A convenient synthesis of E-alkenylferrocenes

Article abstract of DOI:10.1016/S0022-328X(01)00862-2

Alkenylferrocenes, FcCHCHR [R=(CH₂)_nCH₃, n=0-4], and 1,1′-bisalkenylferrocenes, Fc(CHCHR)₂ (R=CH₃, CH₂CH₃) were synthesized by elimination reaction from the corresponding α-hydroxyferrocenylalkanes using methanesulfonylchloride and triethylamine.

Full text of DOI:10.1016/S0022-328X(01)00862-2

Journal of Organometallic Chemistry 629 (2001) 208–212
www.elsevier.com/locate/jorganchem
Short Communication
A convenient synthesis of E-alkenylferrocenes
Walther G. Jary, Arnulf-Kai Mahler, Thomas Purkathofer, Judith Baumgartner *
Institute for Organic Chemistry, Technical Uni6ersity of Graz, Stremayrgasse 16, A-8010 Graz, Austria
Received 4 January 2001; received in revised form 27 April 2001; accepted 29 April 2001
Abstract
Alkenylferrocenes, FcCHCHR [R=(CH ) CH , n=0–4], and 1,1%-bisalkenylferrocenes, Fc(CHCHR) (R=CH , CH CH )
2
n
3
2
3
2
3
were synthesized by elimination reaction from the corresponding a-hydroxyferrocenylalkanes using methanesulfonylchloride and
triethylamine. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Alkanoylferrocenes; Dialkanoylferrocenes; Hydroxyalkylferrocene; Dihydroxyalkylferrocene; Alkenylferrocene; Dialkenylferrocene
1
. Introduction
alkenylferrocenes as starting materials. However, al-
though there are several methods known for the forma-
tion of vinyl- or propenylferrocene, derivatives with
longer alkenyl chains are hardly known in literature.
The same holds for their precursors, namely, the respec-
tive alkanoyl- and hydroxyferrocenes. For the few
derivatives described in the literature so far, almost no
NMR data have been reported.
The reactivity and chemical properties of ferrocene
derivatives have been widely explored [1]. The ongoing
interest in ferrocene chemistry stems from their increas-
ing use and application in the fields of organic synthe-
sis, catalysis, and material science [2]. The ferrocenyl
ligands represent one of the most important classes
among the different types of chiral ligands used in
asymmetric homogenous catalysis [3] and they find
application in a variety of transition-metal catalyzed
reactions. a-Ferrocenylalkylamines are by far the most
common chiral ferrocene starting materials [4]. The
stereoselective formation of a-chiral ferrocenyl carboca-
tions without loss of chiral information offers the possi-
2
. Results and discussion
The Friedel–Crafts [7] acylation of ferrocene is one
of the most important methods to prepare alkanoylfer-
rocenes. The high reactivity of these carbonyl com-
pounds towards electrophilic substitution [8] makes
them the most often used prochiral starting materials in
ferrocene chemistry. A standard procedure for this
reaction is the use of acid chlorides and aluminum
chloride [9]. Unfortunately, in our hands under these
conditions, we obtained exclusively diacylation (1, 4)
instead of monoacylation. However, employment of the
respective acid anhydride and boron trifluoride etherate
in dichloromethane [10,11] produced the desired prod-
ucts (7, 10 [12]; 13 [13]; 16 [12], 19) in good to excellent
yields.
bility to introduce
a
variety of hetero atom
functionality at this stereogenic center [5]. With this in
mind, we started to investigate methods for the synthe-
sis of new, centrally chiral ferrocenyl diols, which can
serve as precursors for new chiral ligands [6].
Application of Sharpless’ asymmetric dihydroxyla-
tion reaction for this purpose requires isomerically pure
*
Corresponding author. Tel.: +43-316-8738219; fax: +43-316-
8
0
738740.
E-mail address: judith@orgc.tu-graz.ac.at (J. Baumgartner).
022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)00862-2

W.G. Jary et al. / Journal of Organometallic Chemistry 629 (2001) 208–212
209
Recently, an electrochemical acylation of ferrocene
was reported by the in situ generation of the acylating
agent and the catalyst [14]. Under these conditions,
compounds 7, 10, and 13 were obtained. The same
authors also presented a Friedel–Crafts acylation pro-
3
. Experimental
The melting points were recorded on a Tottoli ap-
paratus (B u¨ chi) and are uncorrected. NMR spectra
were recorded on Bruker MSL 300, or Varian Gemini
2
cedure with PCl and AlCl for the formation of com-
3
3
pounds 1, 4, 7, 10, and 16, but unfortunately no
spectral data were reported [15].
00 spectrometers. J-values are reported in Hz. All
NMR spectra were recorded in CDCl . Flash chro-
3
All diols (2, 5, 8, 11, 14, 17, and 20) were prepared by
the reduction of the corresponding ketones with LAH
in diethylether using a standard procedure [10,16].
The synthesis of propenylferrocene has been reported
several times, but only once both isomers were obtained
in pure state, employing modifications of the Wittig
reaction [17]. Under the standard Wittig reaction condi-
tions with alkyltriphenylphosphoranes [18], E/Z ratios
of about 3:1 for the alkenylferrocenes 9, 12, and 15
were reported.
matography was performed on silica gel 60 (0.040–
0.063 mm, Merck). Mixtures of cyclohexane and ethyl
acetate were used as eluents. Reagents were obtained
from commercial sources and used as received.
Dichloromethane was distilled from P O , Et O from
2
5
2
CaH and Et N from KOH prior to use.
2
3
3.1. Synthesis of bisalkanoylferrocenes 1 and 4
Ferrocene (5.0 g, 27 mmol) and AlCl 98% (11.0 g, 83
3
mmol) were suspended in 70 ml CH Cl and cooled to
An alternative method for the synthesis of alkenylfer-
rocenes, is the dehydration of the corresponding alco-
hols with neutral alumina yielding about 90% d.e. of
the E isomer in the case of 9, but the reported yields of
about 50% are not convincing for the preparation of a
starting material [9]. Changing to acidic alumina im-
proves this yield to 60–80% [19]. Another attempt was
reported using Fe (CO) as a dehydration reagent with
2
2
0
°C. The respective acid chloride (three equivalents)
was added dropwise over 10 min and the reaction was
stirred at room temperature (r.t.) for additional 2 h
until complete conversion was achieved. The mixture
was poured on ice water and the layers were separated.
The organic layer was washed with a saturated
NaHCO solution and dried over Na SO . The solvent
3
2
4
2
9
was removed in vacuo and the pure product was ob-
tained after flash chromatography.
a similar yield for 9 [20].
As we were interested in a method which is simple
and produces reliably just the E isomer, we decided to
attempt the elimination of the secondary alcohol via
reaction with methanesulfonyl chloride and triethy-
lamine [21]. By this reaction, we obtained exclusively
the E isomers in good yields for the cases of 6, 12, 15,
3
.1.1. 1,1%-Bis(hydroxypropanoyl)ferrocene (1)
A red–brown oil was obtained in 98% yield. H-
NMR (200 MHz, l ppm): 1.16 (t, J=7.3 Hz, 6H,
CH ); 2.66 (q, J=7.3 Hz, 4H, 2CH ); 4.45 (t, J=1.9
1
2
3
2
13
Hz, 4H, Fc); 4.75 (t, J=1.9 Hz, 4H, Fc). C-NMR (50
MHz, l ppm): 8.2, 33.1, 70.5, 73.3, 80.3, 204.1. HRMS;
Found: 298.06561; Calc. for C H O Fe [M ]:
18, and 21. Only for the propenyl compounds 3 and 9,
+
both isomers were formed under these conditions as
16
18
2
inseparable mixtures.
298.06559.

210
W.G. Jary et al. / Journal of Organometallic Chemistry 629 (2001) 208–212
3
.1.2. 1,1%-Bis(butanoyl)ferrocene (4)
204.8. HRMS; Found: 284.08631; Calc. for C H OFe
[M ]: 284.08633.
16
20
+
Orange crystals (m.p.: 73–74°C, identical with Lit.
1
[22]) were obtained in 93% yield. H-NMR (200 MHz,
l ppm): 1.00 (t, J=7.5 Hz, 6H, 2CH ); 1.72 (m, 4H,
3.2.5. 1-Heptanoylferrocene (19)
A brown oil was obtained in 63% yield. H-NMR
(200 MHz, l ppm): 0.89 (t, J=6.4 Hz, 3H, CH ); 1.32
3
1
2
CH ); 2.63 (t, J=7.4 Hz, 4H, 2CH ); 4.48 (t, J=1.5
2
2
1
3
Hz, 4H, Fc); 4.77 (t, J=1.9 Hz, 4H, Fc). C-NMR (50
MHz, l ppm): 14.1, 17.7, 41.9, 70.6, 73.4, 80.5, 203.7.
HRMS; Found: 326.0977; Calc. for C H O Fe [M ]:
3
(m, 6H, 3CH ); 1.68 (m, 2H, CH ); 2.67 (t, J=7.6 Hz,
2
2
+
2H, CH ); 4.17 (s, 5H, Fc); 4.46 (t, J=1.8 Hz, 2H, Fc);
18
22
2
2
1
3
326.0969.
4.76 (t, J=1.9 Hz, 2H, Fc). C-NMR (50 MHz, l
ppm): 14.2, 22.6, 24.6, 29.3, 31.8, 39.8, 69.4, 69.8, 72.1,
79.2, 204.7. HRMS; Found: 298.10151; Calc. for
3.2. Synthesis of alkanoylferrocenes 7, 10, 13, 16, and 19
+
C H OFe [M ]: 298.10198.
17
22
Ferrocene (5.0 g, 27 mmol) and the respective acid
anhydride (two equivalents) were suspended in 40 ml
3.3. Synthesis of bishydroxyferrocenes 2, 5 and
hydroxyferrocenes 8, 11, 14, 17, and 20
CH Cl and cooled to 0°C. Boron trifluoride etherate
2
2
99% (30 ml) was added via a syringe over 10 min and
the reaction was stirred at r.t. for additional 3 h until
the reaction was complete. The following work-up pro-
cedure was analogous to the one described for the
bisalkanoylferrocenes.
To an ice-cooled solution of the alkanoylferrocene in
Et O, LAH (1.2 equivalents and 2.4 equivalents for the
2
bisalkanylferrocenes) was added in several portions.
After stirring for 3 h, the reaction was complete and a
saturated MgSO solution (4 ml for each gram of LAH)
4
®
3.2.1. 1-Propionylferrocene (7)
was added dropwise. After filtration over Celite , the
Dark-red crystals (m.p.: 67–68°C, Lit. [9]: 30–31°C)
were obtained in 98% yield. H-NMR (200 MHz, l
solvent was removed in vacuo and the product was
purified by flash chromatography.
1
ppm): 1.14 (t, J=7.3 Hz, 3H, CH ); 2.68 (q, J=7.5
3
Hz, 2H, CH ); 4.12 (s, 5H, Fc); 4.42 (s, 2H, Fc); 4.72 (s,
3.3.1. 1,1%-Bis(hydroxypropyl)ferrocene (2)
2
1
3
2H, Fc). C-NMR (50 MHz, l ppm): 8.6, 32.8, 69.3,
An orange oil was obtained in a yield of 66%.
H-NMR (200 MHz, l ppm): 0.94 (m, 6H, 2CH ); 1.10
1
6
9.8, 72.1, 78.9, 204.9. HRMS; Found: 242.03943; Calc.
3
+
for C H OFe [M ]: 242.03936.
(m, 4H, 2CH ); 1.85 (bs, 1H, OH); 2.05 (bs, H, OH);
1
3
14
2
13
4
.11–4.43 (m, 10H, Fc, 2CH). C-NMR (50 MHz, l
3
.2.2. 1-Butanoylferrocene (10)
A dark-red oil was obtained in 98% yield. H-NMR
ppm): 10.0, 10.2, 32.1, 32.8, 65.5, 66.3, 66.5, 67.0, 67.4,
67.5, 67.6, 70.8, 70.5, 93.9, 94.0. HRMS; Found:
1
+
(
300 MHz, l ppm): 0.96 (t, J=7.4 Hz, 3H, CH ); 1.70
302.0971; Calc. for C H O Fe [M ]: 302.0969.
3
16 22
2
(
m, 2H, CH ); 2.63 (t, J=7.3 Hz, 2H, CH ); 4.14 (s,
2
2
5
H, Fc); 4.43 (t, J=1.8 Hz, 2H, Fc); 4.73 (t, J=1.6
3.3.2. 1,1%-Bis(hydroxybutyl)ferrocene (5)
A brown oil was obtained in 94% yield. H-NMR
1
3
1
Hz, 2H, Fc). C-NMR (50 MHz, l ppm): 14.2, 18.0,
4
2
1.6, 69.3, 69.7, 72.1, 79.3, 204.3. HRMS; Found:
(200 MHz, l ppm): 0.94 (m, 6H, 2CH ); 1.29–1.70 (m,
3
+
56.05511; Calc. for C H OFe [M ]: 256.05503.
8H, 4CH ); 1.88 (bs, 1H, OH); 2.28 (bs, H, OH);
1
4
16
2
13
4
.12–4.27 (m, 8H, Fc); 4.45 (m, 2H, 2CH). C-NMR
3
.2.3. 1-Pentanoylferrocene (13)
A red oil was obtained in 98% yield. H-NMR (200
MHz, l ppm): 0.93 (t, J=7.3 Hz, 3H, CH ); 1.37 (m,
(50 MHz, l ppm): 14.0, 14.1, 18.9, 19.0, 41.5, 42.3,
1
65.4, 66.2, 66.5, 66.9, 67.5, 67.6, 69.2, 70.0, 94.0, 94.4.
+
HRMS; Found: 330.1285; Calc. for C H O Fe [M ]:
3
18 26
2
2
H, CH ); 1.64 (m, 2H, CH ); 2.66 (t, J=7.7 Hz, 2H,
330.1282.
2
2
CH ); 4.15 (s, 5H, Fc); 4.44 (t, J=1.9 Hz, 2H, Fc); 4.74
2
13
(
1
t, J=2.0 Hz, 2H, Fc). C-NMR (50 MHz, l ppm):
4.1, 22.7, 26.8, 39.5, 69.4, 69.8, 72.1, 79.2, 204.7.
HRMS; Found: 270.07071; Calc. for C H OFe [M ]:
3.3.3. 1-Hydroxypropylferrocene (8)
Orange crystals (m.p.: 40–41°C) were obtained in
+
1
94% yield. H-NMR (200 MHz, l ppm): 0.95 (t, J=7.3
1
5
18
270.07067.
Hz, 3H, CH ); 1.68 (q, J=7.1 Hz, 2H, CH ); 2.00 (bs,
3
2
13
1
H, OH); 4.21 (m, 10H, Fc, CH). C-NMR (50 MHz,
3
.2.4. 1-Hexanoylferrocene (16)
A dark-red oil was obtained in 73% yield. H-NMR
l ppm): 10.5, 31.0, 65.3, 67.3, 67.8, 67.9, 71.1, 94.3.
1
+
HRMS; Found: 244.05508; Calc. for C H OFe [M ]:
13
16
(
200 MHz, l ppm): 0.92 (t, J=6.2 Hz, 3H, CH ); 1.35
244.05501.
3
(
m, 4H, 2CH ); 1.70 (m, 2H, CH ); 2.69 (t, J=7.6 Hz,
2
2
2
H, CH ); 4.18 (s, 5H, Fc); 4.33 (t, J=1.9 Hz, 2H, Fc);
3.3.4. 1-Hydroxybutylferrocene (11)
A brown oil was obtained in 98% yield. H-NMR
2
1
3
1
4.77 (t, J=2.0 Hz, 2H, Fc). C-NMR (50 MHz, l
ppm): 14.1, 22.6, 24.4, 31.8, 39.8, 69.4, 69.8, 72.1, 79.2,
(300 MHz, l ppm): 0.95 (t, J=7.1 Hz, 3H, CH ); 1.45
3

W.G. Jary et al. / Journal of Organometallic Chemistry 629 (2001) 208–212
211
(
m, 2H, CH ); 1.64 (m, 2H, CH ); 2.13 (bs, 1H, OH);
15.7 Hz, 1H, CH); 6.03 (dd, J=1.3, 15.6 Hz, H,
Fc-CH). C-NMR (50 MHz, l ppm): 18.6, 67.3, 69.1,
2
2
13
4
.18 (m, 9H, Fc); 4.34 (q, J=5.0, 7.4 Hz, 1H, CH).
C-NMR (75 MHz, l ppm): 14.2, 19.3, 40.4, 65.4,
7.2, 67.7, 67.9, 68.4, 69.4, 94.6. HRMS; Found:
1
3
85.0, 122.9, 127.4. HRMS; Found: 266.07598; Calc. for
+
6
2
C H Fe [M ]: 266.07576.
16
18
+
58.07066; Calc. for C H OFe [M ]: 258.07068.
1
4
18
3
.4.2. (E,E%)-1,1%-Dibut-1-enylferrocene (6)
A brown oil was obtained in 67% yield. H-NMR
(200 MHz, l ppm): 1.07 (t, J=7.5 Hz, 6H, 2CH ); 2.11
1
3
.3.5. 1-Hydroxypentylferrocene (14)
A red oil was obtained in 98% yield. H-NMR (200
MHz, l ppm): 0.90 (m, 3H, CH ); 1.35 (m, 4H, 2CH );
1
3
(
dq, J=1.2, 7.5 Hz, 4H, 2CH ); 4.11 (t, J=1.9 Hz, 4H,
2
3
2
Fc); 4.19 (t, J=1.7 Hz, 4H, Fc); 5.84 (dt, J=6.2, 15.7
Hz, 1H, CH); 6.03 (d, J=15.8 Hz, H, Fc-CH). C-
NMR (50 MHz, l ppm): 14.0, 30.4, 67.5, 69.2, 84.9,
1
4
2
.67 (m, 2H, CH ); 1.97 (bs, 1H, OH); 4.21 (m, 9H, Fc);
.31 (m, 1H, CH). C-NMR (50 MHz, l ppm): 14.1,
2
1
3
1
3
2.7, 28.2, 38.0, 65.2, 67.3, 67.8, 67.9, 68.3, 69.7, 94.7.
+
125.3, 130.1. HRMS; Found: 294.10701; Calc. for
HRMS; Found: 272.08630; Calc. for C H OFe [M ]:
1
5
20
+
C H Fe [M ]: 294.10706.
18 22
2
3
72.08632.
3.4.3. (E)-1-Prop-1-enylferrocene (9) and
.3.6. 1-Hydroxyhexylferrocene (17)
(Z)-1-Prop-1-enylferrocene (9a)
A brown solid (m.p.: 92–93°C) was obtained in 85%
1
An inseparable mixture (orange oil) of 9 and 9a in a
yield. H-NMR (200 MHz, l ppm): 0.89 (m, 3H, CH );
1
3
1
ratio of E/Z=4:1 (determined by H-NMR from the
.31 (m, 6H, 3CH ); 1.64 (m, 2H, CH ); 1.96 (d, J=3.4
2 2
1
crude product) was obtained in 74% yield. H-NMR
Hz, 1H, OH); 4.22 (m, 9H, Fc); 4.32 (m, 1H, CH).
1
3
(200 MHz, l ppm): 1.79 (dd, J=1.6, 6.5 Hz, 3H,
C-NMR (50 MHz, l ppm): 14.1, 22.7, 25.8, 31.9,
(
E)-CH ); 1.87 (dd, J=1.6, 7.0 Hz, 3H, (Z)-CH ); 4.16
3
3
38.2, 65.2, 67.3, 67.8, 67.9, 68.3, 69.7, 94.7. HRMS;
+
(m, 5H, Fc); 4.19 (t, J=1.8 Hz, 2H, (E)-Fc); 4.24 (t,
J=1.9 Hz, 2H, (Z)-Fc); 4.32 (t, J=1.8 Hz, 2H, (E)-
Fc); 4.38 (t, J=1.9 Hz, 2H, (Z)-Fc); 5.62 (dq, J=7.0,
Found: 286.10198; Calc. for C H OFe [M ]:
16
22
2
3
86.10198.
1
0.6 Hz, 1H, (Z)-CH); 5.85 (dq, J=6.5, 15.6 Hz, 1H,
.3.7. 1-Hydroxyheptylferrocene (20)
(
E)-CH); 6.15 (dd, J=1.5, 15.5 Hz, 1H, (E)-Fc-CH).
1
A brown oil was obtained in 80% yield. H-NMR
13
C-NMR (200 MHz, l ppm): 15.3 (Z), 18.9 (E), 66.6,
8.6, 69.4, 84.8, 123.3 (E), 123.9 (Z), 127.3 (Z), 128.1
E).
(
200 MHz, l ppm): 0.88 (m, 3H, CH ); 1.28 (m, 8H,
3
6
4CH ); 1.64 (m, 2H, CH ); 1.94 (d, J=2.3 Hz, 1H,
2 2
(
13
OH); 4.21 (m, 9H, Fc); 4.29 (m, 1H, CH). C-NMR
50 MHz, l ppm): 14.2, 22.7, 26.0, 29.3, 31.9, 38.3,
5.2, 67.3, 67.7, 68.3, 94.7. HRMS; Found: 300.11727;
(
6
3
.4.4. (E)-1-But-1-enylferrocene (12)
A brown oil was obtained in 74% yield. H-NMR
1
+
Calc. for C H OFe [M ]: 300.11763.
1
7
24
(
(
300 MHz, l ppm): 1.11 (t, J=7.4 Hz, 3H, CH ); 2.15
3
q, J=6.9 Hz, 2H, CH ); 4.15 (s, 5H, Fc); 4.21 (s, 2H,
2
3.4. Synthesis of bisalkenylferrocenes 3, 4 and
Fc); 4.34 (s, 2H, Fc); 5.91 (dt, J=12.9, 15.7 Hz, 1H,
alkenylferrocenes 9, 12, 15, 18, and 21
13
CH); 6.16 (d, J=15.7 Hz, 1H, Fc-CH). C-NMR (75
MHz, l ppm): 14.1, 26.3, 66.5, 68.3, 69.2, 84.5, 125.7,
The hydroxyalkylferrocenes were dissolved in a 2:1
1
30.2. HRMS; Found: 240.06000; Calc. for C H Fe
14 16
mixture of CH Cl and Et N and cooled to 0°C. After
+
2
2
3
[M ]: 240.06010.
dropwise addition of methylsulfonyl chloride (1.5
equivalents), the solution was refluxed. The reaction
was complete within 3 h and cooled to r.t. The solution
was poured on ice cold 5% HCl and the layers were
separated. The organic layer was washed with saturated
3
.4.5. (E)-1-Pent-1-enylferrocene (15)
A red oil was obtained in 84% yield. H-NMR (200
MHz, l ppm): 0.97 (t, J=7.3 Hz, 3H, CH ); 1.48 (m,
1
3
4H, 2CH ); 2.08 (dq, J=1.2, 7.0 Hz, 2H, CH ); 4.11 (s,
2
2
NaHCO3 and dried over Na SO . The solvent was
2
4
5H, Fc); 4.17 (t, J=1.8 Hz, 2H, Fc); 4.31 (t, J=1.8
Hz, 2H, Fc); 5.82 (dt, J=13.6, 15.7 Hz, 1H, CH); 6.10
removed in vacuo and the pure product was obtained
after flash chromatography.
13
(
d, J=15.7 Hz, 1H, Fc-CH). C-NMR (50 MHz, l
ppm): 13.8, 22.7, 27.0, 35.2, 66.3, 68.2, 69.1, 84.4, 126.8,
128.3. HRMS; Found: 2.07570; Calc. for C H Fe
[M ]: 254.07576.
3
.4.1. (E,E%)-1,1%-Diprop-1-enylferrocene (3)
An inseparable mixture (dark-brown oil) of the
1
5
18
+
(
(
E,E), (Z,Z), and (E,Z) isomers in a ratio of 3:1:1
1
determined by H-NMR from the crude product) was
3.4.6. (E)-1-Hex-1-enylferrocene (18)
A brown oil was obtained in 86% yield. H-NMR
1
1
obtained in 66% yield. H-NMR (200 MHz, l ppm):
0
.97 (t, J=7.3 Hz, 6H, 2CH ); 1.77 (m, 4H, 2CH );
(200 MHz, l ppm): 0.94 (m, 3H, CH ); 1.40 (m, 6H,
3
2
3
4.13 (m, 4H, Fc); 4.17 (m, 4H, Fc); 5.84 (dt, J=6.3,
3CH ); 2.09 (q, J=6.8 Hz, 2H, CH ); 4.10 (s, 5H, Fc);
2
2

212
W.G. Jary et al. / Journal of Organometallic Chemistry 629 (2001) 208–212
(
5
(
(
d) F. Siglm u¨ ller, R. Herrmann, I. Ugi, Tetrahedron 42 (1986)
931;
e) R. Herrmann, I. Ugi, Tetrahedron 37 (1981) 1001;
f) R. Herrmann, G. H u¨ bner, F. Siglm u¨ ller, I. Ugi, Liebigs Ann.
4
.16 (t, J=1.9 Hz, 2H, Fc); 4.30 (t, J=1.8 Hz, 2H,
Fc); 5.81 (dt, J=6.9, 15.7 Hz, 1H, CH); 6.09 (d,
1
3
J=15.6 Hz, 1H, Fc-CH). C-NMR (50 MHz, l ppm):
4.1, 22.3, 31.7, 32.8, 66.3, 68.2, 69.1, 84.4, 126.5, 128.6.
1
Chem. (1986) 251.
+
HRMS; Found: 268.09178; Calc. for C H Fe [M ]:
[6] (a) W.G. Jary, J. Baumgartner, Tetrahedron: Asymmetry 9
16
20
(
(
1998) 2081;
2
3
68.09141.
b) J. Baumgartner, W.G. Jary, in: S.M. Roberts (Ed.), Catalysts
for the Fine Chemical Industry, Wiley, London, 2001 (in press).
7] (a) M. Rosenblum, Chemistry of the Iron Group Metallocenes:
Ferrocene, Ruthenocene, Osmocene, Wiley, New York, 1965 (Pt.
1, pp. 62–119 and references therein);
(b) D.E. Bublitz, K.L. Rinehart Jr., Org. React. 17 (1969) 24.
8] K. Schl o¨ gl, H. Falk, Methodicum Chimicum, vol. 8, 1976, chap.
.4.7. (E)-1-Hept-1-enylferrocene (21)
[
1
A brown oil was obtained in 76% yield. H-NMR
(
200 MHz, l ppm): 0.93 (t, J=6.4 Hz, 3H, CH ); 1.37
3
(m, 8H, 4CH ); 2.08 (q, J=6.1 Hz, 2H, CH ); 4.10 (s,
2
2
[
[
5
H, Fc); 4.16 (s, 2H, Fc); 4.30 (s, 2H, Fc); 5.81 (dt,
3
0 and references therein.
9] B. Floris, G. Illuminati, J. Organomet. Chem. 168 (1979) 203
and references therein).
J=13.6, 15.5 Hz, 1H, CH); 6.09 (d, J=15.8 Hz, 1H,
1
3
Fc-CH). C-NMR (50 MHz, l ppm): 14.2, 22.7, 29.3,
1.5, 33.1, 66.4, 68.2, 69.1, 84.5, 126.6, 128.6. HRMS;
(
3
[10] D.E. Bublitz, K.L. Rinehart, Jr., Organic Reactions, vol. 17, pp.
+
Found: 282.10740; Calc. for C H Fe [M ]: 282.10706.
4–151.
17
22
[
[
[
[
11] C.R. Hauser, J.K. Lindsay, J. Org. Chem. 22 (1957) 482.
12] E.L. DeYoung, J. Org. Chem. 26 (1961) 1312.
13] K. Schl o¨ gl, H. Pelousek, Ann. 651 (1961) 1.
14] R.D. Vukicevic, Z.R. Ratkovic, M.D. Vukicevic, S.K. Kon-
stantinovic, Tetrahedron Lett. 39 (1998) 5837.
Acknowledgements
This work was supported by the Fonds zur
F o¨ rderung der wissenschaftlichen Forschung, Vienna.
[15] R.D. Vukicevic, Z. Ratkovic, M. Vukicevic, S. Konstantinovic,
Synlett (1998) 1329.
[
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(
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1963) 905;
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