using 4:1 (hexane:ethyl acetate) as
eluent to yield 7f1 (96 mg, 31%, orange oil). Rf ¼ 0.64 (4:1, hex-
4.2.7. 2-[(E)-1-Phenylprop-1-en-2-yl]ferrocenecarboxaldehyde
(7d1) and 2-[(1Z,3E)-2,3-dimethyl-1,4-diphenylbuta-1,3-dienyl]
ferrocenecarboxaldehyde (8d)
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(1, 1.00 mmol, 342 mg), 1-phenyl-1-propyne (6d, 4.00 mmol,
464 mg), (dppf)PdCl2(0.03 mmol, 24.48 mg) and i-Pr2NH (7 mL).
Nitrogen was bubbled through the mixture for 2 min and the bottle
ane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
d
¼ 1.17 (s, 9H, t-Bu),
2.18 (s, 3H, CH3), 4.24 (s, 5H, Fc), 4.53 (s, 1H, Fc), 4.58 (s, 1H, Fc), 4.89
(s, 1H, Fc), 5.51 (s, 1H, CH), 10.09 (s, 1H, Ald.). 13C NMR (100.59 MHz,
CDCl3)
d
¼ 18.53 (CH3), 30.84 (CH3, t-Bu), 33.37 (Cquat, t-Bu), 67.31

B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
59
(CH, Fc), 70.40 (5ꢁ CH, Fc), 71.52 (CH, Fc), 71.73 (CH, Fc), 76.93 (Cquat
Fc), 99.86 (Cquat, Fc), 127.06 (Cquat), 142.16 (CH), 192.81 (CH, Ald.). IR
(ATR)
1424.7 (s),1385.0 (w),1361.7 (m),1269.7 (w),1221.3 (m),1106.5 (m),
1020.8 (w), 1001.0 (m), 817.7 (s), 777.8. (m); MS (APCI), m/z (%): 311
(100) [Mþ þ H], 255 (10); HRMS [TOF MS ESþ]: m/z [Mþ þ H] calc.
For C18H23FeO 311.1098, found 311.1086 (ꢂ3.9 ppm).
,
a catalytic amount of DMAP were added. Resulting solution was
stirred at room temperature for 17 h. After removal of the solvents
in a rotatory evaporator, the residue was diluted with ether
(200 mL) and water (100 mL). The organic layer was separated,
dried over Na2SO4 and filtered. The solution was concentrated in a
rotary evaporator and the remaining yellow solid, 1-ferrocenylethyl
acetate (18, 9.71 g, 93%), was directly used in the next step. The
physical and spectroscopic data are in agreement with also those
reported previously for this compound [107].
n
¼ 3095.7 (w), 2952.5 (s), 2863.9 (w), 1662.7 (vs),1463.5 (w),
4.2.10. 2-[(E)-2-Methylhexa-1,3-dien-3-yl]ferrocenecarboxaldeyde
(7g1) and 2-[(E)-5-m methylhexa-3,5-dien-3-yl]
ferrocenecarboxaldeyde (7g2)
4.2.13. N,N-Dimethylaminoethylferrocene (19)
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(1, 1.00 mmol, 342 mg), 2-methyl-1-hexen-3-yne (6g, 4.00 mmol,
376 mg), (dppf)PdCl2 (0.03 mmol, 24.48 mg) and i-Pr2NH (7 mL).
Nitrogen was bubbled through the mixture for 2 min and the bottle
was tightly closed. The mixture was stirred at 120 ꢀC for 7.5 h. After
cooling to room temperature, the mixture was concentrated in
a rotary evaporator and the remaining residue was subjected to the
chromatography on silica gel using 4:1 (hexane:ethyl acetate) as
eluent to yield 7g1 (34 mg, 11%, orange oil) and 7g2 (114 mg, 37%,
orange oil). Compound (7g1): Rf ¼ 0.64 (4:1, hexane:ethyl acetate);
To a solution of 1-ferrocenylethyl acetate (18, 2.00 g, 7.35 mmol)
in MeOH (25 mL), dimethylamine (5 mL, 60% in water) was added.
The solution was stirred at room temperature for 19 h. Then, the
solution was diluted with ether (100 mL) and water (50 mL). The
organic layer was separated, dried over Na2SO4 and filtered.
The solution was concentrated in a rotary evaporator and the
remaining orange-red oil, N,N-dimethylaminoethylferrocene
(19, 1.76 g, 93%), was directly used in the next step. The physical and
spectroscopic data are in agreement with also those reported
previously for this compound [114].
1H NMR (250 MHz, CDCl3)
d
¼ 1.04 (t, 3H, J ¼ 7.4 Hz, CH3), 1.78
(s, 3H, CH3), 2.14e2.26 (m, 2H, CH2), 4.22 (s, 5H, FcH), 4.55 (s, 1H,
CH), 4.60 (s, 1H, CH), 4.86 (s, 1H, CH), 4.90 (s, 1H, CH), 5.08 (s, 1H,
CH), 5.88 (t, 1H, J ¼ 7.5 Hz, CH), 10.19 (s, 1H, Ald.). 13C NMR
4.2.14. 2-(N,N-Dimethylaminoethyl)iodoferrocene (20)
To a solution of N,N-dimetilaminoethylferrocene (19, 6.5 g,
25.28 mmol) in ether (130 mL) at 0 ꢀC under a nitrogen atmosphere,
sec-BuLi (19.85 mL of a 1.4 M of cyclohexane solution, 27.79 mmol)
was added dropwise via a syringe over 10 min. The resulting red
solution was stirred at 0 ꢀC for 1 h and an ether (65 mL) solution of
I2 (7.70 g, 30.34 mmol) was added via cannula. The resulting
solution was stirred firstly at 0 ꢀC for 15 min and then at room
temperature for additional 1 h. The reaction was quenched with
10% Na2S2O3 (100 mL). The mixture was diluted with ether
(100 mL) and the organic layer was separated. The aqueous layer
was extracted with ether (2 ꢁ 50 mL). The combined organic layers
were dried over Na2SO4 and filtered. The solution concentrated in
a rotary evaporator and the remaining reddish-brown oil residue
was subjected to the chromatography on silica gel using 10:10:1
(ethyl acetate:hexane:triethylamine) as eluent to yield 20 (6.00 g,
62%, orange-red oil). Rf ¼ 0.31 (10:10:1, ethyl acetate:hexane:-
(100.59 MHz, CDCl3)
d
¼ 14.73 (CH3), 22.91 (CH3), 23.02 (CH2), 67.37
(CH, Fc), 70.89 (5ꢁ CH, Fc), 71.28 (CH, Fc), 74.07 (CH, Fc), 76.85
(Cquat, Fc), 93.90(Cquat, Fc), 114.83 (CH), 134.29 (CH), 136.65 (Cquat),
143.86 (Cquat), 193.50 (CH, Ald.); IR (ATR)
n
¼ 3083.5 (w), 2964.0
(w), 2931.1 (w), 2871.1 (w),1669.7 (vs),1576.3 (w),1429.4 (s),1372.9
(w), 1319.3 (w), 1258.7 (w), 1199.6 (w), 1107.2 (m), 1003.7 (w), 820.6
(s), 758.7. (w); MS (APCI), m/z (%): 309 (91) [Mþ þ H], 291 (100);
HRMS [TOF MS ESþ]: m/z [Mþ þ Na] calc. For C18H20FeONa
331.0761, found 331.0769 (2.4 ppm). Compound (7g2): Rf ¼ 0.64
(4:1, hexane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
d
¼ 1.08 (t,
3H, J ¼ 7.50 Hz, CH3), 1.95 (s, 3H, CH3), 2.43e2.78 (m, 2H, CH2), 4.26
(s, 5H, Fc), 4.61 (s, 1H, CH), 4.64 (s, 1H, CH), 4.93 (s, 1H, CH), 4.96
(s, 1H, CH), 5.04 (s, 1H, CH), 6.17 (s, 1H, CH), 10.12 (s, 1H, Ald.). 13C
NMR (62.9 MHz, CDCl3)
d
¼ 14.74 (CH3), 23.34 (CH3), 26.30 (CH2),
67.61 (CH, Fc), 70.67 (5ꢁ CH, Fc), 71.58 (CH, Fc), 73.26 (CH, Fc), 76.99
triethylamine); 1H NMR (250 MHz, CDCl3)
d
¼ 1.51 (d, 3H,
(Cquat, Fc), 97.29 (Cquat, Fc), 115.31 (CH), 132.79 (CH), 137.00 (Cquat),
J ¼ 6.79 Hz, CH3), 2.15 (s, 6H, NMe2), 3.63 (q, 1H, J ¼ 6.79 Hz, CH),
141.45 (Cquat), 192.85 (CH, Ald.); IR (ATR):
n
¼ 3084.5 (w), 2969.2
4.12 (s, 5H, Fc), 4.16 (s, 1H, Fc), 4.24 (s, 1H, Fc), 4.46 (s, 1H, Fc). 13C
(w), 2931.0 (w), 2870.1 (w), 1636.6 (vs), 1426.0 (s), 1374.0 (m),
1349.8 (w), 1252.5 (w), 1207.6 (w), 1106.8 (s), 1068.3 (w), 1036.0
(w), 1001.9 (m), 839.1 (m), 818.7 (s), 770.9. (m); MS (APCI), m/z (%):
309 (100) [Mþ þ H], 291 (18); HRMS [TOF MS ESþ]: m/z [Mþ þ H]
calc. For C18H21FeO 309.0942, found 327.0934 (ꢂ2.6 ppm).
NMR (100.58 MHz, CDCl3, CCl4)
(Cquat, Fc), 57.61 (CH), 65.54 (CH, Fc), 68.07 (CH, Fc), 71.68 (5ꢁ CH,
Fc), 74.36 (CH, Fc), 90.31 (Cquat, Fc); IR (ATR)
d
¼ 15.72 (CH3), 41.18 (NMe2), 45.50
n
¼ 3092.3 (w), 2968.6
(m), 2932.0 (m), 2854.4 (w), 2814.4 (m), 2770.0 (m), 1670.4 (w),
1470.6 (w), 1448.9 (s), 1411.5 (w), 1371.4 (s), 1337.7 (w), 1260.4 (m),
1241.9 (m), 1192.1 (m), 1154.9 (m), 1105.9 (s), 1087.7 (s), 1071.3 (s),
1028.3 (m), 999.7 (vs), 964.0 (m), 918.1 (vs), 817.4 (vs), 770.3 (m),
715.0 (m). MS (APCI), m/z (%): 384 (100) [Mþ þ H], 339 (80).
4.2.11. 1-Ferrocenylethanol (17)
To a solution of acetylferrocene (16, 1.00 g, 4.38 mmol) in ether
(15 mL) under nitrogen atmosphere at 0 ꢀC, LiAlH4 (0.40 g,
10.54 mmol) was portionwise added. The resulting yellow solution
was stirred at room temperature for 3 h. After then, the solution was
cooled to 0 ꢀC and water (50 mL) was added slowly. Reaction mixture
was diluted with ether (100 mL) and the organic layer was separated.
The aqueous layer was extracted with ether (2 ꢁ 50 mL). The
combined organic layers were dried over Na2SO4 and filtered. The
solution concentrated in a rotary evaporator and the remaining
yellow solid,1-ferrocenylethanol (17, 0.978 g, 97%), was directly used
in the next step. The physical and spectroscopic data are in agree-
ment with also those reported previously for this compound [107].
4.2.15. 1-(2-Iodoferrocenyl)ethyl acetate (21-I)
To
a solution of 2-(N,N-dimethylaminoethyl)iodoferrocene
(20, 2.00 g, 5.22 mmol) in triethylamine (13 mL), acetic anhydride
(5.00 g, 49.0 mmol) and a catalytic amount of DMAP were added.
The resulting solution was stirred at 40 ꢀC for 48 h. The solution
concentrated in a rotary evaporator and the remaining residue was
subjected to the chromatography on silica gel using 5:1 (hex-
ane:ethyl acetate) as eluent to yield 21-I (1.58 g, 76%, yellow solid).
Mp 115e116 ꢀC, Rf ¼ 0.45 (5:1, hexane:ethyl acetate); 1H NMR
(250 MHz, CDCl3)
d
¼ 1.65 (d, 3H, J ¼ 6.41 Hz, CH3), 2.02 (s, 3H, CH3),
4.15 (s, 5H, Fc), 4.28 (s, 1H, Fc), 4.33 (s, 1H, Fc), 4.51 (s, 1H, Fc), 5.89
4.2.12. 1-Ferrocenylethyl acetate (18)
To a solution of 1-ferrocenylethanol (17, 8.86 g, 38.5 mmol) in
triethylamine (75 mL), acetic anhydride (20.0 g, 196 mmol) and
(q,1H, J ¼ 6.41 Hz, CH). 13C NMR (100.58 MHz, CDCl3, CCl4)
¼ 18.79
d
(CH3), 21.07 (CH3), 44.05 (Cquat, Fc) 65.83 (CH), 68.79 (CH), 69.42
(CH), 71.75 (5ꢁ CH, Fc), 75.55 (CH), 87.73 (Cquat, Fc), 169.62 (Cquat).

60
B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
IR (ATR)
n
¼ 3102.4 (w), 2983.1 (m), 1714.4 (vs), 1455.4 (w), 1410.2
63.79 (CH), 66.51 (CH), 68.30 (CH), 71.25 (5ꢁ CH, Fc), 74.41 (CH),
95.50 (Cquat, Fc); IR (ATR)
¼ 3255.9 (vs), 3094.0 (w), 2967.8 (m),
(m), 1390.4 (m), 1366.7 (s), 1249.2 (vs), 1165.0 (w), 1106.5 (m),
1064.0 (m), 1042.6 (s), 1015.0 (s), 1000.6 (s), 945.9 (s), 927.9 (s),
828.7 (s), 808.9 (s), 719.8 (m); HRMS [TOF MS ESþ]: m/z [Mþ] calc.
For C14H15FeIO2 397.9466, found 397.9477 (2.8 ppm).
n
2920.2 (w), 1472.3 (w), 1444.8 (m), 1411.8 (w), 1369.5 (s), 1344.0
(w),1311.7 (w), 1260.6 (w), 1243.1 (s),1159.7 (m),1098.8 (vs), 1065.7
(s), 1032.1 (m), 1008.9 (vs), 942.6 (m), 881.7 (vs), 848.9 (w), 841.8
(w), 805.2 (vs); MS (APCI), m/z (%): 356 (5) [Mþ], 339 (100) HRMS
[TOF MS ESþ]: m/z [Mþ] calc. For C12H13FeIO 355.9361, found
355.9360 (ꢂ0.3 ppm).
4.2.16. 1-(2-Iodoferrocenyl)ethyl acetate (21-I) and (21-II)
To
a solution of 2-(N,N-dimethylaminoethyl)iodoferrocene
(20, 4.00 g, 10.44 mmol) in toluene (16 mL) at r.t., acetic anhydride
(40 mL) and acetic acid (16 mL) were added. The resulting solution
was stirred at 80 ꢀC for 5 h. Then, the solution was concentrated in
a rotary evaporator and the remaining reddish oil residue was
subjected to the chromatography on silica gel using 5:1 (hex-
ane:ethyl acetate) as eluent to yield 21-I (2.16 g, 52%, yellow solid)
and 21-II (1.41 g, 34%, yellow oil). Rf ¼ 0.60 (5:1, hexane:ethyl
4.2.19. 1-[2-((E)-1,2-Diphenylvinyl)ferrocenyl]ethanone (22a)
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(2-I, 1.00 mmol, 356 mg), diphenylacetylene (6a, 4.00 mmol,
714 mg), (dppf)PdCl2(0.03 mmol, 24.48 mg) and i-Pr2NH (7 mL).
Nitrogen was bubbled through the mixture for 2 min and the bottle
was tightly closed. The mixture was stirred at 100 ꢀC for 6 h. After
cooling to room temperature, the mixture was concentrated in
a rotary evaporator and the remaining residue was subjected to the
chromatography on silica gel using 4:1 (hexane:ethyl acetate) as
eluent to yield 22a (358 mg, 88%, orange solid). Mp 117e118 ꢀC,
Rf ¼ 0.42 (4:1, hexane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
acetate); 1H NMR (250 MHz, CDCl3)
d
¼ 1.39 (d, 3H, J ¼ 6.37 Hz,
CH3), 2.20 (s, 3H, CH3), 4.14 (s, 5H, FcH), 4.21 (s, 1H, Fc), 4.27 (s, 1H,
Fc) 4.41 (s, 1H, Fc), 5.81 (q, 1H, J ¼ 6.37 Hz, CH). 13C NMR
(100.58 MHz, CDCl3)
d
¼ 21.23 (CH3), 22.39 (CH3), 41.20 (Cquat, Fc)
64.91 (CH), 68.34 (CH), 69.03 (CH), 71.52 (5ꢁ CH, Fc), 74.38 (CH),
90.49 (Cquat, Fc), 169.70 (Cquat); IR (ATR)
n
¼ 3096.2 (w), 2977.5 (w),
d
¼ 2.37 (s, 3H, CH3), 4.14 (s, 5H, Fc), 4.54 (s, 2H, Fc), 4.84 (s, 1H, Fc),
1732.7 (vs), 1447.6 (w), 1412.9 (w), 1368.6 (s), 1286.6 (w), 1231.5
(vs), 1106.5 (m), 1074.6 (s), 1048.9 (m), 1022.8 (s), 1001.3 (s), 954.7
(m), 929.2 (s), 809.1 (s), 730.9 (m); HRMS [TOF MS ESþ]: m/z [Mþ]
calc. For C14H15FeIO2 397.9466, found 397.9459 (ꢂ1.8 ppm).
7.09e7.22 (m, 11H, 2ꢁ Ph, CH); 13C NMR (100.59 MHz, CDCl3)
d
¼ 29.24 (CH3), 69.96 (CH, Fc), 70.07 (CH, Fc), 71.19 (5ꢁ CH, Fc),
76.85 (CH, Fc), 78.01 (Cquat, Fc), 96.07 (Cquat, Fc), 126.84 (CH), 127.27
(CH), 128.08 (2ꢁ CH), 128.12 (2ꢁ CH), 129.34 (2ꢁ CH), 129.48
(2ꢁ CH), 131.21 (CH), 137.08 (Cquat), 137.91 (Cquat), 140.74 (Cquat),
4.2.17. 1-(2-Iodoferrocenyl)ethanol (2-I)
201.75 (Cquat); IR (ATR)
n
¼ 3088.7 (w), 3014.2 (w), 2993.7 (w),
To a methanol (9 mL) and THF (18 mL) solution of 1-(2-
iodoferrocenyl)ethyl acetate (21-I, 0.6 g, 1.51 mmol), NaOH (0.8 g)
and H2O (18 mL) were added. The resulting solution was stirred at
room temperature for 5 h and diluted with ether (50 mL). The
organic layer was separated and the aqueous layer was extracted
with ether (2 ꢁ 50 mL). The combined organic layers were dried
over Na2SO4 and filtered. The solution was concentrated in a rotary
evaporator and the remaining orange residue was subjected to the
chromatography on silica gel using 1:4 (ethyl acetate:hexane) as
eluent to yield (2-I, 0.51 g, 95%, yellow solid). Mp 60e61 ꢀC,
Rf ¼ 0.33, (4:1, hexane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
1662.3 (vs), 1598.4 (m), 1572.3 (w), 1491.1 (m), 1437.5 (s), 1417.0 (s),
1362.8 (s), 1339.5 (s), 1251.7 (s), 1234.5 (s), 1175.5 (w), 1146.3 (w),
1108.5 (w), 1072.2 (w), 1039.0 (w), 1010.8 (w), 1001.2 (w), 976.6 (w),
946.6 (m), 910.6 (w), 894.2 (w), 868.0 (w), 849.8 (w), 838.2 (vs),
828.3 (vs), 774.2 (vs), 751.1 (m), 714.1 (vs); MS (APCI), m/z (%): 407
(100) [Mþ þ H], 364 (11); HRMS [TOF MS ESþ]: m/z [Mþ þ Na] calc.
For C26H22FeONa 429.0918, found 429.0916 (ꢂ0.5 ppm).
4.2.20. 1-[2-((Z)-3,3-Diethoxy-1-phenylprop-1-en-2-yl)ferrocenyl]
ethanone (22b1) and 1-[2-((E)-3,3-diethoxy-1-phenylprop-1-en-1-
yl)ferrocenyl]ethanone (22b2)
d
¼ 1.62 (d, 3H, J ¼ 6.41 Hz, CH3), 1.95 (bs, 1H, OH), 4.14 (s, 5H, Fc),
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(2-I, 1.00 mmol, 356 mg), phenylpropiolaldehyde diethyl acetal
(6b, 4.00 mmol, 817 mg), (dppf)PdCl2 (0.03 mmol, 24.48 mg) and
i-Pr2NH (7 mL). Nitrogenwas bubbled through the mixture for 2 min
and the bottle was tightly closed. The mixture was stirred at 120 ꢀC
for 6 h. After cooling to room temperature, the mixture was
concentrated in a rotary evaporator and the remaining residue was
subjected to the chromatography on silica gel using 4:1 (hex-
ane:ethyl acetate) as eluent to yield 22b1 (162 mg, 37.5%, orange oil)
and 22b2 (54 mg, 12.5%, orange solid). Compound (22b1): Rf ¼ 0.41
4.25 (s, 1H, Fc), 4.29 (s, 1H, Fc), 4.47 (s, 1H, Fc), 4.85 (q, 1H,
J ¼ 6.41 Hz, CH). 13C NMR (100.58 MHz CDCl3)
¼ 21.31 (CH3), 43.64
d
(Cquat, Fc), 64.97 (CH), 66.48 (CH), 68.71 (CH), 71.58 (5ꢁ CH, Fc),
74.98 (CH), 91.60 (Cquat, Fc). IR (ATR)
n
¼ 3204.9 (vs), 2973.7 (m),
2932.6 (w), 2882.9 (w), 1637.7 (w), 1449.5 (w), 1410.0 (w), 1435.2
(w), 1387.6 (w), 1370.5 (m), 1316.3 (w), 1300.2 (w), 1278.1 (w),
1260.6 (w), 1242.2 (m), 1160.6 (w), 1103.0 (s), 1094.8 (s), 1058.2 (s),
1027.9 (s), 1000.6 (s), 939.9 (s), 871.3 (s), 804.3 (s), 707.9 (m); MS
(APCI), m/z (%): 356 (5) [Mþ], 339 (100); HRMS [TOF MS ESþ]: m/z
[Mþ] calc. For C12H13FeIO 355.9361, found 355.9372 (3.1 ppm).
(4:1, hexane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
(t, 3H, J ¼ 6.99 Hz, CH3), 1.16 (t, 3H, J ¼ 6.99 Hz, 2.48 s, 3H, CH3),
3.34e3.57 (m, 4H, CH2), 4.28 (s, 5H, Fc), 4.50 (s, 1H, Fc), 4.63 (s, 1H,
Fc), 4.81 (s, 1H, Fc), 5.16 (s, 1H, CH), 7.32e7.41 (m, 6H, Ph, CH), 13C
d
¼ 1.05
4.2.18. 1-(2-Iodoferrocenyl)ethanol (2-II)
To a methanol (18 mL) and THF (36 mL) solution 1-(2-
iodoferrocenyl)ethyl acetate (21-II, 1.2 g, 3.02 mmol), NaOH
(1.6 g) and H2O (36 mL) were added. The resulting solution was
stirred at room temperature for 5 h and diluted with ether
(100 mL). The organic layer was separated and the aqueous layer
was extracted with ether (2 ꢁ 50 mL). The combined organic layers
were dried over Na2SO4 and filtered. The solution was concentrated
in a rotary evaporator and the remaining orange residue was sub-
jected to the chromatography on silica gel using 1:4 (ethyl aceta-
te:hexane) as eluent to yield (2-II, 0.97 g, 90%, yellow solid). Mp
76e77 ꢀC, Rf ¼ 0.47, (4:1, hexane:ethyl acetate); 1H NMR (250 MHz,
NMR (100.59 MHz, CDCl3)
d
¼ 14.99 (CH3), 15.24 (CH3), 29.46 (CH3)
61.93 (CH2), 63.03 (CH2), 69.18 (CH, Fc), 69.91 (CH, Fc), 70.94 (5ꢁ CH,
Fc), 76.10 (CH, Fc), 79.90 (Cquat, Fc), 90.83 (Cquat, Fc), 100.08 (CH),
127.37 (CH, Ph), 128.27 (2ꢁ CH, Ph), 128.93 (2ꢁ CH, Ph), 135.47
(Cquat),135.94 (CH),136.52 (Cquat), 202.76 (Cquat); IR (ATR)
n
¼ 3088.6
(w), 3058.2 (w), 3022.8 (w), 2973.9 (m), 2872.5 (w), 1660.6 (vs),
1599.6 (w), 1492.8 (w), 1441.6 (m), 1412.0 (m), 1353.3 (m), 1269.9
(w), 1233.5 (w), 1107.6 (vs), 1054.5 (vs), 1001.4 (vs), 924.2 (w), 891.5
(w), 819.3 (m), 760.4 (m), 699.2 (m); MS (APCI), m/z (%): 387.15 (100)
[Mþ ꢂ OCH2CH3]; MS (APCI), m/z (%): 387 (100) [Mþ ꢂ OCH2CH3],
341 (8), 221 (12); HRMS [TOF MS ESþ]: m/z [Mþ þ Na] calc. For
C25H28FeO3Na 455.1286, found 455.1293 (þ1.6 ppm). Compound
(22b2): Mp 84e85 ꢀC, Rf ¼ 0.41 (4:1, hexane:ethyl acetate); 1H NMR
CDCl3)
d
¼ 1.34 (d, 3H, J ¼ 6.34 Hz, CH3), 1.99 (s, 1H, OH), 4.21 (s, 6H,
Fc), 4.32 (s, 1H, Fc), 4.46 (s, 1H, Fc), 4.62 (q, 1H, J ¼ 6.34 Hz, CH). 13C
NMR (100.58 MHz, CDCl3, CCl4)
d
¼ 24.12 (CH3), 41.92 (Cquat, Fc),

B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
61
(250 MHz, CDCl3)
d
¼ 1.19 (t, 3H, J ¼ 6.94 Hz, CH3), 1.29 (t, 3H,
2953.1 (w), 2896.2 (w), 1660.7 (vs), 1596.6 (m), 1410.4 (m), 1353.5
(w), 1245.9 (s), 1217.4 (w), 1107.4 (s), 1094.8 (s), 1040.2 (w), 1001.9
(w), 826.9 (vs), 770.7 (s), 749.3 (m), 717.8 (m); MS (APCI), m/z (%):
341 (44) [Mþ þ H], 269 (100); HRMS [TOF MS ESþ]: m/z [Mþ þ H]
calc. For C18H25FeOSi 341.1024, found 341.1030 (1.8 ppm).
Compound (24e): Rf ¼ 0.45 (4:1, hexane/ethyl acetate); 1H NMR
J ¼ 6.94 Hz, CH3) 2.23 (s, 3H, CH3) 3.39e3.79 (m, 4H, 2ꢁ CH2), 4.20
(s, 5H, Fc), 4.49 (s,1H, Fc), 4.56 (s, 1H, Fc), 4.78 (s,1H, Fc), 4.95 (d,1H,
J ¼ 7.85 Hz, CH), 6.42 (d, 1H, J ¼ 7.85 Hz, CH), 7.21e7.25 (m, 5H, Ph),
13C NMR (100.6 MHz, CDCl3)
d
¼ 15.31 (CH3), 15.42 (CH3), 28.88
(CH3) 60.31 (CH2), 61.54 (CH2), 69.78 (CH, Fc), 69.98 (CH, Fc) 71.11
(5ꢁ CH, Fc), 77.42 (CH, Fc), 77.54 (Cquat), 94.40 (Cquat), 99.21 (CH),
127.43 (CH), 127.66 (2ꢁ CH, Ph), 128.97 (2ꢁ CH, Ph), 129.48 (CH),
(250 MHz, CDCl3)
d
¼ 0.10 (s, 9H, SiMe3), 0.23 (s, 9H, SiMe3), 1.93
(s, 3H, CH3), 2.03 (s, 3H, CH3), 2.45 (s, 3H, CH3), 4.23 (s, 5H, Fc), 4.45
(s, 1H, Fc), 4.49 (s, 1H, Fc) 4.73 (s, 1H, Fc), 6.31 (s, 1H, CH); MS (APCI),
m/z (%): 453 (100) [Mþ þ H], 291 (5); HRMS [TOF MS ESþ]: m/z [Mþ]
calc. For C24H36FeOSi2 452.1654, found 452.1657 (0.7 ppm).
Compound (25e): Rf ¼ 0.32 (4:1, hexane/ethyl acetate); 1H NMR
139.97 (Cquat), 140.89 (Cquat), 201.30 (Cquat). IR (ATR)
n
¼ 3093.1 (w),
2974.4 (m), 2916.7 (m), 2869.7 (m), 1725.1 (m), 1658.9 (vs), 1411.4
(m), 1386.6 (m), 1349.0 (m), 1267.2 (s), 1227.7 (w), 1172.1 (w), 1141.5
(s), 1115.9 (s), 1099.4 (s), 1046.9 (vs),1020.7 (s), 991.1 (vs), 932.1 (m),
895.9 (m), 857.6 (m), 828.2 (s), 782.8 (s), 735.1 (s), 707.4 (s); MS
(APCI), m/z (%): 387 (100) [Mþ ꢂ OCH2CH3], 359 (31), 341 (18);
HRMS [TOF MS ESþ]: m/z [Mþ þ Na] calc. For C25H28FeO3Na
455.1286, found 455.1282 (ꢂ0.9 ppm).
(250 MHz, CDCl3)
d
¼ 0.17 (s, 9H, SiMe3), 1.57 (s, 1H, OH),1.64 (d, 3H,
J ¼ 6.42 Hz, CH3), 2.20 (s, 3H, CH3), 4.09 (s, 5H, Fc), 4.18 (s, 1H, Fc),
4.27 (s, 1H, Fc), 4.33 (s, 1H, Fc), 4.98 (q, 1H, J ¼ 6.62 Hz, CH), 5.97
(s, 1H, CH); 13C NMR (62.9 MHz, CDCl3)
d
¼ 0.14 (SiMe3), 22.70
(CH3), 23.20 (CH3), 65.12 (CH), 66.54 (CH), 66.82 (CH), 68.88 (CH),
4.2.21. 1-[2-((E)-2-Trimethylsilyl-1-phenylvinyl)ferrocenyl]
ethanone (22c1)
69.71 (5ꢁ CH, Fc), 88.80 (Cquat, Fc), 90.64 (Cquat, Fc), 127.65 (CH),
149.48 (Cquat); IR (ATR)
n
¼ 3407.6 (w), 3095.8 (w), 2952.8 (m),
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(2-I, 1.00 mmol, 356 mg), 1-phenyl-2-(trimethylsilyl)acetylene
(6c, 4.00 mmol, 697 mg), (dppf)PdCl2 (0.03 mmol, 24.48 mg) and
i-Pr2NH (7 mL). Nitrogenwas bubbled through the mixture for 2 min
and the bottle was tightly closed. The mixture was stirred at 120 ꢀC
for 46 h. After cooling to room temperature, the mixture was
concentrated in a rotary evaporator and the remaining residue was
subjected to the chromatography on silica gel using 4:1 (hex-
ane:ethyl acetate) as eluent to yield 22c1 (170 mg, 42%, orange
solid). Mp 76e77 ꢀC, Rf ¼ 0.55 (4:1, hexane:ethyl acetate); 1H NMR
2886.1 (w), 1590.8 (m), 1370.9 (m), 1245.8 (s), 1204.1 (w), 1106.2
(m), 1058.2 (m), 1000.1 (m), 940.8 (w), 854.3 (vs), 837.2 (vs), 827.3
(vs), 770.8 (m), 749.7 (m), 712.8 (m); MS (APCI), m/z (%): 325 (100)
[Mþ ꢂ OH], 269 (7), 253 (46); HRMS [TOF MS ESþ]: m/z [Mþ] calc.
For C18H26FeOSi 342.1102, found 342.1086 (ꢂ4.7 ppm).
4.2.23. 1-[2-((E)-4,4-Dimethylpent-2-en-2-yl)ferrocenyl]ethanone
(22f1) and 6-tert-butyl-2,5-dimethylferroceno[c]pyran (23fI)
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(2-I, 1.00 mmol, 356 mg), 4,4-dimethyl-2-pentyne (6f, 4.00 mmol,
385 mg), (dppf)PdCl2 (0.03 mmol, 24.48 mg) and i-Pr2NH (7 mL).
Nitrogen was bubbled through the mixture for 2 min and the bottle
was tightly closed. The mixture was stirred at 120 ꢀC for 6 h. After
cooling to room temperature, the mixture was concentrated in
a rotary evaporator and the remaining residue was subjected to the
chromatography on silica gel using 4:1 (hexane:ethyl acetate) as
eluent to yield 22f1 (146 mg, 45%, red oil) and 23fI (65 mg, 20%,
orange solid). Compound (22f1): Rf ¼ 0.58 (4:1, hexane:ethyl
(250 MHz, CDCl3)
(s, 5H, Fc), 4.43 (s, 1H, Fc), 4.46 (s, 1H, Fc), 4.75 (s, 1H, Fc), 6.22 (s, 1H,
CH), 7.26e7.28 (m, 5H, Ph), 13C NMR (100.59 MHz, CDCl3)
d
¼ ꢂ0.10 (s, 9H, SiMe3), 2.39 (s, 3H, CH3), 4.09
d
¼ ꢂ0.10
(SiMe3), 29.38 (CH3), 69.60 (CH), 69.89 (CH), 71.03 (5ꢁ CH, Fc), 75.76
(CH), 77.70 (Cquat), 96.91 (Cquat), 127.45 (CH), 127.22 (2ꢁ CH, Ph),
128.62 (2ꢁ CH, Ph),134.71 (CH),143.29 (Cquat), 153.07 (Cquat), 201.74
(Cquat); IR (ATR)
n
¼ 3052.9 (w), 2948.9 (m), 1671.5 (vs), 1607.5 (m),
1592.0 (m), 1573.9 (m), 1489.3 (m), 1440.1 (s), 1415.5 (s), 1357.7 (s),
1337.8 (s), 1305.9 (m), 1248.1 (vs),1208.1 (m), 1181.0 (w), 1157.9 (w),
1146.4 (w),1107.8 (m),1068.9 (m),1038.0 (m),1031.1 (m),1014.1 (m),
1002.0 (m), 939.9 (m), 880.7 (s), 842.4 (vs), 831.2 (vs), 780.8 (s),
763.8 (s), 748.9 (s), 726.7 (m), 701.8 (vs); MS (APCI), m/z (%): 373.07
(100) [Mþ þ H], 331 (16), 193 (7); HRMS [TOF MS ESþ]: m/z [Mþ]
calc. For C23H26FeOSi 402.1102, found 402.1104 (0.5 ppm).
acetate); 1H NMR (250 MHz, CDCl3)
d
¼ 1.17 (s, 9H, t-Bu), 2.13 (s, 3H,
CH3), 2.44 (s, 3H, CH3), 4.20 (s, 5H, Fc), 4.39 (bs, 2H, Fc), 4.71 (s, 1H,
Fc), 5.59 (s, 1H, CH); 13C NMR (100.59 MHz, CDCl3)
d
¼ 19.74 (CH3),
29.28 (CH3), 30.54 (CH3, t-Bu), 32.82 (Cquat, t-Bu), 69.61 (CH, Fc),
69.45 (CH, Fc), 70.41 (5ꢁ CH, Fc), 73.18 (CH, Fc), 77.99 (Cquat, Fc),
99.08 (Cquat, Fc), 128.73 (Cquat), 141.42 (CH), 202.29 (Cquat). IR (ATR)
n
¼ 3092.4 (w), 2952.4 (s), 2896.4 (w), 2862.7 (w), 1658.7 (vs),
4.2.22. 1-[2-((E)-1-Trimethylsilyl-prop-1-en-2-yl)ferrocenyl]
ethanone (22e1), 1-[2-((1E,3E)-2,3-dimethyl-1,4-bis(trimethylsilyl)
buta-1,3-dienyl)ferrocenyl]ethanone (24e) and 1-[2-((E)-1-
trimethylsilyl-prop-1-en-2-yl)ferrocenyl]ethanol (25e)
1460.1 (w), 1406.9 (s), 1351.0 (s), 1269.9 (m), 1239.2 (m), 1191.6 (w),
1160.8 (w), 1001.4 (m), 959.4 (w), 925.9 (w), 816.8 (s); MS (APCI), m/
z (%): 325 (100) [Mþ þ H]; HRMS [TOF MS ESþ]: m/z [Mþ] calc. For
C19H24FeO 324.1177, found 324.1185 (2.5 ppm). Compound (23fI):
Mp 43e44 ꢀC, Rf ¼ 0.44 (4:1, hexane:ethyl acetate); 1H NMR
A
screw-cap Pyrex bottle was charged with ferrocenyl
alcohol (2-I, 1.00 mmol, 356 mg), 1-trimethylsilyl-1-propyne
(6e, 4.00 mmol, 452 mg), (dppf)PdCl2 (0.03 mmol, 24.48 mg) and
i-Pr2NH (7 mL). Nitrogen was bubbled through the mixture for
2 min and the bottle was tightly closed. The mixture was stirred at
120 ꢀC for 24 h. After cooling to room temperature, the mixture was
concentrated in a rotary evaporator and the remaining residue was
subjected to the chromatography on silica gel using 4:1 (hex-
ane:ethyl acetate) as eluent to yield 22e1 (44 mg, 13%, orange oil),
24e (59 mg, 13%, yellow oil) and 25e (24 mg, 7%, yellow liquid).
Compound (22e1): Rf ¼ 0.58 (4:1, hexane/ethyl acetate); 1H NMR
(250 MHz, CDCl3)
d
¼ 1.25 (s, 9H, t-Bu),1.30 (d, 3H, J ¼ 6.44 Hz, CH3),
2.02 (s, 3H, CH3), 3.98 (s, 1H, Fc), 4.02 (s, 5H, Fc), 4.07 (s, 1H, Fc), 4.11
(s, 1H, Fc), 5.18 (q, 1H, J ¼ 6.44 Hz, CH); 13C NMR (100.59 MHz,
CDCl3)
d
¼ 14.17 (CH3), 20.43 (CH3), 29.77 (CH3, t-Bu), 36.97 (Cquat
,
t-Bu), 61.72 (CH), 62.74 (CH), 65.14 (CH), 69.70 (5ꢁ CH, Fc), 71.98
(CH) 83.73 (Cquat, Fc), 84.17 (Cquat, Fc), 102.55 (Cquat), 153.11 (Cquat);
IR (ATR)
n
¼ 3092.4 (w), 2963.6 (s), 2913.2 (m), 2857.1 (w), 1608.4
(s), 1356.6 (s), 1317.5 (w), 1258.7 (w), 1180.4 (w), 1104.9 (vs), 1048.9
(s), 998.6 (s), 967.8 (m), 878.3 (w); MS (APCI), m/z (%): 325 (100)
[Mþ þ H]; HRMS [TOF MS ESþ]: m/z [Mþ þ H] calc. For C19H25FeO
325.1255, found 325.1245 (ꢂ3.1 ppm).
(250 MHz, CDCl3)
(s, 3H, CH3), 4.21 (s, 5H, Fc), 4.44 (s, 1H, Fc), 4.47 (s, 1H, Fc) 4.72
(s, 1H, Fc), 5.66 (s, 1H, CH), 13C NMR (62.9 MHz, CDCl3)
d
¼ 0.16 (s, 9H, SiMe3), 2.19 (s, 3H, CH3), 2.42
d
¼ ꢂ0.20
4.2.24. 1-[2-((E)-1,2-Diphenylvinyl)ferrocenyl]ethanone (22a) and
2-methyl-5,6-diphenylferroceno[c]pyran (23a)
(SiMe3), 23.41 (CH3), 29.26 (CH3) 69.75 (CH, Fc), 69.92 (CH, Fc),
70.65 (5ꢁ CH, Fc), 73.31 (CH, Fc), 76.99 (Cquat, Fc), 97.84 (Cquat, Fc),
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(2-II, 1.00 mmol, 356 mg), diphenylacetylene (6a, 4.00 mmol,
131.55 (CH), 148.53 (Cquat), 201.21 (Cquat); IR (ATR)
n
¼ 3097.3 (w),

62
B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
714 mg), (dppf)PdCl2(0.03 mmol, 24.48 mg) and i-Pr2NH (7 mL).
Nitrogen was bubbled through the mixture for 2 min and the bottle
was tightly closed. The mixture was stirred at 120 ꢀC for 6 h. After
cooling to room temperature, the mixture was concentrated in
a rotary evaporator and the remaining residue was subjected to the
chromatography on silica gel using 4:1 (hexane:ethyl acetate) as
eluent to yield 22a (110 mg, 27%, orange solid) and 23a (175 mg,
43%, red solid). Compound (23a): Mp 117e118 ꢀC, Rf ¼ 0.23 (30:1,
(250 MHz, CDCl3)
d
¼ 1.26 (s, 9H, t-Bu),1.65 (d, 3H, J ¼ 6.07 Hz, CH3),
1.97 (s, 3H, CH3), 3.91 (s, 1H, Fc), 4.00 (s, 1H, Fc), 4.09 (s, 5H, Fc), 4.16
(s, 1H, Fc), 4.36 (q, 1H, J ¼ 6.07 Hz, CH); 13C NMR (100.59 MHz,
CDCl3)
d
¼ 14.09 (CH3), 19.46 (CH3), 29.99 (CH3, t-Bu), 37.03 (Cquat
,
t-Bu), 61.74 (CH), 62.90 (CH), 65.15 (CH), 69.59 (5ꢁ CH, Fc), 70.27
(CH) 84.10 (Cquat, Fc), 88.50 (Cquat, Fc), 102.62 (Cquat), 155.59 (Cquat);
IR (ATR)
n
¼ 3094.9 (w), 2954.7 (m), 2865.1 (m), 1682.9 (w), 1610.5
(m), 1479.7 (m), 1383.3 (m), 1361.7 (m), 1337.1 (m), 1263.5 (w),
1219.6 (w), 1179.8 (w), 1131.3 (s), 1105.1 (vs),1079.3 (m), 1065.8 (m),
1039.6 (m), 1012.7 (s), 999.4 (s), 983.2 (m), 886.9 (m), 812.8 (vs),
765.0 (w), 709.5 (w), 685.8 (w), 654.7 (w); HRMS [TOF MS ESþ]: m/
z [Mþ] calc. For C19H24FeO 324.1107, found 324.1166 (ꢂ3.4 ppm).
hexane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
d
¼ 1.87 (d, 3H,
J ¼ 6.20 Hz, CH3), 4.09 (s, 1H, Fc), 4.12 (s, 1H, Fc), 4.16 (s, 1H, Fc) 4.28
(s, 5H, Fc), 4.96 (q, 1H, J ¼ 6.20 Hz, CH), 7.16e7.26 (m, 10H, 2ꢁ Ph);
13C NMR (100.59 MHz, CDCl3, DEPT)
d
¼ 18.87 (CH3), 62.56 (CH, Fc),
62.70 (CH), 65.16 (CH, Fc), 68.82 (5ꢁ CH, Fc), 70.66 (CH, Fc) 79.26
(Cquat, Fc), 87.19 (Cquat, Fc), 113.61 (Cquat), 125.44 (CH, Ph), 126.31
(CH, Ph) 126.50 (2ꢁ CH, Ph), 127.28 (2ꢁ CH, Ph), 127.97 (2ꢁ CH, Ph),
129.02 (2ꢁ CH, Ph), 134.97 (Cquat), 136.90 (Cquat), 147.09 (Cquat); IR
4.2.27. 1-(2-Iodoferrocenyl)ethanone (27)
To a solution of ferrocenyl alcohol (2-I, 1.81 g, 5.10 mmol) in
benzene (35 mL), MnO2 (Mn 58% activated, 4.43 g, 51.0 mmol) was
added. The resulting mixture was stirred at 50 ꢀC for 24 h. The
mixture was filtered over a pad of Celite which was washed with
ether (100 mL). The resulting solution was concentrated in a rotary
evaporator and the remaining residue was subjected to the chro-
matography on silica gel using 1:6 (ethyl acetate:hexane) as eluent
to yield 27 (1.13 g, 63%, orange solid). Mp 70e71 ꢀC, Rf ¼ 0.36 (4:1,
(ATR)
n
¼ 3055.2 (w), 2975.9 (w), 2930.7 (w), 2850.6 (w), 1595.5
(m), 1570.6 (w), 1492.0 (m), 1441.9 (m), 1412.0 (w), 1381.9 (w),
1336.9 (m), 1277.3 (w), 1219.9 (m), 1195.7 (m), 1144.0 (w), 1105.4
(m), 1065.9 (s), 1024.1 (m), 1001.1 (m), 932.2 (m), 888.9 (w), 874.3
(w), 860.2 (w), 815.1 (m), 768.3 (w), 752.6 (s), 721.9 (w), 691.3 (vs);
MS (APCI), m/z (%): 407 (100) [Mþ þ H], 341 (10), 286 (7); HRMS
[TOF MS ESþ]: m/z [Mþ] calc. For C26H22FeO 406.1020, found
406.1029 (ꢂ2.2 ppm).
hexane:etil asetat); 1H NMR (250 MHz, CDCl3)
d
¼ 2.52 (s, 3H, CH3),
4.23 (s, 5H, FcH), 4.52 (s, 1H, FcH), 4.78 (s, 2H, FcH). The spectro-
scopic data are also in agreement with those reported previously
for this compound [115].
4.2.25. 1-[2-((E)-2-Trimethylsilyl-1-phenylvinyl)ferrocenyl]
ethanone (22c1) and 2-methyl-6-trimethylsilyl-5-phenylferroceno
[c]pyran (23c)
4.2.28. 2-(2-Iodoferrocenyl)propan-2-ol (28)
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(2-II, 1.00 mmol, 356 mg), 1-phenyl-2-(trimethylsilyl)acetylene
(6c, 4.00 mmol, 697 mg), (dppf)PdCl2 (0.03 mmol, 24.48 mg) and
i-Pr2NH (7 mL). Nitrogen was bubbled through the mixture for
2 min and the bottle was tightly closed. The mixture was stirred at
120 ꢀC for 55 h. After cooling to room temperature, the mixture was
concentrated in a rotary evaporator and the remaining residue was
subjected to the chromatography on silica gel using 4:1 (hex-
ane:ethyl acetate) as eluent to yield 22c1 (110 mg, 27%, orange
solid) and 23c (140 mg, 43%, orange solid). Compound (23c): Mp
To a solution of 1-(2-iodoferrocenyl)ethanone (27, 1.72 g,
4.86 mmol) in THF (40 mL) at 0 ꢀC under nitrogen atmosphere,
MeMgBr (2.25 mL of a 3.2 M of 2-metil-THF solution, 7.2 mmol) was
added dropwise via a syringe over 10 min. The resulting solution
was stirred at 0 ꢀC for 3 h and water (20 mL) was added to quench
the reaction. The mixture was diluted with ether (60 mL) and the
organic layer was separated. The aqueous layer was extracted with
ether (2 ꢁ 50 mL). The combined organic layers were dried over
Na2SO4 and filtered. The solution was concentrated in a rotary
evaporator and the remaining reddish oil residue was subjected to
the chromatography on silica gel using 1:10 (ethyl acetate:hexane)
as eluent to yield 28 (0.7 g, 39%, orange solid). Mp 56e57 ꢀC,
Rf ¼ 0.45 (4:1, hexane:ethyl acetate); 1H NMR (400 MHz, CDCl3)
84e85 ꢀC, Rf ¼ 0.37, hexane; 1H NMR (250 MHz, CDCl3)
d
¼ ꢂ0.09
(s, 9H, SiMe3), 1.74 (d, 3H, J ¼ 6.21 Hz, CH3), 3.92 (s, 1H, Fc), 4.02
(s, 2H, Fc), 4.17 (s, 5H, Fc), 4.54 (q, 1H, J ¼ 6.21 Hz, CH) 7.31e7.33
(m, 5H, Ph). 13C NMR (100.59 MHz, CDCl3)
d
¼ ꢂ0.74 (SiMe3),
d
¼ 1.56 (s, 3H, CH3), 1.57 (s, 3H, CH3), 2.40 (s, 1H, OH), 4.18 (s, 2H,
Fc), 4.26 (s, 5H, Fc), 4.45 (s, 1H, Fc); 13C NMR (100.59 MHz, CDCl3)
¼ 30.54 (CH3), 30.81 (CH3), 38.16 (Cquat), 66.47 (CH, Fc), 68.37 (CH,
Fc), 69.63 (Cquat), 71.29 (5ꢁ CH, Fc), 76.57 (CH, Fc), 96.82 (Cquat); IR
(ATR)
19.79 (CH3), 62.85 (CH), 63.78 (CH), 65.61 (CH), 70.09 (5ꢁ CH, Fc),
70.22 (CH) 79.32 (Cquat, Fc), 88.99 (Cquat, Fc), 127.03 (CH, Ph), 127.90
(2ꢁ CH, Ph), 130.17 (2ꢁ CH, Ph), 138.26 (Cquat) 156.20 (Cquat); IR
d
(ATR)
n
¼ 3080.2 (w), 3052.7 (w), 2953.2 (w), 2896.3 (w), 1599.7
n
¼ 3555.5 (m), 3090.4 (m), 2968.0 (m), 2925.1 (w), 1452.3
(w), 1558.7 (w), 1492.8 (m), 1408.7 (w), 1381.1 (m), 1366.4 (w),
1337.2 (m), 1247.9 (s), 1149.7 (w), 1112.7 (s), 1105.9 (s), 1063.9 (vs),
1022.4 (w), 999.3 (m), 984.7 (m), 936.3 (s), 881.2 (w), 814.7 (vs),
758.5 (s), 749.1 (vs), 716.4 (w); MS (APCI), m/z (%): 403 (100)
[Mþ þ H], 339 (6), 325 (6); HRMS [TOF MS ESþ]: m/z [Mþ] calc. For
C23H26FeSiO 402.1102, found 402.1103 (0.2 ppm).
(w), 1409.1 (w), 1372.5 (s), 1307.2 (m), 1247.3 (m), 1140.2 (s), 1104.9
(s), 1040.2 (m), 1002.1 (s), 954.3 (s), 931.7 (vs), 808.6 (vs); HRMS
[TOF MS ESþ]: m/z [Mþ] calc. For C13H15FeIO 369.9517, found
369.9518 (ꢂ0.3 ppm).
4.2.29. 2-[2-((E)-1,2-Diphenylvinyl)ferrocenyl]propan-2-ol (29a)
and 2,2-dimethyl-5,6-diphenylferroceno[c]pyran (30a)
4.2.26. 1-[2-((E)-4,4-Dimethylpent-2-en-2-yl)ferrocenyl]ethanone
(22f1) and 6-tert-butyl-2,5-dimethylferroceno[c]pyran (23fII)
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(28, 1.00 mmol, 370 mg), diphenylacetylene (6a, 4.00 mmol,
714 mg), (dppf)PdCl2(0.03 mmol, 24.48 mg) and i-Pr2NH (7 mL).
Nitrogen was bubbled through the mixture for 2 min and the bottle
was tightly closed. The mixture was stirred at 120 ꢀC for 6 h. After
cooling to room temperature, the mixture was concentrated in
a rotary evaporator and the remaining residue was subjected to the
chromatography on silica gel using 4:1 (hexane:ethyl acetate) as
eluent to yield 30a (109 mg, 26%, orange oil) and 29a (186 mg, 44%,
orange solid). Compound (30a): Rf ¼ 0.48 (20:1, hexane:ethyl
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(2-II, 1.00 mmol, 356 mg), 4,4-dimethyl-2-pentyne (6f, 4.00 mmol,
385 mg), (dppf)PdCl2 (0.03 mmol, 24.48 mg) and i-Pr2NH (7 mL).
Nitrogen was bubbled through the mixture for 2 min and the bottle
was tightly closed. The mixture was stirred at 120 ꢀC for 6 h. After
cooling to room temperature, the mixture was concentrated in
a rotary evaporator and the remaining residue was subjected to the
chromatography on silica gel using 4:1 (hexane:ethyl acetate) as
eluent to yield 22f1 (70 mg, 22%, red oil) and 23fII (170 mg, 52%,
orange oil). Compound (23fII): Rf ¼ 0.60 (hexane); 1H NMR
acetate); 1H NMR (250 MHz, CDCl3)
d
¼ 1.49 (s, 3H, CH3), 1.95 (s, 3H,
CH3), 4.08 (s, 1H, Fc), 4.09 (s, 1H, Fc), 4.16 (s, 1H, Fc), 4.26 (s, 5H, Fc),

B. Yucel et al. / Journal of Organometallic Chemistry 704 (2012) 49e64
63
7.15e7.26 (m, 10H, Ph); 13C NMR (100.59 MHz, CDCl3)
d
¼ 27.30
[2] A. Togni, T. Hayashi (Eds.), Ferrocenes: Homogeneous Catalysis, Organic
Synthesis, Materials Science, VCH, Weinheim, 1995.
(CH3), 27.84 (CH3), 62.90 (CH, Fc), 63.10 (CH, Fc), 66.01 (CH, Fc),
69.97 (5ꢁ CH, Fc), 76.48 (Cquat), 79.32 (Cquat), 92.08 (Cquat), 113.79
(Cquat), 126.36 (CH), 127.26 (CH), 127.49 (2ꢁ CH), 128.27 (2ꢁ CH),
129.11 (2ꢁ CH), 129.99 (2ꢁ CH), 136.37 (Cquat), 138.03 (Cquat), 146.02
[3] R.D.A. Hudsen, J. Organomet. Chem. 637ꢂ639 (2001) 47.
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ꢀ
ꢀ
ꢀ
P. Stepnicka (Ed.), Ferrocenes: Ligands, Materials and Biomolecules, John
Wiley & Sons Ltd., Chichester, 2008, pp. 393e446.
(Cquat); IR (ATR)
n
¼ 3080.1 (w), 2971.3 (w), 2925.1 (w), 1721.3 (m),
[6] R. Deschenaux, Ferrocene-Containing Thermotropic Liquid Crystals, in:
ꢀ
ꢀ
ꢀ
P. Stepnicka (Ed.), Ferrocenes: Ligands, Materials and Biomolecules, John
Wiley & Sons Ltd., Chichester, 2008, pp. 447e463.
1598.9 (s), 1488.6 (m), 1441.7 (m), 1378.1 (m), 1358.7 (m), 1251.6 (s),
1200.1 (m), 1114.3 (vs), 1057.6 (s), 1125.9 (m), 926.6 (m), 816.2 (vs),
752.1 (vs), 694.5 (vs); MS (APCI), m/z (%): 421 (100) [Mþ þ H], 355
(6); HRMS [TOF MS ESþ]: m/z [Mþ] calc. For C27H24FeO 420.1177,
found 420.1189 (2.9 ppm). Compound (29a): Mp 119e120 ꢀC,
Rf ¼ 0.52, (4:1, hexane:ethyl acetate); 1H NMR (250 MHz, CDCl3)
[7] O. Riant, V. Mamane, Tetrahedron 57 (2001) 2555.
[8] N. Tsuboya, R. Hamasaki, M. Ito, M. Mitsuishi, T. Miyashita, Y. Yamamoto,
J. Mater. Chem. 13 (2003) 511.
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(2003) 202.
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F. Langa, Eur. J. Org. Chem. (2008) 3535.
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10369.
[14] C. Bucher, C.H. Devillers, J.-C. Moutet, G. Royal, E. Saint-Aman, Coord. Chem.
Rev. 253 (2009) 21.
d
¼ 1.28 (s, 3H, CH3), 1.34 (s, 3H, CH3), 1.89 (s, 1H, OH), 4.19 (s, 1H,
Fc), 4.20 (s, 1H, Fc), 4.27 (bs, 6H, Fc), 7.09e7.16 (m, 10H, Ph), 7.43
(s, 1H, CH); 13C NMR (100.59 MHz, CDCl3)
d
¼ 30.51 (CH3), 30.85
(CH3), 65.75 (CH, Fc), 66.91 (CH, Fc), 69.71 (5ꢁ CH, Fc), 70.09 (Cquat),
74.20 (CH, Fc), 92.72 (Cquat), 96.22 (Cquat), 126.71 (CH), 127.28 (CH),
128.05 (2ꢁ CH), 128.15 (2ꢁ CH), 129.39 (2ꢁ CH), 129.59 (2ꢁ CH),
131.21 (CH), 137.31 (Cquat), 139.08 (Cquat), 141.00 (Cquat); IR (ATR)
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P. Vázquez, J. Zyss, F. Agulló-López, T. Torres, Synth. Met. 137 (2003) 1487.
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Lett. 25 (2008) 3257.
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(2005) 5695.
n
¼ 3529.7 (w), 3100.7 (w), 3080.1 (w), 2966.4 (w), 2914.7 (w),
1617.7 (w), 1599.6 (w), 1488.6 (m), 1442.1 (s), 1357.9 (s), 1358.7 (m),
1248.3 (w), 1139.9 (s), 1106.9 (s), 1002.4 (s), 948.6 (s), 841.1(s), 818.7
(vs), 717.1 (vs), 694.0 (vs); MS (APCI), m/z (%): 422 (5) [Mþ], 405
(100) [Mþ ꢂ OH]; HRMS [TOF MS ESþ]: m/z [Mþ þ Na] calc. For
C27H26FeONa 445.1231, found 445.1240 (2.0 ppm).
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4.2.30. Ferroceno[c]furan-1-(3H)-one (31)
A screw-cap Pyrex bottle was charged with ferrocenyl alcohol
(1, 2.00 mmol, 684 mg), diphenylacetylene (6a, 4.00 mmol, 714 mg),
(dppf)PdCl2 (0.06 mmol, 48.96 mg), Mo(CO)6 (4.00 mmol, 1.06 g)
and i-Pr2NH (14 mL). Nitrogen was bubbled through the mixture for
2 min and the bottle was tightly closed. The mixture was stirred at
100 ꢀC for 6 h. After cooling to room temperature, the mixture was
concentrated in a rotary evaporator and the remaining residue was
subjected to the chromatography on silica gel using 2:1 (hex-
ane:ethyl acetate) as eluent to yield 30 (385 mg, 80%, orange solid).
Mp 120e121 ꢀC, Rf ¼ 0.27 (2:1, hexane:ethyl acetate); 1H NMR
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Soc. 125 (2003) 1007.
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(400 MHz, CDCl3)
d
¼ 4.25 (s, 5H, Fc), 4.41 (s, 1H, Fc), 4.63 (s, 1H, Fc),
4.72 (s, 1H, Fc), 5.00e5.25 (AB system, dA ¼ 5.24, dB ¼ 5.03,
JAB ¼ 13.04 Hz, 2H, CH2); 13C NMR (100.59 MHz, CDCl3)
d
¼ 62.38
(CH, Fc), 63.82 (CH, Fc), 68.54 (CH2), 70.50 (Cquat), 70.92 (5ꢁ CH, Fc),
ꢀ
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ꢀ
Derivatives, in: P. Stepnicka (Ed.), Ferrocenes: Ligands, Materials and
Biomolecules, John Wiley, Chichester, U.K., 2008, pp. 33e116.
74.89 (CH, Fc), 95.99 (Cquat), 173.89 (Cquat); IR (ATR)
n
¼ 3105.9 (w),
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2958.4 (w), 1751.1 (vs), 1459.1 (m), 1424.9 (m), 1409.4 (m), 1331.3
(m), 1267.4 (s), 1089.6 (s), 1038.8 (s), 1000.5 (s), 969.2 (s), 838.7 (s),
808.6 (s), 762.2 (s), 635.9 (s); HRMS [TOF MS ESþ]: m/z [Mþ þ Na]
calc. For C12H10FeO2Na 264.9928, found 264.9922 (ꢂ2.3 ppm).
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Acknowledgments
The authors thank the Scientific and Technical Research Council
of Turkey (TBAG-107T811), the Research Board of Istanbul Technical
University (BAP-32464 and BAP-34044) for financial support of this
research. The authors are particularly grateful to Professor Dr.
Süheyla Özbey, Hacettepe University, Department of Physics Engi-
neering, for the X-ray crystal structure analysis of compound 7a.
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Appendix. Supplementary material
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J. Organomet. Chem. 692 (2007) 1219.
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Chem. 690 (2005) 4564.
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jorganchem.2012.01.007.
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