Synthesis of ferrocenes with ene-terminus via water-promoted Barbier-like carbonyl allylation using bimetallic copper(II)/tin(II) reagent

Article abstract of DOI:10.1016/S0022-328X(03)00205-5

Barbier-type γ-regiospecific allylation of formylferrocene (1) with allyl bromides in the presence of stannous chloride dihydrate and catalytic cupric chloride in dichloromethane-water (1:1) afforded corresponding ferrocenyl dienes FcCHC(R¹)C(R

Full text of DOI:10.1016/S0022-328X(03)00205-5

Journal of Organometallic Chemistry 675 (2003) 105ꢀ112
/
www.elsevier.com/locate/jorganchem
Synthesis of ferrocenes with ene-terminus via water-promoted
Barbier-like carbonyl allylation using bimetallic copper(II)/tin(II)
reagent
Paromita Debroy, Sujit Roy *
Organometallics and Catalysis Laboratory, Chemistry Department, Indian Institute of Technology, Kharagpur 721302, India
Received 1 February 2003; received in revised form 21 March 2003; accepted 21 March 2003
Abstract
Barbier-type g-regiospecific allylation of formylferrocene (1) with allyl bromides in the presence of stannous chloride dihydrate
and catalytic cupric chloride in dichloromethaneꢀ
water (1:1) afforded corresponding ferrocenyl dienes FcCHC(R1)C(R2)CH2 (3ꢀ
6). On the other hand, similar reactions of 1,1?-bis-formylferrocene (2) yielded oxa-bridged [3]-ferrocenophanes having allyl
pendants Fc[CH2C(R2)CH(R1)CH-m(O)-CHCH(R1)C(R2)CH2] (8ꢀ
11). The latter appear to result from the dehydration of
/
/
/
intermediate homoallylic alcohols. Dehydration could be arrested in case of reaction of 1 and 2 with 1-bromo-3-methyl-but-2-ene,
which results in the formation of homoallylic alcohols FcCH(OH)C(Me2)CHCH2 (7) and Fc[CH(OH)C(Me2)CHCH2]2 (12),
respectively. All the reactions completely fail in absence of water.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Alkenylferrocene; 1,3-Butadienylferrocene; [3]-Oxa-ferrocenophane; Allyltin; Allylation
1. Introduction
have been achieved via copper-catalyzed coupling of 1-
ethynyl-1?-iodoferrocene, reductive coupling of 1,1?-bis-
formylferrrocene using low-valent titanium reagents,
and base-catalyzed condensation [10].
Ferrocene derivatives having olefinic architecture
gained prominence by virtue of their exciting structure,
chemical reactivity, and potential use as molecular
building blocks and in the realm of supramolecular
A major inspiration towards this study is the recent
reports on the construction of bridged metallocenes
from diallyl metallocenes via ring closing metathesis
(RCM) (Scheme 1) [11]. We believe that this will
promote a new focus on synthesis of ferrocenes with
ene-terminus. Examples of ferrocenes with terminal-
unsubstituted olefin backbone are limited to allyl, vinyl,
and butadienyl ferrocenes. Capping a ferrocene unit
with ene-chromophore majorly relies on Wittig proto-
col, McMurry coupling, and organometallic addition
chemistry as redox switching receptors [1ꢀ4]. Ferroce-
/
nophanes are a class of ferrocene macrocycles which,
beside their bifunctional character, have drawn recent
interest as building blocks for ring opening polymeriza-
tion leading to soluble ferrocene-linked polymers [5ꢀ9].
/
Ferrocenes and ferrocenaphanes having unsaturated
side chains are expected to impart physical and chemical
phenomena arising from electronic communication
through bond processes. The presence of donor func-
tionalities in the bridge can further enhance the possi-
bility of the ferrocenophane to act as potential receptor
towards cation or anion recognition. The synthesis of
ferrocenophanes with conjugated connecting bridges
reactions [12]. We have recently described
HunsdieckerꢀHeck methodology for the synthesis of
ferrocene-capped conjugated polyenes (Scheme 2, where
ZꢁCO2Me, CO2Et, CO2H, CONH2, 4-NO2C6H4Ã
a
/
/
/)
[13]. It is to be noted that due to the known limitation
of Heck reaction, the method cannot be applied for the
synthesis of polyenes with ene-terminus (ZꢁH). In this
article, we present a water-promoted carbonyl allylation
route to gain access to such building blocks from easily
/
* Corresponding author. Tel.: ꢂ
282252.
E-mail address: sroy@chem.iitkgp.ernet.in (S. Roy).
/
91-3222-283338; fax: ꢂ91-3222-
/
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00205-5

106
P. Debroy, S. Roy / Journal of Organometallic Chemistry 675 (2003) 105ꢀ112
/
Scheme 1.
Scheme 2.
available precursors such as formylferrocene and 1,1?-
bis-formylferrocene.
The g-regiospecific allylation reaction was further
extended to 1,1?-bis-formylferrocene (2). Reaction of 2
(0.25 mmol) and 3-bromopropene (2 mmol) in presence
of catalytic cupric chloride (0.05 mmol) and stannous
2. Results and discussion
chloride (1 mmol) in dichloromethaneꢀwater (1:1) at
/
Attempted allylation of 1 (in 1-mM scale) with allyl
magnesium bromide, allylindium, and allyltributyltin
were unsuccessful in our hand, resulting in complicated
and messy product mixtures in all cases. Addition of
catalysts such as Pd2(dba)3 and PtCl2(PPh3)2, which are
known to promote allylation [14], was also found to be
ineffective. Henceforth, we switched to utilize a carbonyl
allylation reaction under Barbier framework. The syn-
thetic potential and operational simplicity of Barbier
reactions are well recognized. Allyltin reagents can be
generated in situ from allyl halides and metal or metal
salts [15]. Attempted reaction of 1 with allylbromide and
tin metal powder in THF led to ferrocenyl diene (3) in
15% yield after 24 h. Most gratifyingly we observed that
a bimetallic combination comprising of catalytic cop-
per(II) halide and stoichiometric tin(II) chloride leads to
effective activation of allyl halides and promote its
reaction with formylferrocenes 1 and 2 in aqueous-
organic media. Thus, reaction of 1 (0.5 mmol) with 3-
bromopropene (1 mmol), stannous chloride dihydrate (1
mmol), and cupric chloride dihydrate (0.05 mmol) in
room temperature led to the isolation of novel oxa-
bridged [3]-ferrocenophane 8 bearing allyl side chains at
1,3-positions (Table 1). The reaction was easily extended
to substituted allyl bromides leading to the formation of
corresponding oxa-[3]-ferrocenophanes 9ꢀ11 in moder-
/
ate yields. However, the reaction of 2 with 1-bromo-3-
methyl-but-2-ene led to the isolation of homoallylic diol
12 in 72% yield (Scheme 4). We believe that the
ferrocenophanes 8ꢀ11 result from the cooperative
/
dehydration of respective diols under acid catalysis
(Scheme 5). The formation of ferrocenophane over the
other plausible dehydration product ferrocene-1,1?-bis-
diene could be due to the higher thermodynamic
stability of the former. Absence of linear or cyclic
intermolecular dehydration products is also noteworthy.
Acid catalyzed internal dehydration have been reported
earlier for 1,1?-ferrocenedimethanol, 1,1?,2,2?-ferrocene-
tetramethanol, and 3-phenyl[5]ferrocenophane-1,5-diol
[18].
The electronic spectra of the complexes 3ꢀ
bands due to dꢀd transition at 440ꢀ456 nm (Table 1).
The high-energy bands in the region 200ꢀ296 nm are
due to side chain olefinic appendage and are character-
/12 show
dichloromethaneꢀ/water (1:1, v/v) afforded ferrocenyl
/
/
diene 3 in 58% isolated yield after 2 h (Tables 1ꢀ
/3).
/
Similar reactions of 1-bromo-2-butene, 3-bromo-2-
methyl-1-propene, and 3-bromo-1-phenyl-1-propene af-
istic of pꢀ
/
p* and nꢀp* transitions [19]. The electro-
/
forded the corresponding dienes 4ꢀ
(Table 1). Most noteworthy is the effect of water [16].
Reactions without water showed B5% conversion.
/6 in moderate yields
chemical response of all the complexes shows a
reversible Fc/Fcꢂ couple. An increase in oxidation
/
potential is observed in case of ferrocenophanes 8ꢀ11,
/
Acid-catalyzed dehydration of ferrocenyl alcohols is
reported earlier [17]. Therefore, we measured the pH
of the aqueous part of the reaction mixture during the
indicative of an enhanced electron density at the metal
center due to the presence of electron-donating ether
moiety in the bridgehead [20].
reaction and found it to be highly acidic (pH 2ꢀ4). The
/
In summary, we have presented a facile carbonyl
allylation of ferrocene aldehydes which provides an easy
access to ferrocenyl building block having unsubstituted
olefinic terminus. The resulting products are potential
precursors towards further evaluation in RCM reaction.
The ferrocenophanes having bridged oxygen along with
terminal unsaturation make them interesting candidate
towards the binding of metal complexes. Further, the
stereospecificity of the reaction needs to be evaluated.
We hope to address these issues in future.
reaction can be rationalized as in Scheme 3, which
involves (a) prior formation of cationic allyltin, (b) allyl
transfer from allyltin to FcÃ/CHO, and (c) dehydration
of the intermediate homoallylic alcohol to the diene 3.
Indeed, using 1-bromo-3-methyl-but-2-ene, dehydration
could be arrested leading to the formation of homo-
allylic alcohol 7 which was isolated in 96% yield (Scheme
4). It is to be noted that the reactions are 100% g-
regioselective, affording products with terminal-unsub-
stituted olefin linkage.

Table 1
Products from the allylation of formylferrocene and 1,1?-bis-formylferrocene using bimetallic copper(II)/tin(II) reagent
d
E1/2 (V)
X
Y
H
R1 R2 R3 Product number a
Time (h)
2
Yield (%)
58
m.p. (8C) b,c
Anal. Found (Calc.) (%)
5.86 (5.93)
lmax(log o) e assignment
CHO
H
H
H
H
H
H
Me
H
H
H
H
3
4
80
70.28 (70.62)
70.99 (71.46)
70.91 (71.46)
76.15 (76.45)
66.94 (67.62)
69.96 (70.15)
70.97 (71.44)
71.19 (71.44)
77.82 (78.26)
68.94 (69.11)
0.48
0.47
0.43
0.47
0.43
0.57
0.52
0.53
0.52
0.43
455 (2.4), dꢀ
203 (4.0), 251 (3.9), 296 (3.9), pꢀ
453 (2.5), dꢀ
206 (4.2), 250 (4.0), 294 (4.0), pꢀ
442 (2.0), dꢀ
205 (4.2), 275(3.4), pꢀ
454 (2.7), dꢀ
/
d
/
p*
p*
c
CHO
CHO
CHO
CHO
H
H
H
H
Me
H
H
2
2
2
2
5
2
3
3
2
60
55
47
96
32
55
30
49
72
6.32 (6.40)
6.49 (6.40)
5.70 (5.77)
6.93 (7.09)
6.22 (6.54)
7.22 (7.19)
6.99 (7.19)
6.01 (6.13)
7.82 (7.91)
/
d
/
c
Me
H
5
/
d
/
p*
Ph
Me
H
6
78
/
d
208 (6.3), 302(3.9), pꢀ
/
p*
H
7
49
440 (1.7), dꢀ
207 (4.3), pꢀ
457 (1.9), dꢀ
201 (4.2), pꢀ
447 (1.9), dꢀ
200 (4.1), pꢀ
453 (2.0), dꢀ
252 (3.4), pꢀ
456 (2.4), dꢀ
203 (4.3), pꢀ
441 (1.9), dꢀ
209 (4.4), pꢀ
/
d
/
p*
d
c
CHO CHO
H
8
/
/
p*
d
c
c
CHO CHO Me
CHO CHO
H
9
/
/
p*
d
H
Me
H
10
11
/
/
p*
d
CHO CHO Ph
CHO CHO Me
77
/
/
p*
d
c
H
Me 12
/
/
p*
a
Homoallylic alcohols and dehydrated product mixtures are also formed.
Uncorrected.
Low-melting solid.
All the potential values are with reference to Fc/Fcꢂ external standard. E1/2
b
c
d
ꢁ/
(Epaꢂ
Epc)/2.0 for reversible oxidation (in volts). All the data are taken from a 50 mV sꢃ1 scan rate for 0.001 M
/
sample solutions in acetonitrile with 0.1 M tetrabutylammonium perchlorate as electrolyte.
lmax (in nanometer) for acetonitrile solutions (1ꢄ
10ꢃ4 M).
e
/

Table 2
2
4
4
3
2
1
4
3
2
1
1
3
5
1H-NMR data for the allylation products of formylferrocene FcC H C(R?)C(R?)C H (3ꢀ
/
6), FcC H(OH)C(Me)2C H C H (7), 1,1?-bis-formylferrocene FcC H C(R2)C H(R1)C Hꢃmꢃ(O)ꢃ
4
2
2
2
2
2
5
3
1
5
3;4
2
1
C H C H(R1)C(R2)C H] (8ꢀ
/
11), and Fc[C H(OH)C(Me)2C H C H]2 (12)
2
2
Product num- Fc
ber
H1
H2
H3
H4
H5
OH
3
4
4.12, s, 5H; 4.37, s, 2H; 4.25, s, 5.09, d, 1H, Jꢁ
2H
4.13, s, 5H; 4.33, s, 2H; 4.22, s, 5.13, d, 1H, Jꢁ
/
10; 5.27, d, 1H, Jꢁ
/
15
6.84ꢃ
/
7.20, m, 1H
6.34, dd, 1H, Jꢁ
15
/
10, 6.06, d, 1H, Jꢁ
/
11
/11; 5.27, d, 1H, Jꢁ
/
17
7.05, dd, 1H, Jꢁ
17
/
10, 1.90, s, 3H
5.75, d, 1H, Jꢁ
8, 7.20ꢃ7.50, m, 5H
11, 1.07, s, 6H
6.13, s, 1H
2H
5
4.18, s, 5H; 4.38, s, 2H; 4.60, s, 5.30, s, 2H
2H
1.88, s, 3H
/10
5.65, d, 1H, Jꢁ
/
10
6
4.00, s, 5H; 4.01, s, 2H; 4.18, s, 5.18, d, 1H, Jꢁ
/
10; 5.29, d, 1H, Jꢁ
11; 5.05, d, 1H, Jꢁ
10; 5.07, d, 2H, Jꢁ
11; 5.01, d, 2H, Jꢁ
/
16
16
15
16
6.28, dd, 1H, Jꢁ
16
/
/
6.02, s, 1H
2H
7
4.51, s, 9H
5.01, d, 1H, Jꢁ
/
/
5.89, dd, 1H, Jꢁ
16
/
3.65, s, 1H
1.7, brs,
1H
8
4.23, m, 4H; 4.12, m, 2H; 4.04, 5.01, d, 2H, Jꢁ
/
/
5.92ꢃ
/
5.75, m, 2H
2.69ꢃ
2.60ꢃ
2.67ꢃ
2.58ꢃ
10, 1.05, s, 6H
/
2.41, m, 2H
2.40, m, 2H
2.57, m, 2H
2.40, m, 2H
2.69ꢃ
2H
1.29, s, 6H
/
2.41, m,
3.67ꢃ
/
3.60, m,
m, 2H
2H
9
4.19, m, 4H; 4.16, m, 2H; 4.03, 4.89, d, 2H, Jꢁ
/
/
6.07ꢃ
/
5.98, m, 2H
/
3.37ꢃ
2H
3.78, t, 2H, Jꢁ
/
3.27, m,
m, 2H
10
11
12
4.23, m, 4H; 4.13, m, 2H; 4.04, 4.72, s, 4H
m, 2H
1.72, s, 6H
6.08ꢃ5.90, m, 2H
/
2.44ꢃ
2H
/
2.36, m,
7.32, m,
/
7
4.16, m, 4H; 4.13, m, 2H; 4.02, 4.98, d, 2H, Jꢁ
/
11; 5.08, d, 2H, Jꢁ
/
17; 5.04, d,
/
/
7.44ꢃ
/
3.61ꢃ3.59, m,
/
m, 2H
4.50, s, 8H
2H, Jꢁ
5.12, d, 2H, Jꢁ
/
11
10H
1.05, s, 6H
2H
3.75, s, 2H
/
16
5.89, dd, 2H, Jꢁ
/
1.9, brs,
2H
17

P. Debroy, S. Roy / Journal of Organometallic Chemistry 675 (2003) 105ꢀ
/
112
109
Table 3
13C-NMR data for the allylation products of formylferrocene Fc C H C(R1) C(R2) C H2 (3ꢀ
3?
2?
4
3
2
1
4
3
3?
2
1
/
6), Fc C H(OH) C(Me)2 C H C H2 (7), 1,1?-bis-
2?
3?
3?
2?
1
2
3
4
4
3
2
1
4
3 2 1
3?
formylferrocene Fc C H2 C(R2) C H(R1) C Hꢃmꢃ(O)ꢃC H C H(R1) C(R2) C H2] (8ꢀ
11), and Fc[C H(OH) C(Me)2 C H C H2]2 (12)
/
Product number
Fc
C1
C2
C2?
C3
C3?
C4
C5H5
C5H4
3
4
5
6
7
69.0
69.4
68.9
69.8
71.1
66.5, 68.6, 82.5
68.7, 68.5, 82.3
66.6, 68.1, 84.3
69.1, 68.7, 81.9
69.7, 70.8, 84.2
114.4
113.8
112.4
113.9
112.4
137.2
135.5
128.2
134.9
145.5
127.1
127.3
130.9
130.0
129.1
129.5
91.8
20.1
20.3 133.8
127.0
41.1
128.9, 128.6, 128.4, 128.1
22.2, 23.9
Cpunsubs
Cpsubs
8
9
68.3, 70.1, 71.6
68.3, 70.0, 72.0
71.5, 70.0, 68.2
72.1, 70.2, 68.4
71.0, 70.4, 69.7
88.8
88.3
89.1
87.7
84.0
116.3
114.2
112.2
113.9
113.4
135.6
140.9
125.3
141.6
146.0
40.3
42.9
65.4
65.7
65.4
65.9
92.6
17.3
10
11
12
22.8
43.9
55.7
41.9
129.6, 128.5, 128.4, 127.1
24.1, 21.0
3. Experimental
range 60ꢀ
/
80 8C. Silica gel (60ꢀ120-mesh SRL) was used
/
for all column chromatography. For reaction monitor-
ing, precoated silica gel 60 F254 TLC sheets (MERCK)
were used. All reactions were performed under an inert
atmosphere of argon using standard Schlenk technique.
Starting materials 1 and 2 were prepared by known
method [21]. Allyl bromides were prepared by the
reaction of the corresponding allyl alcohols with phos-
phorus tribromide and pyridine in ether. Stannous
chloride dihydrate and cupric chloride dihydrate are
commercially available.
Melting points were measured using a Toshniwal
1
melting point apparatus and are uncorrected. H (200
MHz)- and 13C (54.6 MHz)-NMR spectra were re-
corded in CDCl3 on BRUKER-AC 200 MHz spectro-
meter. Me4Si was used as the internal standard. EIMS
(70 eV) spectra were recorded using Autospec-M mass
spectrometer. IR spectra were obtained using a Perkinꢀ
/
Elmer 883 spectrophotometer. Electronic absorption
spectra were recorded in HPLC grade acetonitrile using
Shimadzu UV-1601 UVꢀvis Spectrometer. Cyclic vol-
/
tammetry (CV) experiments were carried out with
Model CH-600A Electrochemical Analyser at room
temperature with a conventional three-electrode config-
uration consisting of platinum working, and auxiliary
electrodes and Ag/AgCl reference electrode containing
aqueous 3 M KCl. HPLC grade acetonitrile was used as
solvent in all cases. The supporting electrolyte was (0.1
M) tetrabutylammonium perchlorate (Fluka) and used
as-received. The redox potentials (E1/2) were measured
in volts with respect to Ag/Agꢂ. The data were
3.1. General procedure (A) for the allylation of
formylferrocene 1
The appropriate allyl bromide (1.0 mmol) dissolved in
distilled dichloromethane (0.5 ml) was added to a stirred
solution of SnCl2×
/
2H2O (225.6 mg, 1 mmol) and CuCl2×
/
2H2O (8.50 mg, 0.05 mmol) in water (2.5 ml) at ambient
temperature. Formylferrocene (107 mg, 0.5 mmol)
dissolved in distilled dichloromethane (2.0 ml) was
added dropwise to the clear solution and the reaction
was monitored (TLC monitoring on silica gel, eluent
calibrated using Fc/Fcꢂ couple (E1/2
ꢁ0.46 V). Dichlor-
/
omethane was distilled from phosphorus pentoxide.
Petroleum ether refers to the fraction boiling in the
ethyl acetateꢀ
tion, the product was extracted with dichloromethane
(3ꢄ15 ml). The organic layer was washed with 5%
aqueous sodium bicarbonate (10 ml), water (2ꢄ5 ml),
and brine (2ꢄ10 ml), dried over MgSO4, and concen-
/
petroleum ether, 1:9 (v/v)). Upon comple-
/
/
/
Scheme 3.
Scheme 4.

110
P. Debroy, S. Roy / Journal of Organometallic Chemistry 675 (2003) 105ꢀ112
/
3.1.5. Synthesis of 2,2-dimethyl-1-ferrocenyl-but-3-en-1-
ol (7)
Following general procedure A, reaction of 1-bromo-
3-methyl-but-2-ene (149 mg, 1.0 mmol) and 1 (107 mg,
0.5 mmol) gave a yellow solid (136 mg, 96%) after 2 h.
Rfꢁ
0.58. EIMS: m/z (relative intensity), 284 (Mꢂ, 26);
/
Scheme 5.
215 (72); 186 (100); 121 (42); 56 (14). IR (CHCl3, cmꢃ1):
3450 vs, 2926 w, 1722 w, 1631 m, 1391 w, 1107 w, 770 w.
HRMS Calc. for C16H20FeO, m/z: 284.0863; Found, m/
z: 284.0798.
trated under reduced pressure. The pure products were
obtained after column chromatography on silica gel
using an ethylacetateꢀ
/
petroleum ether (2:98, v/v) mix-
ture as the eluent.
3.2. General procedure (B) for the allylation of 1,1?-bis-
formylferrocene (2)
3.1.1. Synthesis of buta-1,3-dienyl-ferrocene (3)
Following general procedure A, reaction of 3-bromo-
propene (121 mg, 1.0 mmol) and 1 (107 mg, 0.5 mmol)
gave a red plate-like crystalline solid (70 mg, 58%) after
The appropriate allyl bromide (1.0 mmol) dissolved in
distilled dichloromethane (0.5 ml) was added to a stirred
2 h. Rfꢁ
0.8. IR (CHCl3, cmꢃ1): 3440 vs, 2760 w, 1660
/
solution of SnCl2×
/
2H2O (225.6 mg, 1 mmol) and CuCl2×
/
w, 1620 m (gCÄCstr), 1102 w, 769 w. HRMS Calc. for
C14H14Fe, m/z: 238.0444; Found, m/z: 238.0570.
2H2O (8.50 mg, 0.05 mmol) in water (2.5 ml) at ambient
temperature. 1,1?-Bis-formylferrocene (2) (61 mg, 0.25
mmol) dissolved in distilled dichloromethane (2.0 ml)
was added dropwise to the clear solution and the
reaction was monitored (TLC monitoring on silica gel,
3.1.2. Synthesis of (2-methyl-buta-1,3-dienyl)-ferrocene
(4)
Following general procedure A, reaction of 1-bromo-
2-butene (135 mg, 1.0 mmol) and 1 (107 mg, 0.5 mmol)
eluent ethyl acetateꢀ
product was extracted with dichloromethane (3ꢄ
ml). The organic layer was washed with 5% aqueous
sodium bicarbonate (10 ml), water (2ꢄ5 ml), and brine
(2ꢄ10 ml), dried over MgSO4, and concentrated under
/
petroleum ether, 2:8 (v/v)). The
/
15
gave a deep orange liquid (76 mg, 60%) after 2 h. Rfꢁ
/
/
0.8. EIMS: m/z (relative intensity), 252 (Mꢂ, 100); 237
(9); 186 (49); 129 (18); 121 (30); 91 (5); 56 (27); 44 (11).
IR (CHCl3, cmꢃ1): 3450 m, 2930 w, 1633 w, 1220 w, 771
vs. HRMS Calc. for C15H16Fe, m/z: 252.0601; Found,
m/z: 252.0595.
/
reduced pressure. The pure products were obtained after
column chromatography on silica gel using
ethylacetateꢀ
/
petroleum ether (2:98) mixture as the
eluent.
3.1.3. Synthesis of (3-methyl-buta-1,3-dienyl)-ferrocene
(5)
Following general procedure A, reaction of 3-bromo-
2-methyl-1-propene (135 mg, 1.0 mmol) and 1 (107 mg,
0.5 mmol) gave a brown low-melting solid (70 mg, 55%)
3.2.1. Synthesis of 1,3-bis-(2-propenyl)-2-oxa-[3]-
(1,1?)ferrocenophane (8)
Following general procedure B, reaction of 3-bromo-
propene (121 mg, 1.0 mmol) and 2 (61 mg, 0.25 mmol)
gave a red oil (25 mg, 32%) after 5 h. Rfꢁ0.86. EIMS:
/
after 2 h. Rfꢁ0.64. EIMS: m/z (relative intensity), 252
/
m/z (relative intensity), 308 (Mꢂ, 100); 238 (30); 172
(34); 121 (42); 115 (30); 56 (71). IR (CHCl3, cmꢃ1): 3435
m, 1634 w, 1206 m, 1180 w, 771 vs. HRMS Calc. for
C18H20FeO, m/z: 308.0863; Found, m/z: 308.0858.
(Mꢂ, 12); 237 (11); 186 (19); 121 (90); 84 (100); 69 (9);
56 (52); 49 (31). IR (CHCl3, cmꢃ1): 3438 m, 1633 w,
1221 w, 771 vs. HRMS Calc. for C15H16Fe, m/z:
252.0601; Found, m/z: 252.0611.
3.1.4. Synthesis of (2-phenyl-buta-1,3-dienyl)-ferrocene
(6)
3.2.2. Synthesis of 1,3-bis-(1-methyl-2-propenyl)-2-oxa-
[3]-(1,1?)ferrocenophane (9)
Following general procedure A, reaction of 3-bromo-
1-phenyl-1-propene (197 mg, 1.0 mmol) and 1 (107 mg,
0.5 mmol) gave a deep red crystalline solid (74 mg, 47%)
Following general procedure B, reaction of 1-bromo-
2-butene (135 mg, 1.0 mmol) and 2 (61 mg, 0.25 mmol)
gave a yellow low-melting solid (46 mg, 55%) after 2 h.
after 2 h. Rfꢁ
/
0.64. EIMS: m/z (relative intensity), 314
Rfꢁ
0.8. EIMS: m/z (relative intensity), 336 (Mꢂ, 44);
/
(Mꢂ, 100); 248 (24); 192 (26); 165 (22); 121 (38); 91 (26);
56 (26). IR (CHCl3, cmꢃ1): 3431 s, 2854 w, 1632 m, 1219
w, 1103 w, 770 m. HRMS Calc. for C20H18Fe, m/z:
314.2081; Found, m/z: 314.2096.
252 (22); 185 (16); 135 (10); 129 (20); 121 (28); 77 (10).
IR (CHCl3, cmꢃ1): 3439 m, 1634 w, 1219 m, 1180 w,
1102 w, 771 vs. HRMS Calc. for C20H24FeO, m/z:
336.1176; Found, m/z: 336.1198.

P. Debroy, S. Roy / Journal of Organometallic Chemistry 675 (2003) 105ꢀ
/
112
111
Inorg. Chem. 39 (2000) 953;
(c) R.W. Heo, F.B. Somoza, T.R. Lee, J. Am. Chem. Soc. 120
(1998) 1621.
3.2.3. Synthesis of 1,3-bis-(2-methyl-2-propenyl)-2-oxa-
[3]-(1,1?)ferrocenophane (10)
Following general procedure B, reaction of 3-bromo-
2-methyl-1-propene (135 mg, 1.0 mmol) and 2 (61 mg,
0.25 mmol) gave an orange solid (26 mg, 30%) after 3 h.
[3] (a) H. Nock, H. Schottenberger, J. Org. Chem. 58 (1993) 7045;
(b) A. Togni, G. Rihs, Organometallics 12 (1993) 3368;
(c) A. Togni, M. Hobi, G. Rihs, G. Rist, A. Albinati, P. Zanello,
D. Zech, H. Keller, Organometallics 13 (1994) 1224;
(d) L.M. Tolbert, X. Zhao, Y. Ding, L.A. Bottomley, J. Am.
Chem. Soc. 117 (1995) 12891;
Rfꢁ
0.86. EIMS: m/z (relative intensity), 336 (Mꢂ,
/
100); 316 (44); 281 (65); 252 (67); 186 (72); 121 (62); 56
(56). IR (CHCl3, cmꢃ1): 3200 m, 2738 w, 1620 w, 1385
w, 1220 m, 762 vs. HRMS Calc. for C20H24FeO, m/z:
336.1176; Found, m/z: 336.1166.
(e) E. Stankovic, S. Toma, R.V. Boxel, I. Asselberghs, A.
Persoons, J. Organomet. Chem. 637ꢀ639 (2001) 426;
/
(f) B. Bildstein, W. Skibar, M. Schweiger, H. Kopacka, K. Wurst,
J. Organomet. Chem. 622 (2001) 135.
[4] (a) A.E. Kaifer, S. Mendza, in: G.W. Gokel (Ed.), Comprehensive
Supramolecular Chemistry I, Pergamon Press, Oxford, 1996, pp.
3.2.4. Synthesis of 1,3-bis-(1-phenyl-2-propenyl)-2-oxa-
[3]-(1,1?)ferrocenophane (11)
701ꢀ732;
/
Following general procedure B, reaction of 3-bromo-
1-phenyl-1-propene (197 mg, 1.0 mmol) and 2 (61 mg,
0.25 mmol) gave a deep red solid (56 mg, 49%) after 3 h.
(b) P.D. Beer, A.R. Graydon, A.O.M. Johnson, D.K. Smith,
Inorg. Chem. 36 (1997) 2112;
(c) E.C. Constable, Angew. Chem. Int. Ed. Engl. 30 (1991) 407.
[5] (a) R.W. Heo, T.R. Lee, J. Organomet. Chem. 578 (1999) 31 (and
references therein);
Rfꢁ
0.87. EIMS: m/z (relative intensity), 460 (Mꢂ, 91);
/
442 (69); 343 (20); 314 (14); 249 (100); 191 (16); 178 (10);
165 (11); 147 (10); 117 (42); 91 (24); 57 (9). IR (CHCl3,
cmꢃ1): 3438 vs, 2928 w, 1724 w, 1633 m, 1221 w, 1110
w, 770 s. HRMS Calc. for C30H28FeO, m/z: 460.3987;
Found, m/z: 460.3992.
(b) P. Nguyen, P. Go´mez-Elipe, I. Manners, Chem. Rev. 99 (1999)
1515;
(c) R. Resendes, J.M. Nelson, A. Fischer, F. Jakle, A. Bartole,
¨
A.J. Long, I. Manners, J. Am. Chem. Soc. 123 (2001) 2116.
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1621.
[7] (a) M. Rosenblum, J.O. Santer, W.G. Howells, J. Am. Chem. Soc.
85 (1963) 1450;
3.2.5. Synthesis 1,1?-bis-2,2-dimethyl-1-ferrocenyl-but-3-
en-1-ol (12)
(b) H.L. Lentzner, W.E. Watts, Chem. Commun. (1970) 26.;
(c) T.E. Bitterwolf, M.J. Golightly, Inorg. Chim. Acta 84 (1984)
153;
Following general procedure B, reaction of 1-bromo-
3-methyl-but-2-ene (149 mg, 1.0 mmol) and 2 (61 mg,
0.25 mmol) gave a yellow solid (69 mg, 72%) after 2 h.
(d) A.F. Cunningham, J. Am. Chem. Soc. 113 (1991) 4864;
(e) M.L. McKee, J. Am. Chem. Soc. 115 (1993) 2818;
(f) U.T. Mueller-Westerhoff, T.J. Hass, G.F. Swiegers, T.K.
Leipert, J. Organomet. Chem. 472 (1994) 229.
[8] U.T. Mueller-Westerhoff, A. Nazzal, W. Prossdorf, J. Am. Chem.
Soc. 103 (1981) 7678.
Rfꢁ
0.7. EIMS: m/z (relative intensity), 382 (Mꢂ, 30);
/
229 (72); 215 (72); 186 (100); 129 (5); 121 (42); 56 (14); 44
(8). IR (CHCl3, cmꢃ1): 3435 vs, 2938 w, 1642 m, 1219
m, 1105 w, 1060 w; 768 s; 617 w. HRMS Calc. for
C22H30FeO2, m/z: 382.1595; Found, m/z: 382.1532.
[9] I. Manners, Adv. Organomet. Chem. 37 (1995) 131.
[10] (a) M. Rosenblum, N.M. Brawn, D. Ciappenelli, J. Tancrede, J.
Organomet. Chem. 24 (1970) 469;
(b) A. Kasahara, T. Izumi, Chem. Lett. (1978) 21.;
(c) A. Kasahara, T. Izumi, I. Shimizu, Chem. Lett. (1979) 1317.;
(d) S. Kamiyam, A. Kasahara, T. Izumi, I. Shimizu, H. Watabe,
Bull. Chem. Soc. Jpn. 54 (1981) 2079.
Acknowledgements
Financial support from DST and CSIR is thankfully
acknowledged. We thank Dr. M. Vairamani for mass
spectral analyses. P.D. thanks the institute for the award
of a Junior Research Fellowship.
[11] (a) M. Ogasawara, T. Nagano, T. Hayashi, J. Am. Chem. Soc.
124 (2002) 9068;
(b) A.J. Locke, C. Jones, C.J. Richards, J. Organomet. Chem.
637ꢀ639 (2001) 669.
/
[12] (a) S.-J. Jong, J.-M. Fang, J. Org. Chem. 66 (2001) 3533 (and
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(b) W.-Y. Liu, Q.-H. Xu, Y.-X. Ma, Y.-M. Liang, N.-L. Dong,
D.-P. Guan, J. Organomet. Chem. 625 (2001) 128;
(c) For recent reports on the synthesis of alkenylferrocenes, please
see: S. El-Tamany, F.W. Raulfs, H. Hopf, Angew. Chem. Int. Ed.
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