Mutual Z-/E-isomerization of ferrocenylmethylene- and arylidene-substituted carbo- and heterocycles

Article abstract of DOI:10.1016/s0022-328x(98)00383-0

The treatment of Z-2-ferrocenylmethylene-, Z-2-arylidene-3-quinuclidinones and 3-methylene-quinuclidines, as well as E-3-ferrocenylmethylenecamphor, -menthone, and -cyclohexanone with NaBPh₄ in acetic acid results in their reversible Z-/E-isomerization. The reaction proceeds via hydroxyallyl and crotyl carbocations with a fixed s-cis-conformation.

Full text of DOI:10.1016/s0022-328x(98)00383-0

Journal of Organometallic Chemistry 559 (1998) 43–53
Mutual Z-/E-isomerization of ferrocenylmethylene- and
arylidene-substituted carbo- and heterocycles
Elena I. Klimova a,c,*, Lena Ru´ız Ram´ırez a, Tatiana Klimova a, Marcos Mart´ınez Garc´ıa b
a Uni6ersidad Nacional Auto´noma de Me´xico, Facultad de Qu´ımica, Circuito Interior, Cd. Uni6ersitaria, Coyoaca´n, CP 04510,
Me´xico D.F., Mexico
b Uni6ersidad Nacional Auto´noma de Me´xico, Facultad de Qu´ımica, Circuito Exterior, Cd. Uni6ersitaria, Coyoaca´n, CP 04510,
Me´xico D.F., Mexico
c M.V. Lomonoso6 Moscow State Uni6ersity, Department of Chemistry, Vorob’e6y Gory, 119899, Moscow, Russia
Received 7 October 1997
Abstract
The treatment of Z-2-ferrocenylmethylene-, Z-2-arylidene-3-quinuclidinones and 3-methylene-quinuclidines, as well as E-3-fer-
rocenylmethylenecamphor, -menthone, and -cyclohexanone with NaBPh4 in acetic acid results in their reversible Z-/E-isomeriza-
tion. The reaction proceeds via hydroxyallyl and crotyl carbocations with a fixed s-cis-conformation. © 1998 Elsevier Science S.A.
All rights reserved.
Keywords: Ferrocene; Quinuclidinone; Carbocation; Z-/E-isomerization
1. Introduction
which is rationalized as being due to their different
membrane-permeation properties and anomalous
metabolism [3–6].
Incorporation of
a ferrocene fragment into a
molecule of an organic compound imparts the chemi-
cal and physicochemical properties that are absent or
little manifested in the parent substance. This allows
one to use ferrocene derivatives as models suitable to
reveal the features that have not been observed in,
albeit inherent to, the analogous classes of com-
pounds [1,2]. In addition, ferrocene-containing com-
pounds often possess unexpected biological activity,
Recently, we have reported on the sufficiently high
antiviral activity of compounds containing ferrocene
and quinuclidine [7] and camphane [8] moieties. They
were synthesized starting from Z-2-ferrocenyl-
methylene-3-quinuclidinone
1
or E-3-ferrocenyl-
methylenecamphor 2, which in turn were prepared by
a base-promoted, high-yielding condensation of 3-
quinuclidinone hydrochloride or camphor, respec-
tively, with ferrocenecarbaldehyde. Z- and E-
Configuration of C(1)ꢀC(2) double bond was re-
tained in s-cis-ferrocenyl-1,3-dienes 3 and 4 obtained
from the chalcones 1 and 2:
* Corresponding author. Fax +52
5
6225366; e-mail:
klimova@servidor.unam.mx
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00383-0

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E. I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 43–53
It is well known that isomeric compounds may pos-
The hindered rotation around the bond with the order
of 1.5 [9–11], the geometry of allyl cations and steric
interactions between bulky substituents therein [11–13]
are studied with hydroxyallyl carbocations including
ferrocenyl-substituted ones [14]. Ferrocenylchalcones
that have been used previously for the protonation and
generation of hydroxyallyl cations possessed linear
structure and existed as mixtures of s-cis- and s-trans-
conformers. With account of chirality of h-ferrocenyl-
carbocations [13,14], the cations could be present in
solutions as mixtures of two diastereomers due to the
free rotation around the C(2)–C(3) ordinary bond in the
initial compounds [14].
sess different biological activity. Therefore, the compar-
ative structure-activity study of derivatives of isomeric
(E- and Z-) compounds with s-cisoid conformation is
desirable. However, the methods of synthesis of such
difficult to access geometrical isomers with ‘internal’
position of the bulky substituents in compounds with
s-cisoid conformation have never been reported in liter-
ature. In the present work, we describe the Z-/E-iso-
merization of ferrocenylmethylene and arylidene
derivatives of some carbo- and heterocycles which al-
lows to obtain pure Z- and E-isomers with satisfactory
yield.
Ferrocenylmethylenequinuclidinone 1 exists in a fixed
s-cis-conformation, and the isomerization can only re-
sult from the rotation around the C(1)···C(2) bond of the
order 1.5 despite the hindered character of this rotation.
In our opinion, this is facilitated by the following factors.
1. The pronounced ability of ferrocene to stabilize the
positive charge in h-ferrocenylcarbocations [9,10].
In the absence of other potent stabilizers of the
carbocationic center at position 3 of the allylic
system, this results in the concentration of the posi-
tive charge at position 1 (see the above scheme).
2. Strong steric interactions of the ‘outer’ and ‘apical’
Z substituents [15–17] that may manifest themselves
only in the change in arrangement of substituents
relative to the C(1)···C(2) bond.
2. Results and discussion
2.1. Mutual Z-/E-isomerization of
2-ferrocenylmethylene- and 2-arylidene-substituted
3-quinuclidinones
We have found that Z-2-ferrocenylmethylene-3-quin-
uclidinone 1 underwent smooth isomerization on treat-
ment with NaBPh4 in acetic acid to give 80% of the
E-isomer 7. The isomerization occurs presumably via
the ferrocenylhydroxyallyl carbenium–ammonium ion
8:

E. I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 43–53
45
3. The effect of a bulky anion BPh4−, which facilitates the isomerization with the ‘inward’ orientation of the OH and
Fc groups. This effect should be manifested the most strongly for nitrogenous heterocycles possessing an
additional cationic center.
A detailed examination of this process has shown that Z-2-arylidene-3-quinuclidinones 10a–c isomerize under
similar conditions to give 40–50% of the E-isomers 11a–c:
2.2. Mutual Z-/E-isomerization of ferrocenylmethylene-substituted camphor and cyclohexanones
E-3-Ferrocenylmethylenecamphor 2 [8,18] also isomerizes to give 40% of the corresponding Z-isomer 14 on
treatment with NaBPh4 in acetic acid:
Likewise, ferrocenylmethylene-substituted cyclohexanones 15a,b undergo E-/Z-isomerization, although the extent
of inversion of configuration (ca. 20%) is much less than that for quinuclidine derivatives:
These data are in full agreement with the concept of the factors that favor the isomerization and confirm the
suggestion on the participation of the tetraphenylborate anion in this process.
1
Satisfactory H NMR spectra could be obtained in CF3COOH, which show the protonation of the carbonyl group
and the formation of hydroxyallyl carbenium–ammonium cations 8a and 8b thereby. Decomposition of the samples
precluded monitoring of the dynamics of the chalcone Z-/E-isomerization.
2.3. Synthesis of Z- and E-isomeric s-cis-1,3-dienes
The reaction of carbo- and hetero-cyclic Z- (14 and 10b) and E-chalcones (7 and 11b) with methyllithium afforded
the corresponding alcohols (17, 19, 20a, 20b). Their dehydration by POCl3 in pyridine resulted in 1,3-dienes (18, 21,
22a, 22b) with the fixed s-cis-conformation of the double bonds:

46
E. I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 43–53
The dienes 18 (Z-) and 21 (E-) were also smoothly
prepared by base-promoted deprotonation of salts of
ferrocenylcrotyl carbocations [7,8]:
Neither could Z- and E-2-arylidene-3-quinuclidi-
nones 22a and 22b be prepared by deprotonation of the
corresponding salts of arylcrotyl carbocations. Unlike
Of many salts of ferrocenylcrotyl carbocations stud-
ied so far [1,2,20,21] only 23b and 24b underwent
deprotonation under analogous conditions, whereas all
others gaveterpenoid cyclodimers.
ferrocenyl-substituted analogs, they underwent dimer-
ization and polymerization resulting in a complex mix-
ture of unidentified products.
2.4. Synthesis and fragmentation reactions of the linear
dimers of 1,3-dienes 21 and 18
These dienes do not produce linear or cyclic dimers
in acidic medium (proton-catalyzed dimerization) ei-
ther, which is typical of many ferrocenyl-1,3-dienes
[1,2,5,8,20–22]. The linear dimers 25 and 26 were ob-
tained as mixtures of two isomers (25a:25b ca. 1:2,
26a:26b ca. 1:1, according to NMR data) by the reac-
tion of the E- and Z-dienes 21 and 18 with the corre-
sponding E- and Z-carbocations 24a and 23a,
respectively. One of the isomers (25b) was isolated in
the pure state. The E- or Z-configuration of the dimers
has not been assigned yet.

E. I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 43–53
47
The linear dimers 25 and 26 are obviously formed
upon base-promoted deprotonation of the intermedi-
ate, dimeric allylic carbocation salts 27 and 28, re-
spectively, which result from the addition of the
secondary cationic center of the cations 24a and 23a
at the methylene group of the dienes 21 and 18
[7,8,20,21].
same as those discussed above for the ferrocenylhy-
droxyallyl carbocations.
2.6. Biological acti6ity of the synthesized compounds
According to a preliminary biological assay, fer-
rocene-containing compounds 3a, 7, 7a, 19, 21, 21a, 25,
and 26 possess high antiviral (relative to smallpox, tick
caused encephalitis, type I and II herpes viruses) and
also antistaphylococcus activity. It should be men-
tioned, that the biological activity of water-soluble
methyliodides is higher than that of the initial bases. In
addition we observed higher biological activity of the
E-isomeric derivatives of quinuclidine as compared to
that of the corresponding Z-isomers.
The action of HBF4 etherate on the dimers 25 and
26 results in their complete fragmentation, which is
similar to that found earlier for terpenoid ferrocenylcy-
clodimers [23]. The fragmentation of the dimers 25a
and 25b affords mixtures of isomeric tetrafluorobo-
1
rates 24a and 24b (~3:1, H NMR data), whereas that
of 26a,b gives a mixture of 23a and 23b (~2:3).
Obviously, the fragmentation is the process oppo-
site to the dimerization. It occurs in the presence of
large excess of a strong acid necessary to protonate
the C(3)ꢀC(4) double bond of the linear dimers (see
the above scheme).
3. Experimental
1H and 13C NMR spectra were recorded on a ‘Gem-
ini 200 Varian’ spectrometer (200 and 50 MHz) for
solutions in CDCl3, CD2Cl2, and CF3COOH with
Me4Si as the internal standard. Column chromatogra-
phy was carried out on Al2O3 (activity grade III accord-
ing to Brockmann).
2.5. Mutual Z-/E-isomerization of s-cis-1,3-dienes
The formation of mixtures of isomeric linear dimers
25a,b and 26a,b from the homoisomeric reactants sug-
gests that the isomerization accompanies the dimeriza-
tion. Hence, either the original ferrocenylcrotyl
cations 24a and 23a or the intermediate dimeric
cations 27 and 28 undergo the isomerization in solu-
tions. Therefore, we have studied by NMR spec-
troscopy the solution behaviour of the salts 24a,b and
23a,b in more detail.
3.1. Z-2-ferrocenylmethylene-3-quinuclidinone 1
Z-2-ferrocenylmethylene-3-quinuclidinone 1 was ob-
tained by a standard procedure [7] from ferrocenecar-
baldehyde and 3-quinuclidinone hydrochloride in an
aqueous-ethanolic alkali as dark-red crystals, yield 85%,
m.p. 122–123°C [6].
The terafluoroborates 24a, 24b, 23a, and 23b,
which were prepared as black powders from the alco-
hols 19, 5, 17, and 6, are sufficiently stable on storage
1
in a dry, inert atmosphere. The H NMR spectra of
3.2. Z-2-ferrocenylmethylene-3-hydroxyquinucli-
dinium-3-cation 8a
the salts 24b and 23b in CD2Cl2 revealed their grad-
ual isomerization into 24a and 23a, respectively,
which followed from the duplication of all the signals.
In the respective equilibrium mixtures A and B after
16 h, the isomers 24a and 23b predominated (24a:24b
ca. 3:1 and 23b:23a ca. 3:2):
The mutual, reversible isomerization of the te-
traphenylborate 24c into 24d and of 23c into 23d,
and vice versa, occurs faster. The equilibrium is at-
tained already after 5 h at ambient temperature, the
isomer ratios in the mixtures A and B being 24c:24d
ca. 1:4 and 23c:23d ca. 1:1.
Compound 1 was dissolved in CF3COOH, and the
1H NMR spectrum of Z-2-ferrocenylmethylene-3-hy-
droxyquinuclidinium-3-cation 8a was recorded at 20°C,
(l): 2.12 (2 H, m), 2.28 (2 H, m), 2.98 (1 H, m), 3.25 (2
H, m), 3.71 (2 H, m), 5.68 (1 H, m, C5H4), 5.73 (1 H,
m, C5H4), 5.78 (5 H, s, C5H5), 6.25 (2 H, m, C5H4), 8.05
(1 H, s, ꢀCH–Fc), 8.40 (1 H, br.s, +NH).
3.3. Z-2-Arylidene-3-quinuclidinones 10a–c
Treatment of the equilibrium mixtures A and B
with N,N-dimethylaniline yielded the isomeric s-cis-
1,3-dienes: 3b (16%), 21 (80%), 4 (45%), and 18b
(40%). The same results were obtained on the treat-
ment of the alcohols 5 and 6b with NaBPh4 in acetic
acid.
Obviously, the mutual Z-/E-isomerization of ferro-
cenylcrotyl carbocations 24b/24a, 24c/24d, 23b/23a,
and 23c/23d, as well as the governing factors are the
Z-2-Arylidene-3-quinuclidinones 10a–c were ob-
tained analogously from the corresponding aromatic
aldehydes and 3-quinuclidinone hydrochloride.
10a (71%), yellow crystals, m.p. 134–135°C [24].
10b (76%), yellow crystals, m.p. 119–120°C, 1H
NMR (CDCl3), l: 2.04 (4 H, m, CH2), 2.65 (1 H, m,
CH), 3.15 (4 H, m, CH2), 6.99 (1 H, s, CHꢀ), 7.07 (2 H,
m, C6H4), 8.08 (2 H, m, C6H4). 13C NMR (CDCl3), l:

48
E. I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 43–53
25.79 (CH2), 40.15 (CH), 47.34 (CH2), 115.24, 115.53,
123.71, 134.01, 134.15 (CH), 144.13, 161.47, 206.11 (C),
147.5 (d, JCF 259.9 Hz, CF). Anal. Calcd. for
C5H4), 6.68 (1 H, s, CHꢀ). Anal. Calcd. for C21H26FeO,
%: C, 72.01; H 7.48; Fe, 15.94. Found: C, 71.81; H,
7.62; Fe, 16.08%.
1
C14H14FNO, %: C, 72.71; H 6.10; F, 8.21; N, 6.06.
Found: C, 71.83; H, 5.89; F, 8.19; N, 5.84%.
15b, eluted with 3:1 hexane–benzene, yield 2.27 g
(65%), red crystals, m.p. 210–211°C. 1H NMR
(CDCl3), l: 0.89 (3 H, d, J=6.85 Hz, CH3), 0.91 (3 H,
d, J=6.85 Hz, CH3), 1.28 (3 H, d, J=7.16 Hz, CH3),
1.55 (1 H, m), 1.70 (1 H, m), 1.80–2.20 (4 H, m), 3.18
(1 H, m), 4.15 (5 H, s, C5H5), 4.46 (2 H, m, C5H4), 4.53
(2 H, m, C5H4), 7.45 (1 H, s, CHꢀ). Anal. Calcd. for
C21H26FeO, %: C, 72.01; H 7.48; Fe, 15.94. Found: C,
71.93; H, 7.23; Fe, 16.18%.
10c (74%), yellow crystals, m.p. 102–103°C, 1H
NMR (CDCl3), l: 1.98 (4 H, m, CH2), 2.60 (1 H, m,
CH), 3.03 (4 H, m, CH2), 3.76 (3 H, s, CH3), 3.80 (3 H,
s, CH3), 6.50 (2 H, m, J=9.1 Hz, C6H3), 7.53 (1 H, s,
CHꢀ), 8.63 (1 H, d, J=9.1 Hz, C6H3). Anal. Calcd. for
C16H19NO3, %: C, 70.31; H 7.01; N, 5.12. Found: C,
70.48; H, 6.79; N, 5.27%.
3.4. E-3-ferrocenylmethylenecamphor 2
3.7. E-2-ferrocenylmethylene-3-quinuclidinone 7
A solution of ferrocenecarbaldehyde (2.1 g, 10 mmol)
and camphor (2.3 g, 15 mmol) in dry benzene (100 ml)
was added to a solution of ButOK (from 0.1 g of
metallic K) in dry ButOH (20 ml), and the mixture was
refluxed for 6 h. The solvent was evaporated in vacuo,
and the residue was chromatographed on alumina to
give Z-3-ferrocenylmethylenecamphor 14 and E-3-fer-
rocenylmethylenecamphor 2.
14, eluted with hexane, yield 0.21 g (6%), red crystals,
m.p. 78–79°C [18].
2, eluted with 3:1 hexane–benzene, yield 2.34 g
(67%), dark-orange plates, m.p. 130–131°C (cf. [8,18]).
A mixture of the chalcone 1 (0.96 g, 3 mmol) and
NaBPh4 (2.60 g, 7.5 mmol) in glacial acetic acid (50 ml)
was stirred in an atmosphere of argon at 40–50°C for 6
h. Then it was cooled to room temperature, poured in
10% aqueous Na2CO3 (200 ml), and the product was
extracted with benzene (3×50 ml). The solvent was
evaporated in vacuo and the residue was chro-
matographed on alumina to give the original chalcone 1
(eluted with hexane, yield 0.15 g, 15%), m.p. 122–
124°C [7], and its isomer 7 eluted with benzene, yield
0.77 g (80%), violet crystals, m.p. 113–114°C. 1H NMR
(CDCl3), l: 1.94 (4 H, m), 2.61 (1 H, m), 3.06 (4 H, m),
4.13 (5 H, s, C5H5), 4.44 (2 H, m, C5H4), 5.00 (2 H, m,
C5H4), 6.61 (1 H, s, CHꢀ). 13C NMR (CDCl3), l: 25.50
(CH2), 42.42 (CH), 49.22 (CH2), 69.54 (C5H5), 71.39,
72.93 (C5H4), 82.34 (Cipso Fc), 135.88 (CHꢀ), 139.91,
203.05 (C). Anal. Calcd. for C18H19FeNO, %: C, 67.30;
H 5.98; Fe, 17.39; N, 4.36. Found: C, 67.12; H, 6.12;
Fe, 17.50; N, 4.21%.
3.5. E-2-ferrocenylmethylenecyclohexanone 15a
E-2-ferrocenylmethylenecyclohexanone 15a was ob-
tained by the standard procedure from ferrocenecar-
baldehyde (10 mmol) and cyclohexanone (25 mmol) in
aqueous-ethanolic alkali. The precipitate was filtered
off and washed with ethanol to give 2,6-bis(ferrocenyl-
methylene)cyclohexanone (3.0 g, 60%), m.p. 163–164°C
(cf. [18]). The filtrate was diluted with water (100 ml)
and the product was extracted with benzene (3×50
ml). Following concentration of the extract and column
chromatography on alumina with hexane as the eluent,
the monochalcone 15a was obtained, yield 0.3 g (10%),
m.p. 113–114°C (cf. [18]).
3.8. E-2-ferrocenylmethylene-3-quinuclidinone
methiodide 7a
To a solution of the chalcone 7 (0.32 g, 1 mmol) in
chloroform, MeI (0.5 ml) was added, and the precipita-
tion of violet needles of the methiodide 7a began after
several min. The reaction mixture was left for 1 h at
20°C, and the crystals that sedimented were filtered off,
1
3.6. E-3-ferrocenylmethylenementhone 15b and its Z-
isomer 16b
yield 0.40 g (87%), m.p. ca. 315°C (decomp.). H NMR
(DMSO-d6), l: 2.30–2.65 (4 H, m), 3.20 (1 H, m), 3.70
(3 H, s), 3.85–4.30 (4 H, m), 4.61 (5 H, s, C5H5), 5.05
(2 H, m, C5H4), 5.42 (2 H, m, C5H4), 8.40 (1 H, br.s,
CHꢀ). Anal. Calcd. for C19H22FeINO, %: C, 49.26; H,
4.78; Fe, 12.06; I, 27.42; N, 3.02. Found: C, 49.43; H,
4.49; Fe, 11.89; I, 27.46; N, 2.95%.
E-3-Ferrocenylmethylenementhone 15b and its Z-
isomer 16b were obtained analogously from ferrocene-
carbaldehyde (2.1 g, 10 mmol) and menthone (2.3 g, 15
mmol).
16b, eluted with hexane, yield 0.18 g (5%), red crys-
1
tals, m.p. 76–77°C. H NMR (CDCl3), l: 0.68 (3 H, d,
3.9. E-2-ferrocenylmethylene-3-hydroxyquinuclidinium-
3-cation 8b
J=6.8 Hz, CH3), 0.98 (3 H, d, J=6.8 Hz, CH3), 1.23
(3 H, d, J=7.0 Hz, CH3), 1.60 (1 H, m), 1.75 (1 H, m),
1.80–2.10 (4 H, m), 3.35 (1 H, m), 4.16 (5 H, s, C5H5),
4.38 (1 H, m, C5H4), 4.43 (2 H, m, C5H4), 4.51 (1 H, m,
Compound 1 was dissolved in CF3COOH, and the
1H NMR spectrum of E-2-ferrocenylmethylene-3-hy-

E. I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 43–53
49
droxyquinuclidinium-3-cation 8b was recorded at 20°C:
3.12. Z-2-ferrocenylmethylenementhone 16b
(l): 2.10 (2 H, m), 2.30 (2 H, m), 2.87 (1 H, m), 3.34 (2
H, m), 3.84 (2 H, m), 5.28 (1 H, m, C5H4), 5.64 (5 H,
m, C5H5), 5.68 (1 H, m, C5H4), 6.23 (2 H, m, C5H4),
7.98 (1 H, s, ꢀCH–Fc), 8.23 (1 H, br.s, +NH).
Z-2-ferrocenylmethylenementhone 16b was obtained
analogously from 0.7 g (2 mmol) of 15b, yield 0.16 g
(20%), m.p. 76–77°C; recovery of 15b was 0.45 g (65%),
m.p. 210–211°C.
3.10. E-2-arylmethylene-3-quinuclidinones 11a–c
3.13. Z-2-ferrocenylmethylenecyclohexanone 16a
E-2-Arylmethylene-3-quinuclidinones 11a–c were
obtained by a procedure identical with that used in the
synthesis of 7: 3 mmol of the corresponding chalcone
10a–c in acetic acid (50 ml) was treated with 7.5 mmol
of NaBPh4. The following products were isolated by
column chromatography on alumina.
Z-2-ferrocenylmethylenecyclohexanone 16a was ob-
tained analogously from 0.6 g (2 mmol) of 15a, yield
0.13 g (20%), dark red crystals, m.p. 182–183°C (cf.
[19]); recovery of 15a was 0.42 g (70%), m.p. 113–
115°C. (cf. [18]).
10a , eluted with 3:1 hexane–benzene, yield 45%,
m.p. 134–135°C [24], and 11a, eluted with 2:1 hexane–
3.14. E-2-ferrocenylmethylene-3-hydroxy-3-methyl-
quinuclidine 19
1
benzene, yield 50%, yellow crystals, m.p. 74–75°C. H
NMR (CDCl3), l: 2.00 (4 H, m, CH2), 2.62 (1 H, m,
CH), 2.90–3.30 (4 H, m, CH2), 7.016 (1 H, s, CHꢀ),
7.35 (3 H, m, Ph), 8.05 (2 H, m, Ph). Anal. Calcd. for
C14H15NO, %: C, 78.84; H 7.09; N, 6.56. Found: C,
79.03; H, 6.85; N, 6.49%.
A suspension of the chalcone 7 (3.2 g, 10 mmol) in
dry benzene (50 ml) was added to an ethereal solution
of methyllithium (30 mmol) with stirring, stirring was
continued for 1 h, and the reaction mixture was
quenched with 5% aqueous NaOH. The organic layer
was separated, washed with water, and dried with
Na2SO4. Following evaporation of the solvent in vacuo,
the residue was crystallized from ethanol to give 2.75 g
(78%) of the alcohol 19 as orange crystals, m.p. 206–
10b, eluted with 2:1 hexane–benzene, yield 29%, m.p.
119–120°C, and 11b, eluted with 1:3 hexane–benzene,
1
yield 60%, m.p. 84–85°C. H NMR (CDCl3), l: 2.01 (4
H, m, CH2), 2.64 (1 H, m, CH), 2.97 (2 H, m, CH2),
3.13 (2 H, m, CH2), 6.78 (1 H, s, CHꢀ), 7.05 (2 H, m,
C6H4), 7.95 (2 H, m, C6H4). 13C NMR (CDCl3), l:
25.32 (CH2), 42.58 (CH), 48.94 (CH2), 114.87, 115.16,
123.76, 133.25, 133.36 (CH), 143.45, 161.83, 203.69 (C),
1
207°C. H NMR (CDCl3), l: 1.40–2.20 (4 H, m), 1.60
(3 H, s), 2.33 (1 H, s, OH), 2.85 (1 H, m), 3.00–3.08 (4
H, m), 4.17 (5 H, s, C5H5), 4.29 (2 H, m, C5H4), 4.48 (1
H, m, C5H4), 4.78 (1 H, m, C5H4), 6.32 (1 H, s, CHꢀ);
13C NMR (CDCl3), l: 21.79, 24.24 (CH2), 24.16 (CH3),
37.48 (CH2), 47.54 (CH2), 49.89 (CH), 68.91 (C), 69.19
(C5H5), 70.01, 71.10, 71.91 (C5H4), 79.13 (Cipso Fc),
122.52 (CHꢀ), 131.4 (C). Anal. Calcd. for C19H23FeNO,
%: C, 67.66; H 6.87; Fe, 16.56; N, 4.15. Found: C,
67.48; H, 7.01; Fe, 16.34; N, 3.94%.
1
147.30 (d, JCF 267 Hz, CF). Anal. Calcd. for
C14H14FNO, %: C, 72.71; H 6.10; F, 8.21; N, 6.06.
Found: C, 72.54; H, 5.93; F, 8.32; N, 5.85%.
10c, eluted with 1:1 hexane–benzene, yield 40%, m.p.
102–103°C, and 11b, eluted with 3:1 benzene–ethyl
1
acetate, yield 45%, yellow crystals, m.p. 117–118°C. H
NMR (CDCl3), l: 1.99 (4 H, m, CH2), 2.61 (1 H, m,
CH), 3.10 (4 H, m, CH2), 3.80 (3 H, s, CH3), 3.83 (3 H,
s, CH3), 6.50 (2 H, m, J=9.4 Hz, C6H3), 7.37 (1 H, s,
CHꢀ), 8.36 (1 H, d, J=9.4 Hz, C6H3). Anal. Calcd. for
C16H19NO3, %: C, 70.31; H 7.01; N, 5.12. Found: C,
70.28; H, 6.82; N, 4.95%.
The isomerization of E-configurated chalcones into
Z-isomers was performed analogously to yield ca. 17%
of 1, ca. 40% of 10a, ca. 32% of 10b, and ca. 50% of
10c.
The alcohol 5 was obtained analogously from the
chalcone 1, yield 70%, m.p. 161–162°C (cf. [7]).
3.15. E- and Z-2-ferrocenylmethylene-3-methyl-
quinuclidinium-3-cation tetrafluoroborates (24a and
24b)
E- and Z-2-ferrocenylmethylene-3-methylquinucli-
dinium-3-cation tetrafluoro-borates (24a and 24b) were
prepared by the addition of HBF4 etherate to solutions
of the alcohols 19 and 5, respectively, in dry ether [7].
24a, yield 71%, black powder, decomposes on heat-
3.11. Z-3-ferrocenylmethylenecamphor 14
A mixture of the chalcone 2 (0.7 g, 2 mmol) and
NaBPh4 (1.02 g, 3 mmol) in glacial acetic acid (50 ml)
was boiled under reflux for 6 h. The reaction mixture
was poured in water, the products were extracted with
benzene to give after column chromatography 0.36 g
(50%) of the original chalcone 2 and 0.28 g (40%) of the
chalcone 14, m.p. 78–80°C (cf. [18]).
1
ing. H NMR (CD2Cl2), l: 2.06 (2 H, m), 2.25 (2 H,
m), 2.37 (3 H, s), 3.25 (1 H, m), 3.44 (2 H, m), 3.96 (2
H, m), 4.97 (1 H, m, C5H4), 5.26 (5 H, s, C5H5), 5.30 (1
H, m, C5H4), 6.47 (1 H, m, C5H4), 6.50 (1 H, m, C5H4),
7.80 (1 H, s, ꢀCH–Fc), 8.80 (1 H, s, +NH). Anal.
Calcd. for C19H23B2F8FeN, %: C, 46.08; H 4.68; Fe,

50
E. I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 43–53
3.18. E- and Z-3-ferrocenylmethylene-1,2,7,7-
tetramethylbicyclo[2.2.1]heptane-2-cation
tetra-fluoroborates (23a and 23b)
11.28; N, 2.82. Found: C, 45.48; H, 4.33; Fe, 11.12; N,
3.01%.
24b, yield 80%, black powder, decomposes on heat-
1
ing. H NMR (CD2Cl2), l: 2.08 (2 H, m), 2.32 (2 H,
E- and Z-3-Ferrocenylmethylene-1,2,7,7-tetramethyl-
bicyclo[2.2.1]heptane-2-cation tetra-fluoroborates (23a
and 23b [8]) were prepared as described above, starting
from the alcohols 6 and 17, respectively, and HBF4
etherate.
m), 2.42 (3 H, s), 3.30 (1 H, m), 3.46 (2 H, m), 3.98 (2
H, m), 4.98 (1 H, m, C5H4), 5.29 (5 H, s, C5H5), 5.34 (1
H, m, C5H4), 6.52 (2 H, m, C5H4), 7.84 (1 H, s,
ꢀCH–Fc), 9.01 (1 H, s, +NH). Anal. Found: C, 46.12;
H, 4.77; Fe, 11.31; N, 3.07%.
23a, yield 70%, dark brown powder, decomposes on
1
heating. H NMR (CD2Cl2), l: 0.79 (3 H, s), 0.92 (3 H,
3.16. Tetraphenylborates 24c and 24d
s), 1.13 (3 H, s), 1.81 (3 H, s), 1.65 (2 H, m), 1.72–1.83
(2 H, m), 3.46 (1 H, m), 4.85 (5 H, s, C5H5), 4.96 (1 H,
m, C5H4), 5.38 (1 H, m, C5H4), 6.07 (1 H, m, C5H4),
6.20 (1 H, m, C5H4), 8.42 (1 H, s, ꢀCH–Fc). Anal.
Calcd. for C22H27BF4Fe, %: C, 60.87; H 6.27; Fe, 12.86.
Found: C, 60.59; H, 6.32; Fe, 13.01%.
Tetraphenylborates 24d and 24c were obtained by the
standard procedure, viz., using NaBPh4 in glacial acetic
acid [7,8] at 10–15°C. After 20 min, the crystalline salts
were filtered off and washed on the filter with dry ether.
24c, yield 65%, brown powder, decomposes on heat-
ing. Anal. Calcd. for C67H63B2FeN, %: C, 83.82; H,
6.61; Fe, 5.82; N, 1.46. Found: C, 83.97; H, 6.42; Fe,
5.59; N, 1.58%.
3.19. Tetraphenylborates 23c and 23d
Tetraphenylborates 23c and 23d were obtained from
the alcohols 6 and 17 and NaBPh4 in glacial acetic acid
[1].
24d, yield 68%, brown powder, decomposes on heat-
ing. Anal. Found: C, 83.75; H, 6.82; Fe, 6.01; N, 1.21%.
23c, yield 64%, brown crystals, decomposes on heat-
ing. Anal. Calcd. for C46H47BFe, %: C, 82.87; H, 7.10;
Fe, 8.38. Found: C, 82.63; H, 6.94; Fe, 8.21%.
23d, yield 67%, brown crystals, decomposes on heat-
ing. Anal. Found: C, 82.59; H, 7.23; Fe, 8.17%.
3.17. 3-ferrocenylmethylene-2-hydroxy-2-
methylcamphanes 6 and 17
3-Ferrocenylmethylene-2-hydroxy-2-methylcampha-
nes (6 [7] and 17) were synthesized from the corre-
sponding chalcones, 2 and 14. A suspension of the
chalcone 2 (1.05 g, 3 mmol) in dry benzene (50 ml) was
added to an ethereal solution of methyllithium (10
mmol) with stirring, stirring was continued for 1 h, and
the reaction mixture was quenched with 5% aqueous
NaOH. The organic layer was separated, concentrated
in vacuo, and the residue was dissolved in ethanol (25
ml) with heating. The product that crystallized on
cooling was filtered off, washed with ethanol, and dried
to give 3-(1-ferrocenylethyl)camphor, yield 0.44 g (40%)
from 2 and 0.65 g (60%) from 14, yellow crystals, m. p.
3.20. Z- and E-2-ferrocenylmethylene-3-
methylenequinuclidines (3 and 21)
1. POCl3 (2 ml) was added dropwise to a solution of
the alcohol 5 or 19 (1.12 g, 3.3 mmol) in dry
pyridine (50 ml), the mixture was stirred for 3 h at
ambient temperature and diluted with water. The
diene that formed was extracted with benzene. Fol-
lowing concentration of the extract in vacuo, the
residue was purified by column chromatography on
alumina in hexane.
1
152–153°C. H NMR (CDCl3), l: 0.86 (3 H, s), 0.89 (3
3, yield 0.76 g (70%), orange crystals, m.p. 92–
93°C (cf. [7]). 13C NMR (CDCl3), l: 28.08 (CH2),
34.39 (CH), 47.85 (CH2), 68.87 (C5H5), 68.66, 69.76
(C5H4), 80.05 (Cipso Fc), 101.14 (CH2ꢀ), 115.00
(CHꢀ), 144.80, 150.78 (C).
H, s), 0.92 (3 H, s), 1.15–1.70 (4 H, m), 1.62 (3 H, d,
J=6.6 Hz), 1.82 (1 H, m), 2.52 (1 H, m, J=6.6 Hz),
3.98 (1 H, m, C5H4), 4.01 (1 H, m, C5H4), 4.11 (2 H, m,
C5H4), 4.14 (5 H, s, C5H5). Anal. Calcd. for
C22H28FeO, %: C, 72.53; H, 7.74; Fe, 15.33. Found: C,
72.71; H, 7.58; Fe, 15.43%.
21, yield 0.78 g (72%), orange crystals, m.p. 63–
1
64°C. H NMR (CDCl3), l: 1.72 (4 H, m), 2.50 (1
The ethanolic filtrate was taken to dryness and the
residue was chromatographed on alumina in benzene to
yield 0.46 g (42%) of alcohol 6 (from 2), m.p. 96–97°C
(cf. [7]), and 0.33 g (30%) of alcohol 17 (from 14b),
H, m), 3.01 (4 H, m), 4.11 (5 H, s, C5H5), 4.20 (2 H,
m, C5H4), 4.45 (2 H, m, C5H4), 4.99 (1 H, d,
J=1.38 Hz), 5.47 (1 H, d, J=1.38 Hz), 6.22 (1 H,
s, CHꢀ); 13C NMR (CDCl3), l: 28.08 (CH2), 35.78
(CH), 49.66 (CH2), 68.36 (C5H5), 69.27, 69.54
(C5H4), 81.25 (Cipso Fc), 110.02 (CH2ꢀ), 120.60
(CHꢀ), 145.40, 147.65 (C). Anal. Calcd. for
C19H21FeN, %: C, 71.49; H 6.63; Fe, 17.50; N, 4.38.
Found: C, 71.28; H, 6.72; Fe, 17.63; N, 4.61%.
1
orange oil. H NMR (CDCl3), l: 0.84 (3 H, s), 0.96 (3
H, s), 1.00 (3 H, s), 1.35 (3 H, s), 1.25–2.00 (4 H, m),
2.76 (1 H, m), 4.10 (1 H, m, C5H4), 4.12 (5 H, s, C5H5),
4.15 (1 H, m, C5H4), 4.30 (2 H, m, C5H4), 6.38 (1 H, s,
CHꢀ). Anal. Found: C, 72.29; H, 7.91; Fe, 15.52%.

E. I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 43–53
51
2. Freshly distilled N,N-dimethylaniline (2 ml) was
added dropwise with stirring to a solution of 3.3
mmol of tetrafluoroborate 24a or 24b or of the
tetraphenylborate 24d or 24c in CH2Cl2 (20 ml).
After 1 h, the mixture was washed with water, 1%
aqueous HCl, and again with water. The solvent
was distilled off and the residue was chro-
matographed on alumina to yield 0.74–0.77 g (69–
72%) of the diene 21, m.p. 63–65°C, and 0.75–0.78
g (70–73%) of the diene 3, m.p. 92–93°C (cf. [7]).
22a, yield 1.5 g (65.2%), colorless crystals, m.p. 93–
94°C. 1H NMR (CDCl3), l: 1.72 (4 H, m, CH2), 2.57 (1
H, m, CH), 2.90 (2 H, m, CH2), 3.01 (2 H, m, CH2),
4.80 (1 H, s, CH2ꢀ), 5.28 (1 H, s, CH2ꢀ), 6.42 (1 H, s,
CHꢀ), 6.97 (2 H, m, C6H4), 7.88 (2 H, m, C6H4); 13C
NMR (CDCl3), l: 27.85 (CH2), 34.25 (CH),
47.41(CH2), 103.16 (CH2ꢀ), 114.71, 114.99, 115.40,
131.32, 131.41 (CH), 147.38, 150.60, 159.90 (C), 147.88
1
(d, JCF 229.5 Hz, CF). Anal. Calcd. for C15H16FN, %:
C, 78.57; H 7.04; F, 8.28; N, 6.11. Found: C, 78.69; H,
6.93; F, 8.11; N, 5.98%.
3.21. Methiodide 3a
22b, yield 1.61 g (70%), colorless crystals, m.p. 38–
39°C. 1H NMR (CDCl3), l: 1.70 (4 H, m, CH2), 2.51 (1
H, m, CH), 3.06 (4 H, m, CH2), 4.85 (1 H, s, CH2ꢀ),
4.98 (1 H, d, Jꢀ1.0 Hz, CH2ꢀ), 6.46 (1 H, s, CHꢀ), 6.97
(2 H, m, C6H4), 7.31 (2 H, m, C6H4); 13C NMR
(CDCl3), l: 29.07 (CH2), 30.71 (CH), 47.75(CH2),
102.17 (CH2ꢀ), 114.11, 114.73, 128.84, 130.89, 131.08
A solution of the diene 3 (0.32 g, 1 mmol) and MeI
(0.5 ml) in acetonitrile (20 ml) was kept for 7–10 days
in darkness at ambient temperature until the starting
diene disappeared (TLC, Silufol), and the product was
precipitated with dry ether. The precipitate was filtered
off and washed with ether to yield 0.37 g (80%) of the
salt 3a as the orange powder, which decomposes on
1
(CH), 149.56 (d, JCF 272 Hz, CF). Anal. Found: C,
78.41; H, 6.89; F, 8.34; N, 6.23%.
1
heating. H NMR (DMSO-d6), l: 1.80–2.28 (4 H, m),
2.57 (1 H, m), 2.95–3.10 (4 H, m), 3.35 (3 H, s, CH3),
4.34 (5 H, s, C5H5), 4.50 (2 H, m, C5H4), 4.60 (2 H, m,
C5H4), 5.47 (1 H, s, CH2ꢀ), 5.60 (1 H, s, CH2ꢀ), 6.90 (1
H, s, CHꢀ). Anal. Calcd. for C20H24FeIN, %: C, 52.08;
H, 5.25; Fe, 12.11; I, 27.53; N, 3.03. Found: C, 51.83;
H, 5.34; Fe, 12.23; I, 27.28; N, 2.87%.
3.24. E- and Z-3-ferrocenylmethylene-2-
methylenecamphanes 4 and 18
E- and Z-3-Ferrocenylmethylene-2-methylenecam-
phanes 4 and 18 were prepared by two methods as
described above for the synthesis of the dienes 3 and 21.
1. The dienes 4 and 18 were obtained from 1.21 g (3.3
mmol) of the alcohols 6 and 17, respectively: 4, yield
0.80 g (70%), orange crystals, m.p. 73–74°C [8]; 18,
3.22. Methiodide 21a
1
MeI (0.5 ml) was added to a solution of the diene 21
(0.32 g, 1 mmol) in chloroform (10 ml), and crystalliza-
tion began in several min. After 1 h, the crystals that
precipitated were filtered off and washed with dry ether
to yield 0.36 g (78%) of the salt 21a, which decomposes
yield 0.84 g (82%), orange oil, H NMR (CDCl3), l:
0.63 (3 H, s), 0.93 (3 H, s), 1.00 (3 H, s), 1.20–1.95
(4 H, m), 2.77 (1 H, m), 4.10 (5 H, s, C5H5), 4.17 (2
H, m, C5H4), 4.30 (2 H, m, C5H4), 4.53 (1 H, s,
CH2ꢀ), 5.00 (1 H, s, CH2ꢀ), 6.17 (1 H, s, CHꢀ).
Anal. Calcd. for C22H26Fe, %: C, 76.30; H 7.57; Fe
16.13. Found: C, 76.42; H, 7.28; Fe, 16.18%.
1
on heating. H NMR (DMSO-d6), l: 1.91–2.20 (4 H,
m), 2.50 (1 H, m), 2.80–2.95 (4 H, m), 3.41 (3 H, s,
CH3), 4.28 (5 H, s, C5H5), 4.42 (2 H, m, C5H4), 4.55 (2
H, m, C5H4), 5.45 (1 H, s, CH2ꢀ), 5.53 (1 H, s, CH2ꢀ),
6.81 (1 H, s, CHꢀ). Anal. Found: C, 52.12; H, 5.04; Fe,
11.93; N, 3.20%.
2. Starting from 2.22 g (3.3 mmol) of the tetrafluorob-
orate 23b, the diene 4, m.p. 73–75°C (cf. [8]), was
obtained in a yield of 0.86 g (76%), and the te-
trafluoroborate 23a gave 74% of the diene 18.
3.23. Z- and E-2-(p-fluorobenzylidene)3-methylenequin-
uclidines 22a and 22b
3.25. Mutual Z-/E-isomerization of s-cis-ferrocenyl-
1,3-dienes
An ethereal solution of MeLi (30 mmol) was added
to a solution of the chalcone 10b or 11b (2.32 g, 10
mmol) in dry ether, the mixture was stirred for 1 h at
20°C and quenched with 5% aqueous NaOH (20 ml).
The ethereal layer was separated, washed with water,
and concentrated to dryness. The residue was dissolved
in pyridine (50 ml) and POCl3 (2 ml) was added. The
mixture was stirred for 3 h at 40°C and diluted with
benzene (100 ml). Pyridine was washed out with water
(3×50 ml), the solvent was removed in vacuo, and the
residue was crystallized from hexane.
1. A mixture of the Z-diene 3 (0.64 g, 2 mmol) and
NaBPh4 (1.7 g, 5 mmol) in glacial acetic acid (50 ml)
was stirred in an inert atmosphere for 4 h at 50–
60°C. Then it was cooled to room temperature and
poured into 10% aqueous Na2CO3 (100 ml). The
product was extracted with benzene, the extract was
concentrated to dryness, and the residue was chro-
matographed on alumina to give 0.083 g (13%) of
the Z-diene 3 (eluted with hexane) [6] and 0.52 g
(81%) of the E-diene 21 (eluted with 2:1 hexane–
benzene), m.p. 63–64°C.

52
E. I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 43–53
Analogous treatment of the E-diene 21 (0.64 g, 2
mmol) gave 0.13 g (20%) of 3 and 0.46 g (72%) of
the starting 21.
The treatment of the E-diene 4 (0.69 g, 2 mmol)
with NaBPh4 (1.02 g, 3 mmol) in glacial acetic acid
(50 ml) yielded 0.27 g (33%) of the Z-diene 18,
recovery of the starting E-diene 4 was 0.3 g (43%)
[8].
l: 0.68 (3 H, s), 0.71 (3 H, s), 0.88 (6 H, s), 0.91 (3 H,
s), 0.94 (6 H, s), 0.96 (3 H, s), 0.98 (6 H, s), 1.10 (6 H,
s), 1.12–1.60 (8 H, m), 1.53 (3 H, s), 1.64 (3 H, s), 2.80
(1 H, m), 2.82 (1 H, m), 2.88 (1 H, m), 2.91 (1 H, m),
4.06, 4.08, 4.13, 4.14 (20 H, 4 s, 4 C5H5), 4.00–4.22 (8
H, m, 2 C5H4), 4.30–4.50 (8 H, m, 2 C5H4), 5.61 (1 H,
d, J=6.4 Hz, CH–Fc), 5.70 (1 H, d, J=6.4 Hz,
CH–Fc), 6.36 (1 H, d, J=6.4 Hz, CHꢀ), 6.47 (1 H, s,
CHꢀ), 6.58 (1 H, d, J=6.4 Hz, CHꢀ), 7.29 (1 H, s,
CHꢀ). Anal. Calcd. for C44H52Fe2, %: C, 76.30; H 7.57;
Fe 16.13. Found: C, 76.21; H, 7.64; Fe, 16.27%.
2. The interaction of the Z-alcohol 5 (0.68 g, 2 mmol)
with NaBPh4 (1.7 g, 5 mmol) in glacial acetic acid
(50 ml) for 5 h at 50°C yielded 0.11 g (17%) of the
Z-diene 3, m.p. 92–93°C [7], and 0.48 g (75%) of
the E-diene 21, m.p. 63–64°C.
3.27. Fragmentation of the dimers 25 and 26
Analogously, the action of NaBPh4 (1.02 g, 3
mmol) on the E-alcohol 6 (0.73 g, 2 mmol) yielded
0.28 g (40%) of the Z-diene 18 and 0.31 g (45%) of
the E-diene 4 [8].
To a solution of the dimer 25 (or 26) (1 mmol) in dry
ether (50 ml), HBF4 etherate (2 ml) was added with
stirring. The corresponding salts sedimented as black
precipitates were filtered off and washed with dry ether,
the yield was almost quantitative. The ratio of the
3.26. Condensation of dienes 21 and 18 with
tetrafluoroborates 24a and 23a
1
isomeric salts was determined from the H NMR spec-
tra recorded in CD2Cl2.
A solution of the E-diene 21 (0.53 g, 1.65 mmol) in
CH2Cl2 (20 ml) was added with stirring to a solution of
the salt 24a (0.83 g, 1.65 mmol) in CH2Cl2 (30 ml).
After 15 min, N,N-dimethylaniline (2 ml) was added
dropwise and stirring was continued for an additional
30 min. Then the mixture was diluted with benzene (50
ml) and washed with water, 1% aqueous HCl, and
water. Following removal of the solvent, the residue
was chromatographed on SiO2 (hexane–benzene-di-
ethyl ether, 1:1:1) to give 0.64 g (60%) of 3-[2-ferro-
cenyl-2-(3-methyl-D2-dehydroquinuclid-2-yl)ethylidene]-
2-ferrocenylmethylenequinuclidine as a mixture of Z-
and E-isomers 25a,b in a ratio of ~1:2, Rf 0.52, orange
crystals, m.p. 146–148°C. The isomer 25b (0.21 g) was
isolated by recrystallization from hexane, m.p. 171–
Acknowledgements
Financial support from CONACyT (Mexico) is
gratefully acknowledged.
References
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1
172°C. H NMR (CDCl3), l: 1.30–1.78 (8 H, m), 1.87
(3 H, s, CH3), 2.38 (1 H, m), 2.56 (1 H, m), 2.75–3.20
(8 H, m), 4.20 (5 H, s, C5H5), 4.21 (5 H, s, C5H5),
4.02–4.25 (8 H, m, C5H4), 4.80 (1 H, m, CH–Fc), 6.67
(1 H, m, CHꢀ), 7.85 (1 H, s, CH&z.rbond3;). Anal.
Calcd. for C38H42Fe2N2, %: C, 71.49; H 6.63; Fe 17.50;
N, 4.38. Found: C, 71.53; H, 6.51; Fe, 17.29; N, 4.23%.
25a, 1H NMR (CDCl3), l: 1.50 (4 H, m), 1.70 (2 H, m),
1.92 (3H, s, CH3), 2.30 (1 H, m), 2.32 (2 H, m), 2.60
(1 H, m), 2.80–3.10 (8 H, m), 4.10 (5 H, s, C5H5),
4.11 (5 H, s, C5H5), 4.10–4.40 (8 H, m, C5H4), 4.62
(1 H, m, CH–Fc), 6.58 (1 H, m, CHꢀ), 7.80 (1 H, s,
CHꢀ).
The condensation of the Z-diene 18 (0.52 g, 1.5
mmol) with the Z-tetrafluoroborate 23a (0.65 g, 1.5
mmol) was carried out analogously to yield 0.75 g
(72%) of 2-[2-ferrocenyl-2-(2-methyl-D2-dehydrocamph-
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a
mixture of Z- and E-isomers 26a,b in a ratio of ~1:1,
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1
orange powder, m.p. 210–211°C.7 H NMR (CDCl3),

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