Synthesis and Reactivity of Ferrocenyl-Substituted Allylamine Derivatives

Article abstract of DOI:10.1002/ejic.201600860

[(2-Ferrocenylvinyl)methyl]dimethylamine (2) was obtained in good yields and with perfect regio- and stereoselectivity by reaction of dimethylmethylideneammonium salts with vinylferrocene. After methylation of amine 2, [(2-ferrocenylvinyl)methyl]trimethyl

Full text of DOI:10.1002/ejic.201600860

A Journal of
Accepted Article
Title: Synthesis and reactivity of ferrocenyl allylamine derivatives.
Authors: Eric Manoury; Rafika Bouchene; Jean-Claude Daran; Sofiane Bouacida
This manuscript has been accepted after peer review and the authors have elected
to post their Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by using the Digital
Object Identifier (DOI) given below. The VoR will be published online in Early View as
soon as possible and may be different to this Accepted Article as a result of editing.
Readers should obtain the VoR from the journal website shown below when it is pu-
blished to ensure accuracy of information. The authors are responsible for the content
of this Accepted Article.
To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201600860
Link to VoR: http://dx.doi.org/10.1002/ejic.201600860

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
1
Synthesis and reactivity of ferrocenyl allylamine derivatives.
Rafika Bouchene, a,b,c Jean-Claude Daran, a,b Sofiane Bouacida,c,d Eric Manoury*a,b
aCNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP 44099,
F-31077 Toulouse Cedex 4, France CNRS. Fax: +33-561553003; Tel: +33-561333174; E-
mail: eric.manoury@lcc-toulouse.fr.
bUniversité de Toulouse, UPS, INPT, F-31077 Toulouse Cedex 4, France
cDépartement Sciences de la Matière, Faculté des Sciences Exactes, Université Oum El
Bouaghi, 04000, Algeria
dUnité de Recherche de Chimie de l’Environnement et Moléculaire Structurale CHEMS,
Université Constantine 1, Algeria.
Abstract
((2-ferrocenylvinyl)methyl)dimethylamine 2 was obtained in good yields with perfect
regio and stereoselectivity. by reaction of dimethylmethylideneammonium salts on
vinylferrocene.
After
methylation
of
amine
2,
((2-
ferrocenylvinyl)methyl)trimethylammonium 4 was obtained in high yields and used to
transfer ferrocene-containing allyl group on various amines. By controlling reaction
conditions, various linear and branched ferrocenyl allylamines could be obtained with good
yields and selectivities. When anilines were used as substrates against ammonium 4,
compounds from Friedel-Crafts reaction with a complete regioselectivty for the para position
were also obtained.
Introduction
Many efforts have been devoted to the synthesis of allylamines[1] because of their interesting
[2]
biological activities
and because they are valuable synthetic intermediates.[3] However,
although ferrocene derivatives are of great interest in many fields like asymmetric catalysis,[4]
biology,[5] materials chemistry, …, only very few ferrocene-containing allylamines have been
described to the best of our knowledge.[6] In this article, we will present an efficient and
straightforward general synthesis of new ferrocenyl allylic amines.

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
2
Results and discussion
Iminium salts have been largely used as electrophilic reagents or intermediates.[7]
[8]
Because of the strong ability of ferrocene to stabilize carbocation in  positions,
we
imagine that vinyl ferrocene could react with Eschenmoser’s salt[9] or other
dimethylmethylideneammonium salts.[10] We then reacted vinyl ferrocene 1 with two
equivalents
of
commercially
available
dimethylmethylideneammonium
iodide
(Eschenmoser’s salt) or chloride in dichloromethane. After one night at RT, the conversion of
vinylferrocene was complete to yield, after basic work-up, the linear allylic amine 2 with a
perfect regio and stereoselectivity. However, if the reaction is limited to 5h in the same
conditions, the conversion of vinylferrocene 1 is also complete but compound 2 is obtained
with slight traces of the isomer 3 (see scheme 1).
Scheme 1: reaction of vinylferrocene 1 with dimethylmethylideneammonium salts
In principle, the iminium salts could attack on the carbon in  position of the ferrocene
moiety to yield the linear isomer 2 or in  position of the ferrocene to yield a branched isomer
which have not been observed. This very high regioselectivity can be easily explained by the
huge difference in stability of the two carbocations produced on both ways (see scheme 1),
the attack in  position yielding a carbocation strongly stabilized by the presence of the

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
3
ferrocene in  position.[8] We proposed that traces of byproduct 3 came from a rearrangement
of an ammonium intermediate, which is present before basic work-up (see scheme 2). In
addition, ammonium 2H+ is thermodynamically more favored than its isomer 3H+ yielding
after 16h only 2H+ by a slow equilibration before basic work-up (see scheme 2).
Scheme 2: reaction of vinylferrocene 1 with dimethylmethylideneammonium salts.
Rearrangement of tertiary ammonium intermediate.
Next, we explore the ability of 2 to transfer ferrocene-containing allyl group after
simple activation by methylation. Indeed, amine 2 could be quantitatively transformed
into the corresponding ammonium 4 using iodomethane (see scheme 3). We hoped that
trimethylamine could be a good enough leaving group and therefore allow nucleophilic
substitution on ammonium 4. Ammonium are usually poor alkylating agents but, thanks
again
to
the
huge
stabilization
of
carbocations
by
ferrocene,
(ferrocenylmethyl)trimethylammonium salts proved to be efficient alkylating agent. [11]We
then studied the reaction of ammonium 4 with benzylamine in various conditions (see
scheme 3 and table 1) in a polar protic solvent, namely ethanol, to favor the leaving
group’s departure. With a big excess of benzylamine (20 eq.), a full conversion of 4 could
be achieved after 16 h reaction at 80°C to yield the expected amine products with a very
high regioselectivity in favor of the branched regioisomer 6a (see scheme 3 and table 1,
entry 1). This observed regioselectivity is expected because we supposed that the reaction
goes via the carbocationic intermediate C (see scheme 2) in which the positive charge is
essentially present on the carbon in  position of the ferrocene moiety and therefore
would yield the product of the attack of the nucleophile benzylamine on  position,
namely 6a. Encouraged by these very good results, we decreased the amount of

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
4
benzylamine down to 2 equivalents. If full conversions of 4 could also been obtained, in
the same experimental conditions, the regioselectivity was now in favor of the linear
regioisomer 5a (see table 1, entry 2) and significant yields of ethers 7Et and 8Et coming
from nucleophilic substitution by the solvent were obtained. The presence of ethers 7Et
and 8Et is not very surprising because decreasing the amount of the nucleophile
benzylamine favors the reaction with other nucleophiles like ethanol but the reverse in
regioselectivity is more puzzling.
Scheme 3: synthesis of allylammonium 4 and its reaction with various amines in alcoholic
solvents.
We propose a mechanism to explain these experimental results keeping in mind that
the primary products of the nucleophilic substitution reaction are ammoniums and not the
amines obtained after final basic work-up (see scheme 4). We imagined that the
nucleophilic substitution on ammonium 4 took place with very high regioselectivity on the
carbon in  position of the ferrocene to yield (6)H+, which is the kinetic product. With an
excess of base like 20 equivalents of benzylamine, (6)H+ is deprotonated to give 6, which
is stable and is found at the end of the reaction (table 1, entry 1). If the amount of base is
much lower, the deprotonation of (6)H+ is incomplete and a significant amount of (6)H+ in
equilibrium with 6 is always present in the reaction mixture. In this case, (6)H+rearranges
slowly, probably through carbocation C, into the thermodymanic product (5)H+ yielding 5
after basic work-up.

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
5
Scheme 4: proposed mechanism of the reaction of benzylamine with ammonium 4.
If this mechanism is effective, an addition of a base even with only two equivalents of
nucleophile should limit the rearrangement of (6)H+to (5)H+. We then tried the reaction with
20 equivalents of sodium carbonate (table 1, entry 3). As predicted from the proposed
mechanism, the branched regioisomer was obtained with an excellent regioselectivity, even
better than with 20 equivalents of benzylamine. We then tried to even decrease more the
amount of benzylamine with or without potassium carbonate (table 1, entries 4-7). As
expected, with less benzylamine and without carbonate, the regioselectivity in favor of the
linear amine increased and the amount of ethers 7Et and 8Et increased. A new compound 9a
could be also isolated (see scheme 5). This new ferrocene derivative is obtained by a double
allylation and a double rearrangement. When the same reactions with 1 and 0.5 equivalents of
benzylamine (table 1, entries 5 and 7) were carried out in presence of potassium carbonate,
again branched amine 6a could indeed be obtained but no products of double allylation (9a,
9a’ or 9a’’, see scheme 4) could be observed. In presence of base, rearrangement does not
occur significantly and 6a is almost the only amine present in the reaction medium. 6a is
probably too crowded to allow a second allylation to take place.

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
6
Table 1. Reaction of benzylamine with ((2-ferrocenylvinyl)methyl)trimethylammonium iodide
4
Run
1
benzylamine
20 eq.
2 eq.
solvent
EtOH
Na2CO3 5a/6aa
5ab
1%
63%
2%
9%
6%
5%
3%
6ab
76%
22%
65%
-
7b
-
8b
9ab
-
4/96
72/28
3/97
-
-
2
EtOH
-
2%
2%
2%
-
11%
-
3
2 eq.
EtOH
20 eq.
2%
-
26%
-
4
1 eq.
EtOH
-
20 eq.
-
100/0
5/95
13%
5
1 eq.
EtOH
49%
-
-
6
0.5 eq.
0.5 eq.
0.5 eq.
2 eq.
EtOH
100/0
4/96
100/0c 15%
15%
4%
8%
-
4%
73%
-
7
EtOH
20 eq.
-
66%
-
-
-
-
-
-
8
tBuOH
tBuOH
tBuOH
tBuOH
40%
3%
-
9
-
74/26
3/97
2/98
76%
3%
-
22%
75%
73%
10
11d
2 eq.
20 eq.
20 eq.
-
2 eq.
-
-
Reactions with 206 mg of 4 (0.5 mmol) in 6 ml solvent (ethanol or t-butanol) at 80°C or 90°C (solvent reflux)
during 16h. a: measured by 1H NMR analysis of the crude materials. b: isolated yields compared to 4. c: 39% of
4 recovered. d: reaction time= 6h.
Scheme 5: diallylation of benzylamine.

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
7
Because of the presence of significant amount of ethers 7Et and 8Et, we replaced the
solvent ethanol by the more crowded then less nucleophilic t-butanol. If the reaction was
slower in t-butanol (see table 1, entries 6 and 8), the amount of ethers 7 and 8 was much lower
(see, for instance, table 1, entries 2 and 9). In particular, reactions with two equivalents of
amine (table 1, entries 9-11) proved to be especially efficient to obtain 5a or 6a. We selected
these conditions to study the reaction of 4 with various amines. The results are collected in
Tables 2 and 3.
Table 2. Reaction of 4 with different alkylamines
Run
12
amine
Na2CO3
5/6a
100/0
7/93
5b
91%
-
6b
morpholine
morpholine
piperidine
-
-
13
20 eq.
-
72%
8%
88%
-
14
82/18
9/91
60%
-
15
piperidine
20 eq.
-
16
dibenzylamine
dibenzylamine
100/0
7/93
82%
5%
17
20 eq.
78%
Reactions with 206 mg of 4 (0.5 mmol) and 2eq. of amine in 6 ml t-butanol at 90°C (solvent reflux) during 16h.
a: measured by 1H NMR analysis of the crude materials. b: isolated yield.
For all amines, like for benzylamine, the linear isomer 5 was the major compound in absence
of sodium carbonate and branched isomer 6 was the main compound in presence of sodium
carbonate (see tables 2 and 3, entries 12-28) with good to excellent selectivities. The isolated
yields were also quite high (up to 91% for 5b, table 2, entry 12) and no ethers 7 or 8 were
detected.
However, in absence of potassium carbonate, new compounds were obtained with anilines
as substrates, except with 4-methylaniline. These new compounds 10 and 11 are obtained
from a Friedel-Crafts reaction (see scheme 6).
The primary product of the reaction is essentially (6)H+, as already stated above (see
scheme 4). If potassium carbonate is present in the reaction mixture, (6)H+ is deprotonated to
yield 6 which is stable and found at the end of the reaction. In the absence of potassium
carbonate, (6)H+is in equilibrium with (5)H+ and a small amount of C, which is responsible
for the Friedel-Crafts reactivity. To confirm this hypothesis, we study the reaction of 4 with a
tertiary aniline, namely N,N-dimethylaniline. With this substrate in presence or in the absence
of potassium carbonate, large amount of compounds 10 and 11 were found in the reaction

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
8
mixture at the end of the reaction (see table 3, entries 29-30). Indeed, N,N-dimethylaniline
yields a quaternary ammonium as primary product which is in equilibrium with carbocation C
even in presence of potassium carbonate. Friedel-Crafts usually provide essentially ortho and
para isomers. In the reaction of 4 with various anilines, only compounds 10 and 11 from
reaction in para position of anilines were observed, probably because of the steric hindrance
of carbocation C. In addition, the regioselectivity of the attack on the allylic part is in favor of
the  position related to ferrocene yielding 10 as the major product, probably again for steric
reasons.
Table 3. Reaction of 4 with various anilines
Run
18
amine
Na2CO3
5/6a
100/0 50%
6/94 5%
100/0 65%
8/92
100/0 51%
5b
6b
10b
12%c
11b
5% c
aniline
-
-
74%
-
19
aniline
20 eq.
-
-
-
20
4-methylaniline
4-methylaniline
2,4,6-trimethylaniline
2,4,6-trimethylaniline
N-methylaniline
N-methylaniline
N-methylaniline
N-ethylaniline
-
-
21
20 eq.
-
-
75%
-
-
-
22
-
-
23
20 eq.
-
18/82 17% 65%
-
38% c
-
-
7% c
-
24
100/0 33%
100/0 98%
-
25
26d
20 eq.
20 eq.
-
-
73%
-
9/91
7%
-
-
27
100/0 17%
53% c
12% c
28 d
29
N-ethylaniline
20 eq.
-
30/70 51% 30%
-
-
N,N-dimethylanilinee
N,N-dimethylanilinef
-
-
-
30% c
18% c
6% c
3% c
30
20 eq.
Reactions with 206 mg of 4 (0.5 mmol) and 2eq. of amine in 6 ml t-butanol at 90°C (solvent reflux) during 16h.
1
a: measured by H NMR analysis of the crude materials. b: isolated yield. c: as a mixture of 10 and 11. d: the
reaction was carried out in the same conditions than other reactions but the workup was modified (see
experimental section: workup B). e: 58% of 4 recovered. f: 30% of 4 recovered.
Scheme 6: Friedel-Crafts reaction of anilines with allylammonium 4.

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
9
The branched isomers obtained from N-methylaniline and N-ethylaniline are very
sensitive to any acidic traces: a new specific work-up had to be developed in order to isolate
compounds 6h and 6i (see table 3, entries 25-26 and 27-28, see also experimental section). In
addition, if the synthetics targets are the linear isomers 5h or 5i, the best experimental
conditions are to carry out the reaction with potassium carbonate but with the usual work-up
(see experimental section : work-up A) and to carry out the purification step by flash
chromatography on silica gel in slightly acidic conditions, namely with an eluant without any
trimethylamine (see table 3, entries 25 and 28).
Several ferrocene derivatives could be studied by X-ray diffraction analysis on single
crystals. Compounds 4, 5c, 5d, 5f, 5h and 5i present closely related structure based on a
ferrocene moiety, a Cp of which has been substituted by allyl amine chains as shown on
Figures 1, 2, 3, 4, 5 and 6. In compounds 4 and 5f, there are two molecules within the
asymmetric unit. A molecular fitting23 of the two molecules is shown in Figures S1 and S2
(see Supporting Informations). For compound 4, the two independent molecules appear well
superimposed, the only difference being the position of the unsubstituted Cp: in one molecule
the two Cp are nearly eclipsed with a twist angle  of 3.6(8)° whereas in the second one the
two Cp are nearly staggered with a twist angle of 15.2(8)° (Table 4). In 5f, the respective
conformation of the Cp rings is also different with a twist angle of 11.4(8)° and 1.2(9)°
respectively but the more marked difference is the relative conformation of the C1-C2=C3,
there is 180° rotation around the C1-C2 bond between the two molecules.
Scheme 7: numbering scheme for compounds 4 and 5.
The distances within the Fc-C=C-C-N fragment (see scheme 7) are nearly identical within
experimental error as indicated by the comparison of bond distances in Table 4. The Fc-C=C-
N torsion angles are close to 180° as expected owing to the occurrence of the C=C double
bond. The values observed for the C=C-C-N torsion angles which differ obviously for 180°
are related not only to the intramolecular H…H contacts between the amine chain and the

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
10
ferrocene moiety but also to the occurrence of weak intermolecular C-H… interactions (see
Supporting Information, Table S1) which might control the packing.
Table 4 Selected geometrical parameters: Bond distances (Å), Torsion angles (°) and Cp rings
conformation  (°). Selected bond distances (Å)
4
5c
5d
5f
5h
5i
C1 –
C2
1.457(8)
1.522(13)
1.468(4) 1.461(2) 1.470(7)
1.475(8)
1.468(4)
1.4626(18)
C2 –
C3
1.301(8)
1.346(12)
1.322(4) 1.325(2) 1.329(7)
1.292(7)
1.343(4)
1.501(4)
1.464(3)
1.401(4)
1.459(4)
1.326(2)
C3 –
C4
1.487(7)
1.523(12)
1.497(4) 1.494(2) 1.511(8)
1.506(8)
1.5047(19)
1.440(2)
C4 –
N1
1.492(7)
1.475(9)
1.466(3) 1.472(2) 1.445(7)
1.449(7)
N1 –
C5
1.503(6)
1.503(6)
1.459(3) 1.462(2) 1.392(7)
1.378(7)
1.3816(18)
N1 –
C6
1.488(6)
1.470(9)
1.469(4) 1.467(2)
N1 –
C7
1.482(6)
1.426(9)
Selected torsion angles (°)
Compounds
4
5c
5d
5f
5h
5i
C1-C2-C3-
C4
-180.0(5)
175.1(7) 180.0(3)
-
-177.9(1) -176.4(5) -173,4(2) 179.0(1)
-178.8(5)
C2-C3-C4-
N1
-134.4(5)
-128.0(8) 123.4(3)
-
-136.3(2)
9.5(8)
127.3(6)
105.5(3)
-6.1(2)
Cp1/Cp2 conformation  (°)
Cp1/Cp2
4
5c
5d
5f
5h
5i
3.6(8)
11.2(2)
7.5(1)
11.4(8)
5.1(2) 1.03(1)


European Journal of Inorganic Chemistry
10.1002/ejic.201600860
11
15.2(8)
1.2(9)
Figure 1: Molecular view of compound 4 with the atom labelling scheme. Ellipsoids are
drawn at the 50% probability level. H atoms are represented as small circle of arbitrary radii.
Only one molecule of the two building the asymmetric unit is represented.
Figure 2: Molecular view of compound 5c with the atom labelling scheme. Ellipsoids are

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
12
drawn at the 50% probability level. H atoms are represented as small circle of arbitrary radii.
Figure 3: Molecular view of compound 5d with the atom labelling scheme. Ellipsoids are
drawn at the 50% probability level. H atoms are represented as small circle of arbitrary radii.

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
13
Figure 4: Molecular view of compound 5f with the atom labelling scheme. Ellipsoids are
drawn at the 50% probability level. H atoms are represented as small circle of arbitrary radii.
Only one molecule of the two building the asymmetric unit is represented.
Figure 5: Molecular view of compound 5h with the atom labelling scheme. Ellipsoids are
drawn at the 50% probability level. H atoms are represented as small circle of arbitrary radii.
Figure 6: Molecular view of compound 5i with the atom labelling scheme. Ellipsoids are
drawn at the 50% probability level. H atoms are represented as small circle of arbitrary radii.
Conclusions

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
14
((2-ferrocenylvinyl)methyl)trimethylammonium 4 could be easily obtained in high yields in
only two steps from commercially available vinylferrocene. Ammonium 4 proved to be a
valuable reagent to obtain various new ferrocenyl allylamines from various primary and
secondary amines. By controlling the reaction conditions, in particular the amounts of base in
the reaction media, the kinetic products (branched allylamines) or the thermodynamic
products (linear allylamines) could be obtained with good selectivities. Ammonium 4 proved
to be also a reagent for the Friedel-crafts reaction on anilines with a total regioselectivity for
the para position.
Investigations about the reactivity and the biological properties of these new ferrocene
derivatives are now in progress in our laboratories.
Experimental Section
General Information. All reactions were carried out under an argon atmosphere using
standard Schlenk techniques. Solvents were carefully dried by conventional methods and
distilled under argon before use. All commercially available chemicals were used as received.
1H and 13C{1H} NMR spectra were recorded with Bruker Avance 400 FT-NMR
spectrometer. The resonances were calibrated relative to the residual solvent peaks and are
reported with positive values downfield from TMS. For all characterized compounds, the
1
13
peak assignments in the H and C NMR spectra were based on COSY, HSQC and HMBC
2D experiments. HRMS were obtained from dichloromethane solutions with a Xevo G2 Q
TOF spectrometer by the electrospray method from the “Service commun de spectrométrie de
masse de la Structure Fédérative en Chimie Moléculaire de l’Université Paul Sabatier” in
Toulouse.
Synthesis of ((2-ferrocenylvinyl)methyl)dimethylamine 2
In a Schlenk tube under argon were dissolved 936 mg of N,N-dimethylmethyleneiminium
chloride (10 mmol, 2 eq) in 10 ml of anhydrous dichloromethane. To this suspension, were
added with a canula 1.06 g of vinylferrocene 1 dissolved in 20 ml of anhydrous
dichloromethane under argon. The reaction mixture was stirred at RT overnight. 10 mL of an
aqueous sodium hydroxide solution (1M) were then added and the crude materials was
extracted with dichloromethane, washed with brine, dried on sodium sulfate and concentrated
under vacuum.

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
15
After purification by flash chromatography on silicagel (eluent: ethyl acetate /methanol (8/2,
v/v) + ε of triethylamine,), 1.043g of compound 2 (78 % yield) were obtained as a yellow
solid with traces of compound 3.
((2-ferrocenylvinyl)methyl)dimethylamine 2 1H NMR (400MHz, CDCl3): 6.67 (1H, d,
J=15.6Hz, CH vinyl), 6.00 (1H, d of t, J=15.6Hz, J=7.5Hz, CH vinyl), 4.44 (2H, t, J=1.7Hz, subst Cp),
4.35 (2H, t, J=1.7Hz, subst Cp), 4.16 (5H, s, Cp), 3.70 (2H, d, J=7.5Hz, CH2), 2.79 (6H, s, CH3). 13C
NMR (125MHz, CDCl3): 141.0 (s, CH vinyl), 111.5(s, CH vinyl), 79.6 (s, quat. Cp), 70.0 (s, subst.
Cp), 69.3 (s, Cp), 67.6 (s, subst. Cp), 60.2 (s, CH2), 41.7 (s, CH3). HR MS (DCI, CH4): 269.0877
(100%, 269.0867 for C15H19FeN: M); 225.0383 (55%, 225.0367 for C13H13Fe: M-NMe2).
1
(((1-ferrocenyl)(1-vinyl)methyl) dimethylamine 3 H (400MHz, CDCl3): 6.09 (1H, ddd, J=16.6Hz,
J=10.6Hz, J=8.7Hz, CH vinyl), 5.35-5.25 (2H, m, CH vinyl), 4.2-4.1 (4H, m, subst Cp), 4.11 (5H, s,
Cp), 3.73 (1H, d, J=8.8Hz, CH), 3.77 (6H, s, CH3). 13C (125MHz, CDCl3): 136.2 (s, CH vinyl), 116.9
(s, CH vinyl), 86.5 (s, quat. Cp), 68.9 (s, Cp), 68.5 (s, subst. Cp), 67.9 (s, CH), 67.7 (s, subst. Cp), 67.3
(s, subst. Cp), 67.2 (s, subst. Cp), 41.8 (s, CH3). HR MS (ESI+): 270.0948 (2%, 270.0945 for
C15H20FeN: M+H), 225.0377 (100%, 225.0367 for C13H13Fe: M-N(CH3)2)
Synthesis of ((2-ferrocenylvinyl)methyl)trimethylammonium iodide 4
In a round-bottommed flask, 1.6 g of amine 2 (6 mmol) was dissolved in diethylether. 1.7 g of
iodomethane (12 mmol, 2 eq) were then added by syringe. The reaction mixture was stirred at
RT for 48h. An abundant yellow precipitate of 4 (2.38 g, 97%) was then filtered on sintered
glass.
1
((2-ferrocenylvinyl)methyl)trimethylammonium iodide 4: H (400MHz, CDCl3): 6.97 (1H, d,
J=15.4Hz, CH vinyl), 5.85 (1H, d of t, J=15.4Hz, J=7.7Hz, CH vinyl), 4.47 (2H, m, subst Cp), 4. 42
(2H, d, J=7.7Hz, CH2), 4.37 (2H, m, subst Cp), 4.17 (5H, s, Cp), 3.43 (9H, s, CH3). 13C (125MHz,
CDCl3): 144.5 (s, CH vinyl), 109.8 (s, CH vinyl), 79.5 (s, quat. Cp), 70.2 (s, subst. Cp), 69.4 (s, Cp),
68.7 (s, CH2), 67.7 (s, subst. Cp), 52.8 (s, CH3). HR MS (ESI+): 284.1104 (100%, 284.1102 for
C16H22Fe N: M –I-)
Reaction of ammonium 4 with amines
General procedure
In a Schlenk tube under argon, 206 mg of ammonium 4 (0.5 mmol) were dissolved in 6 ml
solvent (ethanol or t-butanol). Amine was added by syringe and sodium carbonate as solid.
The reaction mixture was stirred at reflux overnight.

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
16
At the end of the reaction, the reaction mixture was cooled down to RT and the organic phase
was extracted with dichloromethane, washed by NaCl saturated solution and dried by sodium
carbonate (work-up A).
Due to the sensitivity of branched isomers of N-methylaniline and N-ethylaniline, the crude of
the reaction of these two nucleophilic was treated by 25 ml of diethyl ether after evaporation
of the reaction solvent. The mixture was filtered and the filtrate solution was concentrated
under vacuum. If the conversion is not complete, the ammonium 4 which remains is
recovered on the paper filter (work up B).
Benzylamine:
The crude reaction mixture was separated by flash chromatography on silica gel with ethyl
acetate/petroleum ether (2:8) as eluent to yield 5a and 9a. 0.4% of triethylamine was added to
the eluent to obtain 6a from the crude reaction. Compounds 7-Et and 8-Et or 7-tBu were also
isolated according to the solvent used.
1
((2-ferrocenylvinyl)methyl)benzylamine 5a: H (400MHz, CDCl3): 7.40-7.25 (5H, m, Ph), 6.29
(1H, d of t, J=15.7Hz, J=1.4Hz, CH vinyl), 5.24 (1H, d of t, J=15.7Hz, J=6.5Hz, CH vinyl), 4.34 (2H,
pseudo t, J=1.9Hz, subst Cp), 4.21 (2H, pseudo t, J=1.9Hz, subst Cp), 4.12 (5H, s, Cp), 3.86 (2H, s,
CH2Ph), 3.33 (2H, dd, J=6.5Hz, J=1.4Hz, CH2-vinyl). 13C (125MHz, CDCl3): 140.3 (s, quat. Ph),
129.1 (s, CH vinyl), 128.5 (s, Ph), 128.2 (s, Ph), 126.7 (s, Ph), 125.6 (s, CH vinyl), 83.2 (s, quat. Cp),
69.1 (s, Cp), 68.5 (s, subst. Cp), 66.7 (s, subst. Cp), 53.2 (s, CH2Ph), 51.4 (s, CH2-vinyl). ). HR MS
(ESI+): 331.1017 (88%, 331.1023 for C20H21FeN: M).
1
((1-ferrocenyl)(1-vinyl)methylbenzylamine 6a: H (400MHz, CDCl3): 7.40-7.30 (5H, m, Ph), 5.92
(1H, ddd, J=17.1Hz, J=10.1Hz, J=8.2Hz, CH vinyl), 5.24 (2H, m, CH vinyl), 4.20 (2H, m, subst Cp),
4.14 (2H, m, subst Cp), 4.13 (5H, s, Cp), 3.93 (1H, d, J=13.5Hz, CH2Ph), 3.89 (1H, d, J=8.2Hz, CH),
3.77 (1H, d, J=13.5Hz, CH2Ph). 13C (125MHz, CDCl3): 140.6 (s, quat. Ph), 140.4 (s, CH vinyl), 128.4
(s, Ph), 128.2 (s, Ph), 126.9 (s, Ph), 115.7 (s, CH vinyl), 91.3 (s, quat. Cp), 68.4 (s, Cp), 67.7 (s, subst.
Cp), 67.5 (s, subst. Cp), 66.7 (s, subst. Cp), 66.6 (s, subst. Cp), 59.5 (s, CH), 52.8 (s, CH2Ph). HR MS
(ESI+): 331.1021 (100%, 331.1023 for C20H21FeN: M).
1
Bis-((2-ferrocenylvinyl)methyl)benzylamine 9a: H (400MHz, CDCl3): 7.40-7.25 (5H, m, Ph), 6.31
(2H, d , J=15.7Hz, CH vinyl), 5.24 (2H, d of t, J=15.7Hz, J=6.7Hz, CH vinyl), 4.37 (2H, pseudo t,
J=1.8Hz, subst Cp), 4.22 (2H, pseudo t, J=1.8Hz, subst Cp), 4.11 (5H, s, Cp), 3.68 (2H, s, CH2Ph),
3.18 (2H, d, J=6.7Hz, CH2-vinyl). 13C (125MHz, CDCl3): 139.5 (s, quat. Ph), 130.2 (s, CH vinyl),
129.0 (s, Ph), 128.3 (s, Ph), 126.9 (s, Ph), 124.6 (s, CH vinyl), 83.2 (s, quat. Cp), 69.1 (s, Cp), 68.5 (s,
subst. Cp), 66.7 (s, subst. Cp), 57.6 (s, CH2Ph), 55.8 (s, CH-vinyl). HR MS (ESI+): 556.1396 (24%,

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
17
556.1391 for C33H33Fe2N: M+H), 225.0376 (100%, 225.0367 for C13H13Fe: M-
N(CH2Ph)(CH2CH=CHFc))
1
((2-ferrocenylvinyl)methyl) ethyl oxide 7-Et: H (400MHz, CDCl3): 6.35 (1H, d , J=15.7Hz, CH
vinyl), 5.91 (1H, d of t, J=15.7Hz, J=6.3Hz, CH vinyl), 4.36 (2H, br s, subst Cp), 4.22 (2H, br s, subst
Cp), 4.13 (5H, s, Cp), 4.03 (2H, dd, J=6.3Hz, J=1.1Hz, CH2-vinyl), 3.54 (2H, q, J=7.0Hz, CH2), 1.26
(3H, t, J=7.0Hz, CH3). 13C (125MHz, CDCl3): 130.3 (s, CH vinyl), 123.7 (s, CH vinyl), 82.9 (s, quat.
Cp), 71.5 (s, CH2-vinyl), 69.2 (s, Cp), 68.7 (s, subst. Cp), 66.9 (s, subst. Cp), 65.3 (s, CH2CH3), 15.3
(s, CH2CH3). HR MS (ESI+): 270.0710 (78%, 270.0707for C15H218FeO: M); 225.0369 (100%,
225.0367 for C13H13Fe: M-OEt))
1
((1-ferrocenyl)(1-vinyl)methyl ethyl oxide 8-Et: H (400MHz, CDCl3): 6.06 (1H, ddd, J=17.4Hz,
J=10.2Hz, J=7.4Hz, CH vinyl), 5.35 (1H, ddd, J=17.4Hz, J=1.6Hz, J=1.0Hz, CH vinyl), 5.29 (1H,
ddd, J=10.2Hz, J=1.6Hz, J=1.0Hz, CH vinyl), 4.54 (1H, br d, J=7.4Hz, CH), 4.21 (1H, m, subst Cp),
4.19 (1H, m, subst Cp), 4.17-4.14 (2H, m, subst Cp), 4.16 (5H, s, subst Cp), 3.6-3.4 (2H, m, CH2),
1.21 (3H, t, J=7.0Hz, CH3). 13C (125MHz, CDCl3): 137.9 (s, CH vinyl), 116.1 (s, CH vinyl), 87.9 (s,
quat. Cp), 79.0 (s, CH), 68.8 (s, Cp), 68.08 (s, subst. Cp), 68.06 (s, subst. Cp), 67.9 (s, subst. Cp), 66.6
(s, subst. Cp), 63.6 (s, CH2), 15.4 (s, CH3). HR MS (ESI+): 270.0715 (50%, 270.0707 for
C15H218FeO: M); 225.0715 (100%, 225.0367 for C13H13Fe: M-OEt)).
1
((2-ferrocenylvinyl)methyl) t-butyl ether 7- t-Bu: H (400MHz, CDCl3): 6.33 (1H, d, J=15.7Hz,
J=1.5Hz, CH vinyl), 5.90 (1H, d of t, J=15.7Hz, J=6.1Hz, CH vinyl), 4.33 (2H, t, J=1.9Hz, subst Cp),
4.19 (2H, t, J=1.9Hz, subst Cp), 4.12 (5H, s, Cp), 3.97 (2H, dd, J=6.1Hz, J=1.5Hz, CH2-vinyl), 1.27
(9H, s, CH3). 13C (125MHz, CDCl3): 128.8 (s, CH vinyl), 125.5 (s, CH vinyl), 83.1 (s, quat. Cp), 73.2
(s, C(CH3)3), 69.0 (s, Cp), 68.5 (s, subst. Cp), 66.8 (s, subst. Cp), 63.2 (s, CH2-vinyl), 27.7 (s,
C(CH3)3). HR MS (ESI+): 298.1024 (100%, 298.1020 for C17H22FeO: M).
Morpholine:
The crude reaction mixture was separated by flash chromatography on silica gel with diethyl
ether/petroleum ether (2:8) as eluent to yield 5b. 0.4% of triethylamine was added to the
eluent to obtain 6b from the crude materials.
1
N-(((2-ferrocenylvinyl)methyl) morpholine 5b: 1H (400MHz, CDCl3): H (400MHz, CDCl3): 6.29
(1H, d of t, J=15.7Hz, J=1.4Hz, CH vinyl), 5.85 (1H, d of t, J=15.7Hz, J=6.9Hz, CH vinyl), 4.34 (2H,
pseudo t, J=1.9Hz, subst Cp), 4.21 (2H, pseudo t, J=1.8Hz, subst Cp), 4.11 (5H, s, Cp), 3.76 (4H, t,
J=4.7Hz, CH2 morpholine), 3.04 (2H, dd, J=6.9Hz, J=1.4Hz, CH2-vinyl), 2.51 (4H, t, J=4.7Hz, CH2
morpholine). 13C (125MHz, CDCl3): 131.2 (s, CH vinyl), 123.1 (s, CH vinyl), 82.8 (s, quat. Cp), 69.1
(s, Cp), 68.7 (s, subst. Cp), 67.0 (s, subst. Cp or CH2 morpholine), 66.7 (s, subst. Cp or CH2

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
18
morpholine), 61.7 (s, CH2-vinyl), 53.6 (s, CH2 morpholine). HR MS (ESI+): 311.0971 (2%, 311.0973
for C17H21FeNO: M), 225.0374 (100%, 225.0367 for C13H13Fe: M-morpholyl)
1
1
N-(((1-ferrocenyl)(1-vinyl)methyl) morpholine 6b: H (400MHz, CDCl3): H (400MHz, CDCl3):
6.08 (1H, m, CH vinyl), 5.3-5.30 (2H, m, CH vinyl), 4.18-4.08 (4H, m, subst Cp), 4.11 (5H, s, Cp),
3.68-3.58 (5H, m, 1H CH + 4H CH2 morpholine), 2.49-2.39 (2H, m, 2H CH2 morpholine), 2.39-2.30
(2H, m, 2H CH2 morpholine). 13C (125MHz, CDCl3): 136.7 (s, CH vinyl), 116.8 (s, CH vinyl), 86.1
(s, quat. Cp), 69.5 (s, subst. Cp), 69.0 (s, Cp), 68.3 (s, subst. Cp), 68.0 (s, subst. Cp), 67.24 (s, CH or
subst. Cp), 67.23 (s, CH or subst. Cp), 67.2 (s, CH2 morpholine), 50.7 (s, CH2 morpholine). HR MS
(ESI+): 311.0971 (3%, 311.0973 for C17H21FeNO: M), 225.0377 (100%, 225.0367 for C13H13Fe: M-
morpholyl).
piperidine:
The crude reaction mixture was separated by flash chromatography on silica gel with diethyl
ether/petroleum ether (2:8) as eluent to yield 5c. 0.4% of triethylamine was added to the
eluent to obtain 6c from the crude materials.
1
N-(((2-ferrocenylvinyl)methyl) piperidine 5c: 1H (400MHz, CDCl3): H (400MHz, CDCl3): 6.24
(1H, d of t, J=15.7Hz, J=1.3Hz, CH vinyl), 5.90 (1H, d of t, J=15.7Hz, J=7Hz, CH vinyl), 4.34 (2H,
pseudo t, J=1.9Hz, subst Cp), 4.20 (2H, pseudo t, J=1.9Hz, subst Cp), 4.11 (5H, s, Cp), 3.01 (2H, dd,
J=7Hz, J=1.3Hz, CH2-vinyl), 2.44 (4H, br s, CH2 piperidiine), 1.64 (4H, m, CH2 piperidine), 1.47 (2H,
m, CH2 piperidine). 13C (125MHz, CDCl3): 130.3 (s, CH vinyl), 124.3 (s, CH vinyl), 83.1 (s, quat.
Cp), 69.0 (s, Cp), 68.5 (s, subst. Cp), 66.7 (s, subst. Cp), 62.0 (s, CHCH2), 54.5 (s,2C CH2 piperidine),
26.0 (s, 2C CH2 piperidine), 24.4 (s, CH2 piperidine). HR MS (ESI+): 310.1256 (7%, 310.1258 for
C18H24FeN: M+1), 225.0373 (100%, 225.0367 for C13H13Fe: M-piperidyl).
1
1
N-(((1-ferrocenyl)(1-vinyl)methyl) piperidine 6c: H (400MHz, CDCl3): H (400MHz, CDCl3):
6.13 (1H, ddd, J=17.1Hz, J=10.2Hz, J=8.2Hz, CH vinyl), 5.40-5.25 (2H, m, CH vinyl), 4.18-4.08 (4H,
m, subst Cp), 4.11 (5H, s, Cp), 3.76 (1H, d, J=8.2Hz, NCH), 2.33 (4H, m, CH2 piperidine), 1.51 (4H,
m, CH2 piperidine), 1.36 (2H, m, CH2 piperidine). 13C (125MHz, CDCl3): 137.1 (s, CH vinyl), 116.3
(s, CH vinyl), 86.6 (s, quat. Cp), 69.3 (s, subst. Cp), 69.0 (s, Cp), 68.1 (s, CH ), 67.56 (s, subst. Cp),
67.52 (s, subst. Cp), 67.1 (s, subst. Cp), 51.1 (s, 2C CH2 piperidine), 26.2 (s, 2C CH2 piperidine), 24.6
(s, CH2 piperidine). HR MS (ESI+): 310.1256 (5%, 310.1258 for C18H24FeN: M+1), 225.0369 (100%,
225.0367 for C13H13Fe: M-piperidyl).
N,N-dibenzylamine:

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
19
The crude reaction mixture was separated by flash chromatography on silica gel with diethyl
ether/petroleum ether (1:9) as eluent to yield 5d. 0.4% of triethylamine was added to the
eluent to obtain 6d from the crude materials.
1
((2-ferrocenylvinyl)methyl)dibenzylamine 5d: H (400MHz, CDCl3): 7.45-7.20 (10H, m, Ph), 6.29
(1H, d, J=15.8Hz, CH vinyl), 5.91 (2H, d of t, J=15.8Hz, J=6.6Hz, CH vinyl), 4.35 (2H, pseudo t,
J=1.7Hz, subst Cp), 4.21 (2H, pseudo t, J=1.7Hz, subst Cp), 4.10 (5H, s, Cp), 3.64 (4H, s, CH2Ph),
3.12 (2H, d, J=6.6Hz, CH2-vinyl). 13C (125MHz, CDCl3): 139.8 (s, quat. Ph), 130.1 (s, CH vinyl),
128.8 (s, Ph), 128.2 (s, Ph), 126.8 (s, Ph), 124.7 (s, CH vinyl), 83.3 (s, quat. Cp), 69.0 (s, Cp), 68.5 (s,
subst. Cp), 66.6 (s, subst. Cp), 57.8 (s, CH2Ph), 55.8 (s, CH2-vinyl). HR MS (ESI+): 422.1559 (8%,
422.1571 for C27H28FeN: M+H), 225.0384 (100%, 225.0367 for C13H13Fe: M-N(CH2Ph)2).
1
(((1-ferrocenyl)(1-vinyl)methyl)dibenzylamine 6d: H (400MHz, CDCl3): 7.45-7.40 (4H, m, Ph),
7.37-7.30 (4H, m, Ph), 7.28-7.22 (2H, m, Ph), 6.14 (1H, ddd, J=17.1Hz, J=10.3Hz, J=8.0Hz, CH
vinyl), 5.44 (1H, ddd, J=10.3Hz, J=2.2Hz, J=1.0Hz, CH vinyl), 5.38 (1H, ddd, J=17.1Hz, J=2.2Hz,
J=1.1Hz, CH vinyl), 4.26-4.24 (5H, m, 4H subst Cp + 1H CH), 4.01 (5H, s, Cp), 3.62 (1H, d, J=14Hz,
CH2Ph), 3.47 (1H, d, J=14Hz, CH2Ph). 13C (125MHz, CDCl3): 140.5 (s, quat. Ph), 135.4 (s, CH
vinyl), 128.5 (s, Ph), 128.2 (s, Ph), 126.7 (s, Ph), 117.9 (s, CH vinyl), 87.6 (s, quat. Cp), 68.8 (s, subst.
Cp), 68.7 (s, Cp), 67.7 (s, subst. Cp), 67.6 (s, subst. Cp), 67.3 (s, subst. Cp), 60.4 (s, CH-vinyl), 53.4
(s, CH2Ph). HR MS (ESI+): 421.1498 (8%, 421.1493 for C27H27FeN: M), 225.0377 (56%, 225.0367
+
for C13H13Fe: M-N(CH2Ph)2), 198.1307 (100%, 198.1283 for C14H16N: (PhCH2)2NH2 ).
aniline:
The crude reaction mixture was separated by flash chromatography on silica gel with diethyl
ether/petroleum ether (2:8) as eluent to yield 5e. 1% of triethylamine was added to the eluent
to obtain 6e from the crude materials.
1
N-(((2-ferrocenylvinyl)methyl) aniline 5e: 1H (400MHz, CDCl3): H (400MHz, CDCl3): 7.26-7.21
(2H, m, Ph), 6.78-6.67 (3H, m, Ph), 6.39 (1H, d of t, J=15.7Hz, J=1.4Hz, CH vinyl), 5.93 (1H, d of t,
J=15.7Hz, J=5.7Hz, CH vinyl), 4.35 (2H, pseudo t, J=1.8Hz, subst Cp), 4.23 (2H, pseudo t, J=1.9Hz,
13
subst Cp), 4.12 (5H, s, Cp), 3.83 (2H, dd, J=5.7Hz, J=1.4Hz CH2). C (125MHz, CDCl3): 148.2 (s,
quat. Ph), 129.22 (s, Ph), 129.18 (s, CH vinyl), 124.1 (s, CH vinyl), 117.6 (s, Ph), 113.1 (s, Ph), 82.9

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
20
(s, quat. Cp), 69.1 (s, Cp), 68.6 (s, subst. Cp), 66.7 (s, subst. Cp), 46.4 (s, CH2-vinyl). HR MS (ESI+):
317.0871 (100%, 317.0867 for C19H19FeN: M).
1
1
N-(((1-ferrocenyl)(1-vinyl)methyl) aniline 6e: H (400MHz, CDCl3): H (400MHz, CDCl3): 7.26-
7.21 (2H, m, Ph), 6.78-6.70 (3H, m, Ph), 6.07 (1H, ddd, J=17.2Hz, J=10.2Hz, J=6.2Hz, J=1Hz, CH
vinyl), 5.39 (1H, d of q, J=17.2Hz, J=1.3Hz, CH vinyl), 5.28 (1H, d of q, J=10.2Hz, J=1.3Hz, CH
vinyl), 4.66 (1H, br d, J=6.2Hz, CH), 4.27-4.20 (4H, m, subst Cp), 4.26 (5H, s, Cp). 13C (125MHz,
CDCl3): 147.5 (s, quat. Ar), 138.7 (s, CH vinyl), 129.2 (s, Ar), 117.4 (s, Ar), 115.6 (s, CH vinyl),
113.4 (s, Ar), 91.0 (s, quat. Cp), 68.6 (s, Cp), 68.1 (s, subst. Cp), 67.9 (s, subst. Cp), 67.2 (s, subst.
Cp), 66.6 (s, subst. Cp). HR MS (ESI+): 317.0864 (3%, 317.0867 for C19H19FeN: M). 225.0373 (82%,
225.0367 for C13H13Fe: M-NHPh)
4-methylaniline:
The crude reaction mixture was separated by flash chromatography on silica gel with ethyl
acetate/petroleum ether (2:8) as eluent to yield 5f. 4% of triethylamine was added to the
eluent to obtain 6f from the crude materials.
N-(((2-ferrocenylvinyl)methyl) (4-methylphenyl) amine 5f: 1H (400MHz, CDCl3): 1H (400MHz,
CDCl3): 7.05 (2H, m, Ph), 6.64 (2H, m, Ph), 6.38 (1H, d of t, J=15.8Hz, J=1.6Hz, CH vinyl), 5.93 (1H,
d of t, J=15.7Hz, J=5.8Hz, CH vinyl), 4.34 (2H, t, J=1.8Hz, subst Cp), 4.22 (2H, t, J=1.8Hz, subst
Cp), 4.12 (5H, s, Cp), 3.80 (2H, dd, J=5.8Hz, J=1.6Hz, CH2-vinyl), 2.28 (s, CH3). 13C (125MHz,
CDCl3): 145.9 (s, quat. Ph), 129.7 (s, Ph), 129.0 (s, CH vinyl), 126.8 (s, quat Ph), 124.4 (s, CH vinyl),
113.4 (s, Ph), 82.9 (s, quat. Cp), 69.1 (s, Cp), 68.6 (s, subst. Cp), 66.7 (s, subst. Cp), 46.8 (s, CH2-
vinyl), 20.4 (s, CH3). HR MS (ESI+): 330.0944 (3%, 330.0945 for C20H20FeN: M-H), 225.0374 (82%,
225.0367 for C13H13Fe: M-NHAr)
N-(((1-ferrocenyl)(1-vinyl)methyl) (4-methylphenyl) amine 6f: 1H (400MHz, CDCl3): 1H
(400MHz, CDCl3): 7.05 (2H, m, Ph), 6.65 (2H, m, Ph), 6.06 (1H, ddd, J=17.2Hz, J=10.2Hz, J=6.2Hz,
CH vinyl), 5.38 (1H, d of t, J=17.2Hz, J=1.4Hz, CH vinyl), 5.27 (1H, d of t, J=10.2Hz, J=1.4Hz, CH
vinyl), 4.63 (1H, d of t, J=6.2Hz, J=1.4Hz, CH), 4.29-4.20 (4H, m, subst Cp), 4.26 (5H, s, Cp), 2.30
(3H, s, CH3). 13C (125MHz, CDCl3): 145.3 (s, quat. Ar), 138.9 (s, CH vinyl), 129.7 (s, Ar), 126.6 (s,
quat. Ar), 115.5 (s, CH vinyl), 113.6 (s, Ar), 91.1 (s, quat. Cp), 68.6 (s, Cp), 68.1 (s, subst. Cp), 67.8
(s, subst. Cp), 67.1 (s, subst. Cp), 66.7 (s, subst. Cp), 20.5 (s, CH3). HR MS (ESI+): 330.0944 (20%,
330.0945 for C20H20FeN: M-H), 225.0375 (82%, 225.0367 for C13H13Fe: M-NHAr)
2,4,6-trimethylaniline:

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
21
The crude reaction mixture was separated by flash chromatography on silica gel with ethyl
acetate/petroleum ether (2:8) as eluent to yield 5g. 4% of triethylamine was added to the
eluent to obtain 6g from the crude materials.
N-(((2-ferrocenylvinyl)methyl) (2,4,6-trimethylphenyl) amine 5g: 1H (400MHz, CDCl3): 1H
(400MHz, CDCl3): 6.87 (2H, s, Ar), 6.30 (1H, d of t, J=15.6Hz, J=1.3Hz, CH vinyl), 5.95 (1H, d of t,
J=15.6Hz, J=6.7Hz, CH vinyl), 4.32 (2H, t, J=1.9Hz, subst Cp), 4.20 (2H, t, J=1.9Hz, subst Cp), 4.08
(5H, s, Cp), 3.60 (2H, dd, J=6.7Hz, J=1.3Hz, CH2-vinyl), 2.33 (6H, s, CH3), 2.25 (3H, s, CH3). 13C
(125MHz, CDCl3): 143.2 (s, quat. Ar), 131.4 (s, quat. Ar), 129.8 (s, 2C quat. Ar), 129.4 (s, Ar), 129.0
(s, CH vinyl), 125.4 (s, CH vinyl), 82.9 (s, quat. Cp), 69.1 (s, Cp), 68.6 (s, subst. Cp), 66.7 (s, subst.
Cp), 51.2 (s, CH2-vinyl), 20.6 (s, 2C CH3), 18.5 (s, CH3). HR MS (ESI+): 358.1261 (45%, 358.1258
for C22H24FeN: M-1), 225.0376 (100%, 225.0367 for C13H13Fe: M-NHAr)
1
N-(((1-ferrocenyl)(1-vinyl)methyl) (2,4,6-trimethylphenyl) amine 6g: H (400MHz, CDCl3): 1H
(400MHz, CDCl3): 6.82 (2H, s, Ph), 6.16 (1H, ddd, J=17Hz, J=10Hz, J=7Hz, CH vinyl), 5.20 (1H, d
of t, J=17Hz, J=1.4Hz, CH vinyl), 5.14 (1H, d of dd, J=10Hz, J=1.4Hz, J=1Hz, CH vinyl), 4.37-4.32
(2H, m, 1H subst Cp + 1H CH), 4.21 (5H, s, Cp), 4.19 (1H, m, subst Cp), 4.15 (1H, m, subst Cp), 3.94
13
(1H, m, subst Cp), 2.25 (3H, s, CH3), 2.19 (6H, s, CH)3. C (125MHz, CDCl3): 141.7 (s, quat. Ar),
138.9 (s, CH vinyl), 130.9 (s, Ar), 129.8 (s, 2C quat. Ar), 129.4 (s, Ar), 115.5 (s, CH vinyl), 91.1 (s,
quat. Cp), 68.4 (s, Cp), 67.9 (s, subst. Cp), 67.8 (s, subst. Cp), 67.6 (s, subst. Cp), 65.9 (s, subst. Cp),
58.8 (s, CH2-vinyl), 20.6 (s, 2C CH3), 18.8 (s, CH3). HR MS (ESI+): 359.1332 (18%, 359.1336 for
C22H25FeN: M), 225.0375 (100%, 225.0367 for C13H13Fe: M-NHAr).
N-methylaniline:
The crude reaction mixture was separated by flash chromatography on silica gel with diethyl
ether/petroleum ether (2:8) as eluent to yield 5h and the mixture of 10h and 11h. 4% of
triethylamine was added to the eluent to obtain 6h from the crude materials.
1
N-(((2-ferrocenylvinyl)methyl), N-methyl aniline 5h: H (400MHz, CDCl3): 7.27 (2H, m, Ph), 6.9-
6.7 (3H, m, Ph), 6.27 (1H, d, J=15.7Hz, CH vinyl), 5.24 (1H, d of t, J=15.7Hz, J=5.6Hz, CH vinyl),
4.32 (2H, br s, subst Cp), 4.20 (2H, br s subst Cp), 4.09 (5H, s, Cp), 3.97 (2H, d, J=5.6Hz, CH2-vinyl),
3.00(s, CH3). 13C (125MHz, CDCl3): 149.6 (s, quat. Ph), 129.1 (s, Ph), 129.0 (s, CH vinyl), 122.4 (s,
CH vinyl), 116.5 (s, Ph), 112.7 (s, Ph), 82.9 (s, quat. Cp), 69.1 (s, Cp), 68.6 (s, subst. Cp), 66.7 (s,
subst. Cp), 53.2 (s, CH2Ph), 55.0 (s, CH2-vinyl), 38.1 (s, CH3). HR MS (ESI+): 331.1017 (88%,
331.1023 for C20H21FeN: M), 225.0756(84%, 225.0367 for C13H13Fe: M-NCH2Ph)

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
22
1
1
N-(((1-ferrocenyl)(1-vinyl)methyl), N-methyl aniline 6h: H (400MHz, CDCl3): H (400MHz,
CDCl3): 7.22-7.18 (2H, m, Ph), 6.85-6.83 (2H, m, Ph), 6.69-6.66 (1H, m, Ph), 6.38 (1H, ddd,
J=17.0Hz, J=10.6Hz, J=4.8Hz, CH vinyl), 5.55 (1H, m, CH), 5.30-5.20 (2H, m, CH vinyl), 4.21 (5H,
s, Cp), 4.20-4.17 (3H, m, subst Cp), 4.11 (1H, m, subst Cp), 2.55 (s, CH3). 13C (125MHz, CDCl3):
150.2 (s, quat. Ar), 135.8 (s, CH vinyl), 128.9 (s, Ar), 116.4 (s, Ar), 115.3 (s, CH vinyl), 113.0 (s, Ar),
87.3 (s, quat. Cp), 68.8 (s, Cp), 68.2 (s, subst. Cp), 68.1 (s, subst. Cp), 68.0 (s, subst. Cp), 67.3 (s,
subst. Cp), 60.9 (s, CHFc) 31.9 (s, CH3), HR MS (ESI+): 331.1026 (44%, 331.1023 for C20H21FeN:
M). 225.0376 (100%, 225.0367 for C13H13Fe: M-NCH3Ph).
Mixture of 10h and 11h
HR MS (ESI+): 333.1103 (100%, 332.1102 for C20H22FeN: M+H).
1
N-((4-(2-ferrocenylvinyl)methyl)phenyl), N-methyl aniline 10h: H (400MHz, CDCl3): 7.27 (2H,
m, Ph), 6.9-6.7 (3H, m, Ph), 6.27 (1H, d, J=15.7Hz, CH vinyl), 5.24 (1H, d of t, J=15.7Hz, J=5.6Hz,
CH vinyl), 4.32 (2H, br s, subst Cp), 4.20 (2H, br s subst Cp), 4.09 (5H, s, Cp), 3.97 (2H, d, J=5.6Hz,
CH2-vinyl), 3.00(s, CH3). 13C (125MHz, CDCl3): 147.6 (s, quat. Ph), 129.3 (s, Ph), 129.2 (s, quat. Ph),
127.5 (s, CH vinyl), 127.4 (s, CH vinyl), 112.7 (s, Ph), 84.0 (s, quat. Cp), 69.0 (s, Cp), 68.2 (s, subst.
Cp), 66.5 (s, subst. Cp), 38.5 (s, CH2-vinyl), 31.0 (s, CH3).
1
1-(4-(N-methylamino)phenyl),1-ferrocenyl, 1-vinyl methane 11h: H (400MHz, CDCl3): 7.00 (2H,
m, Ph), 6.57 (2H, m, Ph), 6.29 (1H, ddd, J=17.1Hz, J=10.1Hz, J=7.3Hz, CH vinyl), 5.11 (1H, ddd,
J=10.1Hz, J=1.8Hz, J=1.1Hz, CH vinyl), 4.99 (1H, ddd, J=17.1Hz, J=1.8Hz, J=1.3Hz, CH vinyl),
4.35 (1H, br m, CH), 4.20-4.05 (3H,m, subst Cp), 4.18 (5H, s, Cp), 3.99 (1H, m, subst Cp), 2.83
(3H, s, CH3). 13C (125MHz, CDCl3): 147.7 (s, quat. Ph), 141.7 (s, CH vinyl), 132.9 (s, quat. Ph),
128.8 (s, Ph), 114.2 (s, CH vinyl), 112.3 (s, Ph), 91.9 (s, quat. Cp), 68.6 (s, Cp), 68.0 (s, subst. Cp),
67.46 (s, subst. Cp), 67.38 (s, subst. Cp), 67.2 (s, subst. Cp), 48.8 (s, CH-vinyl), 30.9 (s, CH3).

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
23
N-ethylaniline:
The crude reaction mixture was separated by flash chromatography on silica gel with diethyl
ether/pentane (2:8) as eluent to yield 5i, 10i and 11i. To yields 6i by flash chromatography on
basic alumina, the same eluent with 2% of triethylamine was used.
The crude reaction mixture was separated by flash chromatography on silica gel with diethyl
ether/petroleum ether (2:8) as eluent to yield 5i and the mixture of 10i and 11i. To obtain 6i
by flash chromatography on basic alumina, the same eluent with 2% of triethylamine was
used.
1
N-(((2-ferrocenylvinyl)methyl), N-ethyl aniline 5i: H (400MHz, acetone-D6): 7.18 (2H, m, Ph),
6.79 (2H, m, Ph), 6.61 (1H, m, Ph), 6.30 (1H, d, J=15.7Hz, CH vinyl), 5.80 (1H, d of t, J=15.7Hz,
J=5.6Hz, CH vinyl), 4.37 (2H, br s, subst Cp), 4.19 (2H, br s subst Cp), 4.07 (5H, s, Cp), 3.96 (2H, br
d, J=5.6Hz, CH2-vinyl), 3.48 (2H, q, J= Hz, CH2), 1.20 (2H, t, J= Hz, CH3). 13C (125MHz, acetone-
D6): 148.4 (s, quat. Ph), 128.9 (s, Ph), 128.4 (s, CH vinyl), 123.2 (s, CH vinyl), 115.6 (s, Ph), 112.7
(s, Ph), 83.2 (s, quat. Cp), 68.8 (s, Cp), 68.3 (s, subst. Cp), 66.5 (s, subst. Cp), 51.9 (s, CH2-vinyl), 44.4
(s, CH2- CH3), 11.9 (s, CH3). HR MS (ESI+): 345.1183 (8%, 345.1180 for C21H23FeN: M), 225.0423
(100%, 225.0367 for C13H13Fe: M-NEtPh).
N-(((1-ferrocenyl)(1-vinyl)methyl), N-ethyl aniline 6i: 1H (400MHz, acetone-D6): 7.16 (2H, m, Ph),
6..80 (2H, m, Ph), 6.62 (1H, m, Ph), 6.39 (1H, ddd, J=17.2Hz, J=10.4Hz, J=4.8Hz, CH vinyl), 5.50
(1H, m, CH), 5.25 (1H, d of t, J=10.4Hz, J=1.8Hz, CH vinyl), 5.18 (1H, d of t, J=17.2Hz, J=1.8Hz,
CH vinyl), 4.22 (5H, s, Cp), 4.26-4.17 (4H, m, subst Cp), 3.25-3.20 (2H, m, CH2), 0.84 (t, J=7.0Hz,
CH3). 13C (125MHz, CDCl3): 148.4 (s, quat. Ar), 135.9 (s, CH vinyl), 128.8 (s, Ar), 116.0 (s, Ar),
115.2 (s, CH vinyl), 113. (s, Ar), 87.8 (s, quat. Cp), 68.9 (s, subst. Cp), 68.8 (s, Cp), 68.08 (s, subst.
Cp), 68.05 (s, subst. Cp), 67.4 (s, subst. Cp), 60.5 (s, CHFc) 40.1 (s, CH2), 13.4 (s, CH3). HR MS
(ESI+): 345.1180 (14%, 345.1180 for C21H23FeN: M), 225.0404 (100%, 225.0367 for C13H13Fe: M-
NEtPh).
Mixture of 10i and 11i

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
24
HR MS (ESI+): 346.1262 (100%, 346.1258 for C21H24FeN: M+H).
1
N-((4-(2-ferrocenylvinyl)methyl)phenyl), N-ethyl aniline 10i: H (400MHz, CDCl3): 7.34 (2H, m,
Ph), 6.62 (2H, m, Ph), 6.15 (1H, d of t, J=15.6Hz, J=1.5Hz, CH vinyl), 5.94 (1H, d of t, J=15.7Hz,
J=6.9Hz, CH vinyl), 5.32 (1H, s, NH), 4.32 (2H, t, J=1.9Hz, subst Cp), 4.18 (2H, t, J=1.9Hz, subst
Cp), 4.12 (5H, s, Cp), 3.33 (2H, br d, J=6.9Hz, CH2-vinyl), 3.18 (2H, q, J=7.1Hz, CH2- CH3), 1.29
13
(3H, t, J=7.1Hz, CH3). C (125MHz, CDCl3): 146.7 (s, quat. Ph), 129.4 (s, Ph), 128.9 (s, quat. Ph),
127.5 (s, CH vinyl), 127.4 (s, CH vinyl), 113.0 (s, Ph), 84.0 (s, quat. Cp), 69.0 (s, Cp), 68.2 (s, subst.
Cp), 66.4 (s, subst. Cp), 38.8 (s, CH2CH3), 38.5 (s, CH2-vinyl), 14.9 (s, CH3).
1-(4-(N-ethylamino)phenyl), 1-ferrocenyl, 1-vinyl methane 11i: 1H (400MHz, CDCl3): 6.98 (2H, m,
Ph), 6.57 (2H, m, Ph), 6.29 (1H, ddd, J=15.6Hz, J=10.1Hz, J=7.3Hz, CH vinyl), 5.10 (1H, ddd,
J=10.1Hz, J=1.8Hz, J=1.1Hz, CH vinyl), 4.99 (1H, d of br t, J=17.1Hz, J=1.6Hz, CH vinyl), 4.34
(1H, br m, CH), 4.20-4.05 (3H,m, subst Cp), 4.15 (5H, s, Cp), 3.99 (1H, m, subst Cp), 2.83 (3H, s,
CH3). 13C (125MHz, CDCl3): 146.7 (s, quat. Ph), 132.0 (s, quat Ph), 128.9 (s, Ph), 114.2 (s, CH
vinyl), 113.1 (s, Ph), 112.7 (s, CH vinyl), 91.9 (s, quat. Cp), 68.6 (s, Cp), 68.0 (s, subst. Cp), 67.45 (s,
subst. Cp), 67.40 (s, subst. Cp), 67.2 (s, subst. Cp), 48.8 (s, CH-vinyl), 38.8 (s, CH2CH3), 15.3 (s,
CH3).
N,N-dimethylaniline:
The crude reaction mixture was separated by flash chromatography on silica gel with diethyl
ether/pentane (2:8) as eluent to yield 10j and 11j.
Mixture of 10j and 11j
HR MS (ESI+): 346.1263 (100%, 346.1258 for C21H24FeN: M+H).
1
N-((4-(2-ferrocenylvinyl)methyl)phenyl), N,N-dimethyl aniline 10j: H (400MHz, CDCl3): 7.14
(2H, m, Ph), 6.76 (2H, m, Ph), 6.17 (1H, br d, J=15.6Hz, CH vinyl), 5.96 (1H, d of t, J=15.6Hz,

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
25
J=6.9Hz, CH vinyl), 4.33 (2H, t, J=1.9Hz, subst Cp), 4.18 (2H, t, J=1.9Hz, subst Cp), 4.13 (5H, s,
Cp), 3.35 (2H, br d, J=6.9Hz, CH2-vinyl), 2.96 (6H, s, CH3). 13C (125MHz, CDCl3): 149.2 (s, quat.
Ph), 129.2 (s, Ph), 128.6 (s, quat. Ph), 127.42 (s, CH vinyl), 127.40 (s, CH vinyl), 113.1 (s, Ph), 84.0
(s, quat. Cp), 69.1 (s, Cp), 68.3 (s, subst. Cp), 66.5 (s, subst. Cp), 40.9 (s, CH3), 38.4 (s, CH2-vinyl).
1
1-(4-(N-dimethylamino)phenyl), 1-ferrocenyl, 1-vinyl methane 11j: H (400MHz, CDCl3): 7.00
(2H, m, Ph), 6.57 (2H, m, Ph), 6.29 (1H, ddd, J=17.1Hz, J=10.1Hz, J=7.3Hz, CH vinyl), 5.11 (1H,
ddd, J=10.1Hz, J=1.8Hz, J=1.1Hz, CH vinyl), 4.99 (1H, ddd, J=17.1Hz, J=1.8Hz, J=1.3Hz, CH
vinyl), 4.38-4.32 (1H, br m, CH), 4.20-4.10 (3H,m, subst Cp), 4.16 (5H, s, Cp), 4.01 (1H, m, subst
Cp), 2.93 (3H, s, CH3). 13C (125MHz, CDCl3): 149.2 (s, quat. Ph), 141.7 (s, CH vinyl), 132.2 (s, quat.
Ph), 128.7 (s, Ph), 114.2 (s, CH vinyl), 112.6 (s, Ph), 91.9 (s, quat. Cp), 68.6 (s, Cp), 68.0 (s, subst.
Cp), 67.4 (s, subst. Cp), 67.4 (s, subst. Cp), 67.2 (s, subst. Cp), 48.7 (s, CH-vinyl), 40.8 (s, CH3).
X-ray structural analyses. Single crystal of each compound was mounted under inert
perfluoropolyether at the tip of a feather and cooled in the cryostream of either an Agilent
Technologies GEMINI EOS diffractometer for 5c, 5f and 5h, or a Bruker APEXII diffractometer for
4, 5d and 5i.
]
The structures were solved by direct methods (SIR97[12 ) and refined by least-squares
]
procedures on F2 using SHELXL-97[13 . All H atoms attached to carbon were introduced in calculation
in idealised positions and treated as riding models. The absolute structure for compounds 5f has been
evaluated by refining the Flack’s parameter[14] which indicated the occurrence of an inversion twin.
The drawing of the molecules was realised with the help of ORTEP32.[15] Crystal data and refinement
parameters are shown in Table 6.
Table 6. Crystal Data

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
26
Identification code
4
5c
C1 8 H2 3 FeN
309.22
173(2)
0.71073
Orthorhombic
Pbca
9.6981(3)
8.9351(4)
35.039(2)
5d
C2 7 H2 7 FeN
421.34
173(2)
0.71073
Monoclinic
C2/c
29.8653(9)
7.5243(2)
19.2314(6)
5f
Empirical formula
Formula weight
Temperature, K
Wavelength, Å
Crystal system
Space group
a, Å
C1 6 H2 2 FeIN
822.19
C2 0 H2 0 FeN
330.22
173(2)
0.71073
296(2)
0.71073
Triclinic
P -1
8.1506(3)
9.6976(5)
20.7712(13)
Orthorhombic
Pca21
29.2656(9)
11.0394(4)
10.0116(4)
b, Å
c, Å
87.673(4)
88.773(4)
88.515(4)
1639.54(15)
90.0
90.0
90.0
3036.2(2)
90.0
98.130(1)
90.0
90.0
90.0
90.0
3234.5(2)
, °
b, °
, °
3
4278.2(2)
Volume, Å
Z
4
8
8
8
Density (calc),
1.665
1.353
1.308
1.356
Mg/m3
Abs. coefficient,
mm- 1
2.790
0.983
0.717
0.928
F(000)
816
0.13 x 0.11 x
0.04
1312
0.50 x 0.37 x
0.07
1776
0.50 x 0.13 x
0.08
1384
0.62 x 0.55 x
0.05
Crystal size, mm3
Theta range, °
Reflections
1.963 to 26.37
27300
3.154 to 26.37 1.377 to 26.48
3.079 to 26.372
18032
16807
48162
collected
Indpt reflections
6653 (0.0275)
3098 (0.0290)
4427 (0.0235)
5191 (0.0402)
(Rint
)
Completeness, %
99.5
99.6
100.0
99.5
Absorption
Multi-scan
Multi-scan
Multi-scan
Multi-scan
correction
Max. / min.
0.7462 / 0.5993
1.0 / 0.896
0.7454 / 0.5992
1.0 / 0.6852
transmission
Refinement method
2
2
2
2
F
F
F
F
Data
6653 / 0 / 349
3098 / 0 / 181
4427 / 0 / 262
5191 / 1 / 406
/restraints/paramete
rs
Goodness-of-fit on
1.075
1.181
1.196
1.131
2
F
0.0491, 0.1416
0.0556, 0.1525
0.0495,
0.0978
0.0604,
0.1039
0.0248, 0.0743
0.0298, 0.0938
0.0452, 0.0904
0.0513, 0.0938
R1, wR2 [I>2(I)]
R1, wR2 (all data)
Flack’s parameter
0.39(3)
Residual density,
1.857 / -1.157
0.780 / -0.415
0.428 / -0.348
0.414 / -0.733
-3
e.Å
Identification code
Empirical formula
Formula weight
Temperature, K
Wavelength, Å
Crystal system
Space group
a, Å
5h
C21H22FeN
344.24
5i
C21 H23FeN
345.25
173(2)
173(2)
0.71073
Monoclinic
P 21/c
18.5228(9)
7.6927(4)
11.8163(5)
90.0
0.71073
Monoclinic
P21/n
12.1453(5)
8.9464(4)
15.8968(7)
90.0
b, Å
c, Å
, °
b, °
93.134(4)
96.859(2)°.

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
27
90.0
90.0
, °
3
1681.19(14)
1714.93(13)
Volume, Å
Z
4
4
Density (calc),
1.360
1.337
Mg/m3
Abs. coefficient,
mm-1
0.896
724
0.878
F(000)
728
0.50 x 0.50 x
0.40
Crystal size, mm3
0.370 x 0.330 x 0.100
Theta range, °
Reflections
2.868 to 26.368°.
17898
2.245 to 30.028
23252
collected
Indpt reflections
3443 (0.0661)
5023 (0.0255)
(Rint
)
Completeness, %
99.7
100.0
Absorption
Multi-scan
Multi-scan
correction
Max. / min.
1.0 / 0.708
0.7463 / 0.6672
transmission
Refinement method
2
2
F
F
Data
3443 / 0 / 209
5023 / 0 / 209
/restraints/parameter
s
Goodness-of-fit on
1.118
1.042
2
F
0.0514, 0.1318
0.0606, 0.1387
0.0294, 0.0717
0.0401, 0.0789
R1, wR2 [I>2(I)]
R1, wR2 (all data)
Flack’s parameter
Residual density,
1.148 / -0.560
0.409 / -0.278
-3
e.Å
Crystallographic data for compounds 4, 5c, 5d, 5f, 5h and 5i (excluding structure factors)
have been deposited with the Cambridge Crystallographic Data Centre as supplementary
publication no. CCDC 1494314-1494319. Copies of the data can be obtained free of charge
on application to the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44)
1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
Acknowledgements

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
28
RB thanks the “Ministère de l’Enseignement Supérieur et la Recherche Scientifique” of
Algeria for generous funding of her Internship in Toulouse.
Table of Contents:
((2-ferrocenylvinyl)methyl)trimethylammonium 4 was obtained in high yields in two
steps from commercially available compounds.and used to transfer ferrocene-containing allyl
group on various amines. By controlling reaction conditions, the selectivity of the reaction
could be efficiently modified towards linear or branched ferrocenyl allylamine isomers.
References
[1] a) Q.-A. Chen, Z. Chen, V. M. Dong, J. Am. Chem. Soc. 2015, 137, 8392-8395.
[2] a) A. D. Sai Krishna, G. Panda, A. K. Kondapi, Arch. Biochem. Biophys. 2005, 438, 206-
216; b) C. Ornelas, New J. Chem. 2011, 35, 1973-1985; c) A. A. Simenel, E. A.
Morozova, L. V. Snegur, S. I. Zykova, V. K. Kachala, L. A. Ostrovskaya, N. V.
Blutcherova, M. M. Fomina, Appl. Organomet. Chem. 2009, 219-224.
[3] a) S. C. Ensign, E. P. Vanable, G. D. Kortman, L. J. Weir, K. L. Hull, J. Am. Chem. Soc.
2015, 137, 13748-13751.
[4] For recent reviews about chiral ferrocenyl ligands in asymmetric catalysis: a) T. J.
Colacot, Chem. Rev. 2003, 103, 3101-3118; b) R. C. J. Atkinson, V. C. Gibson, N. J.
Long, Chem. Soc. Rev. 2004, 33, 313-328; c) R. Gomez Arrayas, J. Adrio, J. C.
Carretero, Angew. Chem. Int. Ed. 2006, 45, 7674-7715; d) S. Toma, Jana Csizmadiová,
Mária Mečiarová, R. Sebesta, Dalton Trans. 2014, 43, 16557-16579.

European Journal of Inorganic Chemistry
10.1002/ejic.201600860
29
[5] a) D. R. van Sraveren, N. Metzler-Nolte, Chem. Rev. 2004, 104, 5931-5985; b) C.
Ornelas, N. J. Chem. 2011, 35, 1973-1985; c) V. N. Babin, Y. A. Belousov, V. I. Borisov,
V. V. Gemenyuk, Y. S. Nekrasov, L. A. Ostrovskaya, I. K. Sviridova, N. S. Sergeeva, A.
A. Simenel, L. V. Snegur, Russ. Chem. Bull., Intern. Ed. 2014, 63, 2405-2422.
[6] a) W. A. Wlassoff, C. D. Albright, M. S. Sivashinski, A. Ivanova, J. G. Appelbaum, R. I.
Salganik, J. Pharmacy Pharmacology. 2007, 59, 1549–1553; b) M. A. Sierra, M.
Rodriguez-Fernandez, L. Casarrubios, M. Gomez-Gallego, C. P. Allen, M. J. Mancheno,
Dalton Trans. 2009, 8399-8405; c) S. Chen, Q. Yan, H. Zhao, B. Li, J. Org. Chem.,
2013, 78, 5085-5089.
[7] a) B. E. Maryanoff, H.-C. Zhang, J. H. Cohen, I. J. Turchi, C. A. Maryanoff, Chem. Rev.
2004, 104, 1431-1628; b) A. Erkkilä, I. Majander, P. M. Pihko, Chem. Rev. 2007, 107,
5416-5470; c) T. Nishi, I. Mizota, M. Shimizu, Pure Appl. Chem. 2012, 84, 2609-2017;
d) M. G. Memeo, P. Quadrelli, Chem. Eur. J. 2012, 18, 12554-12582; e) A. O. Kataja, G.
Masson, Tetrahedron 2014, 70, 8783-8815.
[8] a) R. Gleiter, R. Seeger, H. Binder, E. Fluck, M. Cais, Angew. Chem. Intern. Edit. 1972,
11, 1028-1029; b) S. Allenmark, Tetrahedron Lett. 1974, 4, 371-374; c) C. J. Richards,
D. Hibbs, M. H. Hursthouse, Tetrahedron Lett. 1994, 35, 4215-4218; d) S. Taudien, O.
Riant, H. B. Kagan, Tetrahedron Lett. 1995, 36, 3513-3516; e) A. Z. Kreidlin, F. M.
Dolgushin, A. I. Yanovsky, Z. A. Kerzina, P. V. Petrovskii, J. Organomet. Chem. 2000,
616, 106-111.
[9] a) J. Schreiber, H. Maag, N. Hasimoto, A. Eschenmoser, Angew. Chem. Intern. Edit. 1971,
10, 330-331; b) E. Winterfeldt, J. Prakt. Chem. 1994, 336, 91-92.
[10] For precedents of reactions of iminium salts on less activated alkenes, see: a) T. Shono,
Y. Matsumara, K. Inoue, H. Ohmizu, S. Kashimara, J. Am. Chem. Soc. 1982, 104, 5773-
5757; b) A. R. Katritzky, M. F. Gordeev, J. Org. Chem. 1993, 58, 4049-4053; c) A. R.
Katritzky, M. F. Gordeev, Org. Lett. 2004, 6, 2709-2711.
[11] a) J. K. Lindsay, C. R. Hauser, J. Org. Chem. 1957, 22, 355-358; b) D. E. Bublitz, J.
Organomet. Chem. 1970, 23, 225-228; c) O. Delacroix, S. Picart-Goetgheluck, L.
Maciejewski, J. Brocard, Tet. Asym. 1999, 10, 1835-1837; d) J. Alvarez, Y. Ni, T. Ren,
A. E. Kaifer, J. Supramol. Chem. 2001, 1, 7-17; e) N. Mateus, L. Routaboul, J.-C. Daran,
E. Manoury, J. Organomet. Chem. 2006, 691, 2297-2310; f) G. Gasser, A. J. Fischmann,
C. M. Forsyth, L. Spiccia, J. Organomet. Chem. 2007, 692, 3835-3840; g) J.-B. Zhuo,