Mono and diphosphine borane complexes grafted on polypyrrole matrix: Direct use as supported ligands for Rh and Pd catalysis

Article abstract of DOI:10.1016/S0022-328X(98)00684-6

A new versatile method for the synthesis of supported mono and diphosphines on polypyrrole matrix is described, based on the protective borane complexation of the phosphorus atom. For the first time, the unknown alkylation of a diphosphine ethano bridge, was obtained with near yield close to 70%, leading to its derivative 8 bearing the polymerizable pyrrole group on a side chain. The different supported mono and diphosphine boranes 12-15 have been applied with success in palladium-catalyzed allylation, cross-coupling reaction and in rhodium-catalyzed hydrogenation. It is of particular interest that supported phosphine boranes can be used without previous decomplexation, forming in situ the catalytically active species from Pd(OAc)₂ or RhCl₃. Moreover, the recoverable polymer could be used again in rhodium-catalyzed hydrogenation with a very good efficiency after several turn-overs. Nethertheless, we may point out that with palladium catalysis, the addition of Pd(dba)₂ was necessary to recover the catalytic activity. These results demonstrate that the phosphine borane complexes are key precursors for the synthesis of functionalized mono and diphosphines, and for their direct use in generating catalysts.

Full text of DOI:10.1016/S0022-328X(98)00684-6

Journal of Organometallic Chemistry 567 (1998) 219–233
Mono and diphosphine borane complexes grafted on polypyrrole
matrix: direct use as supported ligands for Rh and Pd catalysis
Nade`ge Riegel, Christophe Darcel, Olivier Ste´phan, Sylvain Juge´ *
Uni6ersite´ de Cergy-Pontoise, Equipe ‘Re´acti6ite´s Spe´cifiques’ EA 1389, 5 mail Gay Lussac, 95031 Cergy Pontoise Ce´dex, France
Received 4 February 1998; received in revised form 18 March 1998
Abstract
A new versatile method for the synthesis of supported mono and diphosphines on polypyrrole matrix is described, based on the
protective borane complexation of the phosphorus atom. For the first time, the unknown alkylation of a diphosphine ethano
bridge, was obtained with near yield close to 70%, leading to its derivative 8 bearing the polymerizable pyrrole group on a side
chain. The different supported mono and diphosphine boranes 12–15 have been applied with success in palladium-catalyzed
allylation, cross-coupling reaction and in rhodium-catalyzed hydrogenation. It is of particular interest that supported phosphine
boranes can be used without previous decomplexation, forming in situ the catalytically active species from Pd(OAc)2 or RhCl3.
Moreover, the recoverable polymer could be used again in rhodium-catalyzed hydrogenation with a very good efficiency after
several turn-overs. Nethertheless, we may point out that with palladium catalysis, the addition of Pd(dba)2 was necessary to
recover the catalytic activity. These results demonstrate that the phosphine borane complexes are key precursors for the synthesis
of functionalized mono and diphosphines, and for their direct use in generating catalysts. © 1998 Elsevier Science S.A. All rights
reserved.
Keywords: Phosphine boranes; Supported ligands; Polypyrrole; Rhodium catalysts; Palladium catalysts; Hydrogenation; Allylic
alkylation; Coupling reaction
1. Introduction
over, the recycling of chiral ligand which represents
generally the more important part of the catalytic sys-
tem is a major problem, for new industrial asymmetric
processes [3].
In the recent past, one of the most noteworthy
progresses can be illustrated by the use of hydrosoluble
or amphiphilic ligands, which allow to realize biphasic
catalysis [4,5] or to recover the catalyst by an acid-base
work up ([5]k). The economic interest of catalytic
biphasic reactions is demonstrated by the industrializa-
tion of a propene hydroforming process using an hy-
Homogeneous catalysis via organometallic complexes
is a topic of current interest in organic synthesis, and
spectacular progresses have been obtained toward selec-
tivity and reactivity [1]. Furthermore, selective reactions
under mild conditions giving few by-products and
which satisfy the atom economy criteria, have a great
potential for modern organic synthetic methods [2].
Nevertheless, the cost of the catalytic process and the
presence of traces of transition metals in the final
product, require the salvage and the recycling of the
catalyst which are key points, for applications in medic-
inal-chemistry, agro-chemistry or food industry. More-
drosoluble rhodium complex
associated with
P(m-NaSO3Ph)3 (TPPTS) ([5]c, e). More recently, su-
percritical carbon dioxide [6], perfluorinated solvents [7]
or molten salts [8] were used to realize biphasic catalysis
for oxidation, hydrogenation or palladium-coupling
reactions.
* Corresponding author. Tel.: +33 1 34257066; fax: +33 1
34257067; e-mail: juge@u-cergy.fr
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00684-6

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N. Riegel et al. / Journal of Organometallic Chemistry 41 (1998) 219–233
Scheme 1.
However, another alternative to recover the catalyst
We wish to report herein the preparation of
diphenylphosphine and dppe borane complexes grafted
to a polypyrrole matrix, and their direct use to generate
Pd or Rh catalysts applied in C–C or C–H bond
formation.
is to adsorb or graft it on an inorganic matrix [9,10], a
polymer [11–13] or a dendrimer [14]. In this case, it is
possible to combine the conditions of the heterogeneous
catalysis with the interest of the homogeneous catalysts,
which allow wide steric or electronic modifications. Up
today, the synthesis of functionalized organic and min-
eral matrixes has been largely reported, in view of their
applications for solid support chemistry [15], high tech-
nology materials or surface modifications [16,17]. Re-
cently, the spectacular booming of the combinatorial
chemistry on solid support retained much attention,
due to the spectacular progress in drug discovery ([15]a,
d). In the case of phosphines grafted on polymer, there
are not many examples of this kind of supported lig-
ands and only few are commercially available. This
could be explained by the relative difficulty to function-
alize organophosphorus P(III) compounds, or the prob-
lems of purification and easy oxidation. Until now, the
preparation of supported-phosphine ligands is often
achieved by reacting phosphorus reagents (i.e. sec-
ondary phosphines, phosphides, phosphine chlorides...)
with a functionalized matrix [11] or with an olefin
precursor ([12]d, e). Another approach is based in the
polymerization of a phosphine monomer containing a
polymerizable function such as styrene or acrylate
([11]a).
2. Results and discussion
2.1. Synthesis of mono and diphosphine boranes 5,8
bearing a polymerizable pyrrole group
The use of borane as protective group of the phos-
phorus center, is an efficient method for the synthesis of
achiral or chiral organophosphorus compounds [18,21–
23]. Indeed, phosphine borane complexes present many
advantages in the organophosphorus synthesis, as they
possess an interesting reactivity and do not require any
purification or storage problems. It is also particularly
easy to prepare the carbanion of a methylphosphine
borane, and consequently to introduce a functionalized
group on the side chain ([18]c, [21]a, [22,23]).
We have used this methodology to functionalize the
methyldiphenylphosphine borane 4 and the dppe-dibo-
rane 7 complexes, with a chain bearing a polymerizable
pyrrole group (Scheme 1).
The borane complexes 4, 7 were easily obtained in
high yields (91 and 95%, respectively) as crystalline
solids, by simple addition of BH3 ·DMS to the corres-
ponding phosphines 3 and 6. Then 4 was treated with
sec-BuLi to form an h-anion, which reacted with the
bromide 2 previously prepared from pyrrole 1, to pro-
duce the monomer 5 with 65% yield (Scheme 1a, b).
Following the same procedure, reaction of the dppe
diborane 7 with tert-BuLi led to the h-anion of the
ethano bridge, which reacted with 2 to provide the
compound 8 with 68% yield. As far as we know,
As part of our program on the synthesis of chiral
mono and diphosphine ligands via their borane com-
plexes [18], we have investigated a new way for the
synthesis of phosphinated polymers. In this aim, we
have studied the linkage of mono and diphosphines on
a polypyrrole matrix. Up today, very few examples of
phosphine ligands bound to polypyrrole are known
([18]e, [19]a), and furthermore only few examples of
supported catalysts on this matrix have been applied in
the field of organic catalysis.

N. Riegel et al. / Journal of Organometallic Chemistry 567 (1998) 219–233
221
Scheme 2.
reaction of the diphosphine dioxide 9 with n-BuLi
2.3. Electrochemical polymerization of the substituted
entailed its decomposition into the vinylphosphine ox-
ide 10 and phosphide 11 [24], and the alkylation of the
ethano bridge of a 1,2-diphosphine has never been
reported (Scheme 2).
mono and diphosphine borane complexes 5 and 8
In a preliminary communication, we have described
the electrochemical polymerization of the diphosphine
borane monomer 8 ([18]e). According to this methodolo-
gy, the polymer is obtained in an oxidated state with
approximatively one in three pyrrole ring carrying pos-
itive charge. In order to maintain electroneutrality,
perchlorate anion which came from the electrolytic
media are incorporated in the polymer matrix [19,20].
Nevertheless, if this methodology is particularly
adapted to analytical study, only low quantities (few
mg) of product were obtained under these experimental
conditions. So, in order to obtain easy handled poly-
mer, the monomers 5 and 8 were polymerized on
macroporous carbon electrodes to form the
polypyrroles 14 and 15 (Scheme 3b, d). After crushing
carbon electrodes, the polypyrroles 13 and 14 were
obtained as a powder for their applications in catalysis.
2.2. Chemical polymerization of the substituted mono
and diphosphine borane complexes 5 and 8
The polymerization of the monomers 5 and 8 has
been achieved by the two classical ways leading
to polypyrroles: by chemical oxidation [20,25] or elec-
trochemical preparation [17,19]. In the first case,
reaction of the phosphine borane monomers 5 or 8
with anhydrous FeCl3 in ether, led rapidly to the poly-
mers 12 and 13 as insoluble black powders (Scheme 3a,
c).
The FT-IR spectra of these polymers 12 and 13,
exhibited caracteristic B–H bands in the 2300–2400
cm−1 region, which indicated the presence of phos-
phine borane groups in the polypyrrole matrix. The
elemental analyses of polypyrroles 12 and 13 displayed
an important quantity of chlorine and iron (more than
50% of the material weight, Table 1, entries 1, 3), which
proved that a large part of the ferric (III) chloride used
for the polymerization, was aggregated to the matrix.
The phosphorus analysis of the polypyrroles 12 and 13
gave 3.10 and 4.06%, respectively, in good agreement
with the grafting of a mono and a diphosphine per
pyrrole unit, with respect to the corresponding calcu-
lated values of 3.00 and 4.35 (Table 1, entries 1, 2 and
3, 4). On the other hand, the boron elemental analysis
for 13 gives 1.13% which is lower than the calculated
value of 1.52% (Table 1, entries 3, 4). Although we have
observed significant variation in the elemental analyses
of various prepared samples, a partial loss of the bo-
rane group during the polymerization cannot be ex-
cluded. Finally, the elemental analyses of 12 and 13 are
in good agreement with the molecular formulas of
C21H39NPFe4.2Cl10BO6 and C34H55NP2Fe4.8Cl13.6B2O7,
respectively. The formulas are normalized to 21 and 34
carbon atoms per nitrogen, and the oxygen contents is
determined by difference. These results clearly indicate
that a solid solution of polymer has been generated
with mineral salts, moisture and eventually solvents. It
will be seen later, that the composition of the matrix
have no consequence on their application as supported-
ligands for organometallic catalysis.
2.4. Preparation of supported diphosphine 16 on
polypyrrole by decomplexation of the corresponding
borane complexe 12
The decomplexation of borane complexes is usually
realized by reaction with an amine to give the free
P(III) phosphines and the corresponding amine borane,
in high yields [26]. In order to obtain the decomplexa-
tion of the phosphine borane grafted on polypyrrole,
the compound 12 has been warmed at 50°C overnight
in diethylamine. After filtration and washing with ether,
the polypyrrole phosphine 16 was obtained as a red
brown powder (Scheme 3a), which showed a new FT–
IR B–N band at 1047 cm−1. Likely the observed B–N
band, corresponded to the presence of diethylamine
borane in the polymeric matrix, in spite of the washing
of the solid with solvent. The elemental analysis of 16
confirmed this adsorption of amine by the polypyrrole,
since an important increase of the initial carbon, hydro-
gen and nitrogen percentages was observed, compara-
tively to the corresponding borane complex polymer 12
(Table 1, entries 5 and 2). Finally, the calculated ele-
mental analysis of C66H159PFe4.5Cl11BO13 was in good
agreement with the values obtained for 16 (Table 1,
entries 5, 6). We have shown that such material can be
used with success in catalysis.

222
N. Riegel et al. / Journal of Organometallic Chemistry 41 (1998) 219–233
Scheme 3.
2.5. Application of the supported phosphine and
phosphine boranes 12–16 in catalysis
from Pd(OAc)2 and polypyrrole supported phosphine
borane complexes 12–15, using a phosphorus/palla-
dium ratio of 2:1. After addition of the allylic substrate
17a (or 17b) and the nucleophilic agent 18 (or 20), the
reaction was carried out at r.t. for at least 24 h, before
filtration of the polymer and work up (Scheme 5a, b).
The results are summarized in the Table 2.
Up to now, few examples of organometallic complex
preparations by the direct use of phosphine boranes
were known [27]. In our group, we had shown that it
was possible to prepare palladium(0) complexes, by
reaction of Pd(OAc)2 with phosphine boranes. The
mechanism of this reaction is not well established, but
we think that borane reduces Pd(II) into Pd(0) leading
to complexation of the free phosphine formed as de-
scribed on the Scheme 4.
The possibility of generating low oxidating state cata-
lytic systems from phosphine borane complexes is of
particular interest, since until now, the preparation of
Pd(0) and Rh(I) complexes from Pd(II) or Rh(III) salts
was obtained using an excess of free phosphine as
reducing agent [28,29]. Consequently, the phosphine
boranes grafted on polypyrrole have been tested toward
the well known Pd(0)-catalyzed reactions, without prior
decomplexation. The supported catalysts have been ap-
plicated to the well known catalyzed allylation reaction
with methyl acetoacetate 18 and benzylamine 20, and to
the Heck cross coupling reactions ([30] [31]a) (Schemes
5 and 6).
In order to verify that the formation of the allylated
product 19 was not due to a catalysis with metallic
palladium, or to the presence of nitrogen complex with
polypyrrole matrix, we have prepared the non-function-
alized polymer 25 [33], and used it in the previous
reaction. The mixture of allyl acetate 17a and methy-
lacetoacetate 18 in presence of Pd/C, Pd(dba)2, or
Pd(OAc)2 and polypyrrole 25, gave no reaction under
these conditions (Table 2, entries 1 and 2). In contrast,
the same reaction between 17a and 18 in presence of
complexes obtained from Pd(OAc)2 and supported
mono or diphosphine boranes 12, 13 or 15, led to the
monoallylated product 19a in 55–85% yields [32]
(Table 2, entries 3, 5, 7, 8). It is noteworthy that the
methodology of polypyrroles 12, 13 and 15 preparation
or their chemical composition, have not a dramatic
influence on the catalysis despite of the salt inclusion.
As the surface area of the polypyrrole 12 is surprisingly
low (3.4090.05 m2
g
−1) [35], the efficiency of the
2.5.1. Application of the supported phosphine boranes
12–15 to Pd(0)-catalyzed allylation reaction
In the allylation reaction, the catalyst was prepared
supported ligand must be explained by the high rate of
available P(III) phosphine, linked on the matrix by the
alkyl chain.

N. Riegel et al. / Journal of Organometallic Chemistry 567 (1998) 219–233
223
Table 1
Elemental analyses of phosphines and phosphine boranes supported on polypyrrole, prepared from 5 or 8 by oxidation with FeCl3
polymer prepared via the chemical way using FeCl3,
was inert toward the catalytic base formed during the
reaction (Table 2, entry 7). Finally, reaction of benzy-
lamine 20 with allylacetate 17a in presence of the
catalyst prepared with the supported monophosphine
borane 12, gave the N,N-diallylamine 21 in 74% yield
(Table 2, entry 10), when the monoallylated product
was not detected under these conditions. The recovered
ligand 12 was used again in this reaction after addition
of Pd(dba)2, leading to the formation of N,N-dially-
lamine 21 with 69% isolated yield (Table 2, entry 11).
After reaction, the polypyrrole removed from the
reaction medium can be used again in catalysis, but it is
necessary to add Pd(dba)2 in order to recover the
catalytic properties (Table 2, entries 4, 6, 9). In order to
prevent the oxidation of the free P(III) group, the
Pd(dba)2 used as Pd(0)-source for the recycled ligand
was preferred to Pd(OAc)2. So, it appeared that under
the conditions of the palladium catalysis without any
particular care for the recovery of the supported cata-
lyst, only the polypyrrole supported P(III) ligand was
removed. On the other hand, when the supported
diphosphines 13 and 15 were used again, the allylated
product 19a was then obtained with 35 and 63% yields,
respectively, thus reveling a better efficiency for the
recovered diphosphine polypyrrole 15 prepared by elec-
tropolymerization (Table 2, entries 6, 9).
2.5.2. Application of supported phosphine boranes 12
and 13 to Pd-catalyzed coupling reactions
For the Heck coupling reaction described here, the
catalysts were generated in situ from the supported
mono and diphosphine boranes 12, 13, following the
same procedure described in Section 2.5.1 for the allyla-
tion. The reactions were performed at 65°C between
aromatic iodides 22a,b and olefinic derivatives 23a,c
(Scheme 6), and the results are summarized in Table 3.
In neutral media, the allylation of methylacetoacetate
18 with carbonate 17b was performed in presence of the
catalyst prepared with the supported diphosphine bo-
rane 13. This result indicates that the corresponding

224
N. Riegel et al. / Journal of Organometallic Chemistry 41 (1998) 219–233
Scheme 4.
When the supported monophosphine borane 12 was
filtration without loss of activity, because hydrogena-
tion by means of the recovered catalyst gave the
product 27 in a near quantitative yield (Table 4, entries
2, 5, 7, 9, 11). Thus after three turn-overs, catalysts
initially prepared from the supported phosphines 12
and 16, kept the same efficiency (Table 4, entries 3, 12).
Finally, when the rhodium catalyst was prepared by
complexation of [Rh(COD)Cl]2 with the non-function-
alized polypyrrole 25 [33], quantitatively N-
acetylphenylalanine 27 is obtained (Table 4, entry 13).
Nethertheless after filtration, the recovered polymer
exhibits no more catalytic activity (Table 4, entry 14).
This result clearly demonstrated that the phosphine
groups grafted on polypyrrole are crucial for rhod-
ium(I) complex stabilization, and that allow efficient
recovery.
used, the iodobenzene 22a and the unsaturated com-
pounds 23a, 23c led to the coupling products 24a, 24c
in 72 and 64% yields, respectively (Table 3, entries 1, 4).
The recovered polymer 12 can be used again with an
addition of Pd(dba)2, in a new coupling reaction of
acrylic acid 23a with the iodide 22a, to provide the
product 24a with 60% yield (Table 3, entry 2). In the
case of the cyclohexenone 22b, the catalysis with the
iodobenzene led to the addition product 24b with 50%
yield (Table 3, entry 3). Otherwise, when the supported
diphosphine borane 13 was used with palladium salt or
Pd(dba)2, the coupling reaction between iodobenzene
22a and 23a gave poor yields in cinnamic acid 24a
(Table 3, entries 5, 6). These results can be attributed to
the presence of numerous diphosphine groups in the
polypyrrole matrix, which stabilize the palladium(0)
species as a Pd(P–P)2 complex analogous of Pd(dppe)2,
well known to prevent the oxidative addition with aryl
iodide [36].
3. Conclusion
In summary, we have reported a new versatile
method for the synthesis of supported mono and
diphosphines on polypyrrole matrix, without significally
degradation of the P(III) phosphorus group, resulting
from the protective borane complexation. For the first
time, the diphosphine ethano bridge alkylation, was
achieved here on a borane complex serie in about 70%
yield, which allows now to envisage the structural mod-
ification of the numerous existing chiral or achiral
ligands.
The various supported mono and diphosphine bo-
ranes 12–15 have been applied with success in palla-
dium-catalyzed allylation, the Heck cross-coupling
reactions as well as in the rhodium-catalyzed hydro-
genation. It is noteworthy that supported phosphine
boranes can be used without previous decomplexation,
to form in situ the catalytically active species either
from Pd(OAc)2 or from RhCl3. Furthermore, the recov-
ered polymer can be reused in the rhodium-catalyzed
hydrogenation with a very good efficiency after several
turn-overs, while in the case of the palladium catalysis
the addition of Pd(dba)2 was necessary to recover a
suitable catalytic activity.
2.5.3. Application of supported phosphine boranes
12–16 in rhodium catalysis
Finally, the supported mono and diphosphine bo-
ranes were used in the classical hydrogenation catalysis
of h-acetamidocinnamic acid 26 to N-acetylphenylala-
nine 27, with rhodium complexes [37] (Scheme 7).
As for palladium complexes, the rhodium catalysts
were obtained directly by reaction of RhCl3 with the
supported phosphine boranes 12–15 (ratio P/Rh=3),
by refluxing in ethanol for 1 h. On the other hand,
formation of the catalyst with the free supported phos-
phine 16 was achieved by exchange with the neutral
rhodium (I) complex [Rh(COD)Cl]2, in order to prevent
the oxidation of the free phosphine groups with RhCl3
as for the preparation of the Wilkinson catalyst [29].
The hydrogenation has been performed with 1–3 mol%
of catalyst depending on the polypyrrole preparation
were prepared, i.e. either by electrochemical or chemical
polymerization; The results are summarized in Table 4.
All hydrogenation reactions involving the supported
phosphines were achieved with very good yields, rang-
ing from 75 to 100% yields for the N-acetylphenylala-
nine 27 (Table 4, entries 1, 4, 6, 8, 10). When the
supported ligands prepared either by electropolymeriza-
tion or chemical oxidation were used, the yields of
hydrogenation were similar (Table 4, entries 1–6 and
4–8). For the supported free phosphine 16, the hydro-
genation reaction took place also with satisfactory 75–
100% yields (Table 4, entry 10, 11). It is noteworthy,
that in all cases the catalyst was recovered by simple
In conclusion, these results demonstrate clearly that
the borane P(III) complexes provide key precursors
both for the synthesis of mono and diphosphines
grafted on a polypyrrole matrix, and for their direct
reuse to generate the catalysts. The extensions of this
methodology and its application to the preparation of
supported chiral catalysts, are currently under investi-
gation in our laboratory.

N. Riegel et al. / Journal of Organometallic Chemistry 567 (1998) 219–233
225
Scheme 5.
4.2. N-(4-bromobutyl)pyrrole 2
4. Experimental part
A solution of freshly distilled pyrrole (5.20 ml, 75.0
mmol) in anhydrous THF (50 ml) containing NaH
(1.44 g, 60 mmol), was stirred at r.t. for 3 h; then, 75 ml
of dry THF were added. In a two necked flask
equipped with a condenser, a solution of 1,4-dibro-
mobutane (21.50 ml, 180 mmol, 3 equiv.) in anhydrous
THF (10 ml) was heated at 65°C under argon, and the
anion previously prepared was added dropwise. The
reaction mixture was stirred at r.t. overnight. Then, the
reaction was quenched with a saturated aqueous NH4Cl
solution (30 ml), THF was removed under vacuum and
the mixture was extracted with dichloromethane (3×50
ml). The combinated extracts were washed twice with
water (2×50 ml), dried (MgSO4) and concentrated.
The residue was purified by flash chromatography with
a mixture cyclohexane/toluene as eluent (1:1) to give
the product 2 as a pink oil (9.05 g, 75% yield). This
compound must be kept under inert atmosphere and in
dark.
4.1. General
All reactions were carried out under argon atmo-
sphere in glassware dried overnight. All solvents were
dried and purified according to standard methods. n-
butyllithium, s-butyllithium, tert-butyllithium, 1,4-di-
bromobutane,
allylacetate,
methylacetoacetate,
h-acetamidocinnamic acid 26, pyrrole 1, FeCl3,
Pd(OAc)2, RhCl3, BH3.S(CH3)2 in toluene, diphenyl-
methylphosphine 3 and 1,2-diphenylphosphinoethane 6
(dppe) were purchased from Aldrich or Acros Organics.
The [Rh(COD)Cl]2 complex has been prepared accord-
ing to the previously described procedure [38], and used
without further purification. Thin-layer chromatogra-
phy and flash chromatography were performed on Sil-
icagel 60 (35–70 mm) and silica gel (230–400 mesh;
Merck), respectively.
NMR spectra data were recorded on Bruker AM
200 (1H, 13C), AM and DPX 250 (1H, 13C, 31P)
spectrometers with TMS as internal reference for
1H- and 13C-NMR and 85% H3PO4 as external re-
ference for 31P-NMR. All NMR coupling values
are given in Hertz. IR spectra were recorded on a
Perkin Elmer 1600 FT and a Bruker FT 45 spectrome-
ters.
Melting points were measured on a Buchi melting
point apparatus and are uncorrected. Optical rotations
were measured at 20°C with a Perkin Elmer 241 polar-
imeter. Mass spectra analyses were performed on a
NERMAG R10-10C and a KRATOS MS-50 for exact
mass at the ‘Laboratoire de Spectroscopie de Masse de
l’ENSCP (Paris)’ and the ‘Laboratoire d’Analyses
Structurales’ of the University Pierre and Marie Curie
(Paris) respectively. The major peak m/z is mentionned
with the intensity as percent of the base peak in brack-
ets. Elementary analysis were recorded by the ‘Service
d’Analyses du C.N.R.S.-Vernaison’ and the ‘Labora-
toire de micronalyses’ of the University Pierre et Marie
Curie-Paris.
Rf=0.54 (toluene/cyclohexane 1/1); IR (KBr): w¯ 3098
(w), 2931 (m), 2871 (w), 1499 (s), 1281 (s), 1089 (s), 725
1
(s) cm−1; H-NMR (CDCl3): l 6.64 (2H, t, J=2.1 Hz,
NCH
3J=6.6 Hz, CH2
1.96–1.78 (4H, m, (CH
(NCHC), 110.0 (NCCH), 50.5 (C
31.9 (CCH2C), 31.7 (CCH2C).
6
), 6.14 (2H, t, J=2.1 Hz, NCCH
6
), 3.90 (2H, t,
Br), 3.36 (2H, t, J=6.4 Hz, CH2N),
2)2); 13C-NMR (CDCl3): l 122.3
H2Br), 34.9 (CH2N),
3
6
6
6
6
6
6
6
6
6
4.3. Diphenylmethylphosphine borane 4
The borane dimethylsulfide complex (5.22 ml, 55.0
mmol, 1.1 equiv.) was added dropwise under argon to a
solution of diphenylmethylphosphine 3 (10.00 g, 49.9
mmol) in anhydrous THF (100 ml), at r.t.. The reaction
was stirred at 25°C for 1 h, and the excess of dimethyl-
sulfide borane was removed by a stream of bubbling
argon. Then, the solvent was removed under vacuum
and the resulting solid was recrystallized from cyclohex-
ane, to give the borane complex 4 (9.74 g, 91% yield) as
colorless crystals.

226
N. Riegel et al. / Journal of Organometallic Chemistry 41 (1998) 219–233
Scheme 6.
M.p. 55°C (cyclohexane; lit. ([26]a) m.p. 51°C); Rf=
0.61 (toluene); IR (KBr): w¯ 3054 (w), 2365 (s), 2337(s),
purified by flash chromatography with a mixture cyclo-
hexane/toluene (1/1) as eluent. The air- and light-sensi-
tive product 5 was obtained as a colorless oil, which
crystallized very slowly (2.03 g, 65% yield).
2237 (w), 1483 (m), 1484 (s), 1059 (s), 887 (s), 754 (s)
cm−1 1H-NMR (CDCl3): l 7.71–7.62 (4H, m, H
; 6
arom), 7.51–7.40 (6H, m, H
10.1 Hz, CH3
), 1.50–0.23 (3H, q, 1JBH=93.5 Hz, BH3
13C-NMR (CDCl3): l 132.2–129.1 (C
arom), 12.3 (d,
1JPC=40.3 Hz, PCH3); 31P-NMR (CDCl3): l 9.99 (q,
1JPB=52.8 Hz).
6 =
arom), 1.86 (3H, d, 2JPH
M.p. 37°C; Rf =0.46 (toluene/cyclohexane 1/1); IR
(KBr): w¯ 3056 (w), 2932 (m), 2381 (s), 2343 (m), 2253
(w), 1722 (m), 1499 (m), 1436 (s), 1280 (m), 1062 (s),
6
6 );
6
1
727 (s), 701 (s) cm−1; H-NMR (CDCl3): l 7.68–7.60
6
(4H, m, H6 arom), 7.48–7.40 (6H, m, H6 arom), 6.58
3
3
(2H, t, J=2.0 Hz, NCH
6
), 6.11 (2H, t, J=2.0 Hz,
), 3.81 (2H, t, J=6.9 Hz, NCH2), 2.15 (2H, m,
2), 1.73 (2H, m), 1.53 (2H, m), 1.34 (2H, m),
1.70–0.30 (3H, m, BH
3); 13C-NMR (CDCl3): l 132.2–
128.2 (C arom), 120.4 (NCH), 107.9 (NCCH), 49.2
(NCH2), 31.0 (NCH2C
H2), 28.2 (d, 1JPC=14.2 Hz,
PCC H2), 22.6
H2), 25.6 (d, 2JPC=37.0 Hz, PC
(N(CH2)2C
3
4.4. 1,2-bis-(diphenylphosphino)ethane-bis-borane 7
NCCH
6
6
PCH
6
To a solution of 1,2-bis-(diphenylphosphino)ethane 6
(10.00 g, 25.1 mmol) in anhydrous THF (150 ml), was
added under argon dimethylsulfide borane (5.22 ml,
55.0 mmol, 2.2 equiv.) at r.t. The reaction mixture was
stirred at 25°C for 4 h and the solvent was removed
under vacuum. The residue was recrystallized from
toluene to give the compound 7 as colorless crystals
(10.10 g, 94% yield).
6
6
6
6
6
6
6
6
1
6
H2); 31P-NMR (CDCl3): l 16.11 (q, JPB
=
59 Hz); HRMS (EI) calcd for C21H27BNP [M]+
335.1974, Found 335.1953.
M.p. 166–168°C (toluene; lit. [39] m.p. 162–
167.5°C); Rf=0.82 (toluene); IR (KBr): w¯ 3056 (w),
2916 (w), 2380 (s), 2340 (s), 2252 (w), 1482 (m), 1436
4.6. 1-(N-But-4-yl-pyrrol)-1,2-bis
(diphenylphosphino)ethane-bis-borane 8
1
(s), 1108 (s), 1059 (s), 756 (s), 692 (s) cm−1; H-NMR
tert-Butyllithium (1.5 M in pentane, 0.50 ml, 0.75
mmol) was added dropwise under argon, to a solution
of 1,2-bis(diphenylphosphino)ethane diborane 7 (213
mg, 0.50 mmol) in anhydrous THF (2 ml) at 0°C. The
reaction was stirred at 0°C for 1.5 h, and a solution of
N-(4-bromobutyl)pyrrole 2 (202 mg, 1.00 mmol) in
anhydrous THF (2 ml) was added to the previous
solution, which became rapidly clear. The reaction was
stirred at 0°C for 3 h in the dark. After hydrolysis by a
saturated aqueous NH4Cl solution (5 ml) and twice
extraction with dichloromethane (2×15 ml), the com-
binated extracts were dried (MgSO4), and the solvent
was evaporated. The residue was purified by flash chro-
matography with a mixture of cyclohexane/toluene
(8:2) as eluent, to give the air- and light-sensitive
product 8 as a colorless oil (190 mg, 69%).
(CDCl3): l 7.67–7.60 (8H, m, H
6
arom), 7.50–7.39
arom), 2.37 (4H, dl, JPH=3.2 Hz, CH2),
1.70–0.20 (6H, q, 1JBH=94.0 Hz, BH3); 13C-NMR
2
(12H, m, H
6
6
6
1
(CDCl3): l 132.6–128.1 (C
Hz, PC
H2); 31P-NMR (CDCl3) l 18.0 (m, JPB=40.9
Hz).
6 arom), 19.9 (d, JPC=37.7
1
6
4.5. N-[5-(diphenylphosphinoborane)pentyl]pyrrole 5
To a solution of methyldiphenylphosphine borane 4
(2.00 g, 9.34 mmol) in anhydrous THF (10 ml) and
under argon, was added dropwise at −10°C sec-butyl-
lithium (1.3 M in cyclohexane, 7.90 ml, 10.27 mmol).
The reacting mixture was stirred at this temperature for
1.5 h, and the N-4-bromobutylpyrrole 2 (1.89 g, 9.35
mmol, 1 equiv.) was added to the solution which be-
came rapidly colorless. The reaction was stirred at
−10°C for 2 h and quenched by a saturated aqueous
NH4Cl solution (30 ml). THF was removed under
vaccum and the resulting residue was extracted twice
with dichloromethane (2×25 ml). The combinated or-
ganic layers were dried (MgSO4), and the solvent re-
moved under vacuum to give a residue which was
Rf=0.26 (toluene/cyclohexane; 1:1); IR (neat): w¯
3056 (w), 2929 (m), 2871 (w), 2382 (s), 2258 (w), 1499
1
(m), 1436 (s), 1051 (s), 734 (s), 694 (s) cm−1; H-NMR
(CDCl3): l 7.66–7.59 (8H, m, H
6
arom), 7.47–7.20
), 6.10
), 3.81 (2H, t, J=7.1 Hz,
2), 2.23 (1H, m, PC(H)H), 2.01 (2H, m, PCH(H)),
(12H, m, H
(2H, t, J=2.1 Hz, NCCH
6
arom), 6.56 (2H, t, 3J=2.1 Hz, NCH
6
3
3
6
NCH
6
6
6

N. Riegel et al. / Journal of Organometallic Chemistry 567 (1998) 219–233
227
Table 2
Results of allylic alkylation catalyzed by palladium complexes with phosphine boranes supported on polypyrroles 12–16
a Isolated yields of the major mono allylated product 19 [32].
b Reference [33].
c Reference [34].

228
N. Riegel et al. / Journal of Organometallic Chemistry 41 (1998) 219–233
Table 3
Results of coupling reaction catalyzed by palladium complexes with phosphine boranes linked on polypyrroles 12, 13
a Isolated yield.
b Reference [34].
1.85 (2H, m, NCH2CH2
0.47 (6H, m, BH3
); 13C-NMR (CDCl3): l 132.6–128.6
(C arom), 120.8 (NCH), 108.5 (NCCH), 49.4 (NCH2),
33.2 (NCH2CH2), 33.00 (N(CH2)2CH2), 25.4 (d, JPC
37.0 Hz, PCH2), 20.5(PCHC
H2); 31P-NMR (CDCl3): l
17.02 (m, JPC=67 Hz); Anal. calcd for C34H41B2NP2
(%): C, 74.62; H, 7.55; N, 2.56. Found: C, 74.60; H,
7.68; N, 2.55.
6
), 1.54 (4H, m, (CH2 2
6
) ), 1.50–
4.7. Chemical polymerization of
N-[5-(diphenylphosphinoborane)pentyl]pyrrole 5 into
supported phosphine borane 12
6
6
6
6
6
1
6
6
=
6
6
A solution of anhydrous ferric(III) chloride (592 mg,
3.6 mmol, 4 equiv.) in dry diethylether (1.6 ml) was
added under argon at 0°C to a solution N-[5-
(diphenylphosphinoborane)pentyl]pyrrole 5 (305 mg,
1

N. Riegel et al. / Journal of Organometallic Chemistry 567 (1998) 219–233
229
0.91 mmol) in dry diethylether (1 ml). The previous
brown solution became fastly colorless and a black
precipitate appeared. This suspension was vigourously
stirred at 0°C for 1 h, and then filtered to give a black
powder which was washed with ether (20 ml) and dry
under vacuum overnight (826 mg). This powder was
insoluble in classical organic solvents.
cm−1; Anal. calcd for C34H55NP2Fe4.8Cl13.6B2O7 [M=
1423.61](%): C, 28.69; H, 3.89; N, 0.98; P, 4.35; Fe,
18.83; Cl, 33.87, B, 1.52. Found: C, 28.73; H, 4.07; N,
1.02; P, 4.06; Fe, 18.76; Cl, 33.73, B, 1.13.
4.10. Electrochemical polymerization of
1-(N-but-4-yl-pyrrol)-1,2-bis(diphenylphosphino) ethane
diborane 8 into supported diphosphine borane 15
IR (KBr): w¯ 2926 (m), 2381 (m), 2345 (s), 1654 (w),
1436 (s), 1107 (s), 1063 (s), 736 (s), 692 (s) cm−1; Anal.
calcd for C21H39NPFe4.2Cl10BO6 [M=1032.42] (%): C,
24.43; H, 3.81; N, 1.36; P, 3.00; Fe, 22.72; Cl, 34.34.
Found: C, 23.97; H, 3.78; N, 1.50; P, 3.10; Fe, 22.72;
Polymerization of 1-(N-but-4-yl-pyrrol)-1,2-bis(-
diphenylphosphino) ethane diborane 8 (5×10−3 mol
l
−1) was performed in acetonitrile, in the conditions
Cl, 34.34. Surface area [35]: 3.4090.05 m2 g−1
.
previously described for polypyrrole 14 (Section 4.8).
4.8. Electrochemical polymerization of the
N-[5-(diphenylphosphinoborane)pentyl] pyrrole 5 into
supported phosphine borane 14
4.11. Decomplexation of 12 into phosphine grafted on
supported phosphine 16
Polypyrrole 12 (330 mg, 0.32 mmol) was suspended
in diethylamine (3 ml) and the mixture was heated
under argon overnight at 50°C. The reaction was
filtered and a brown powder of 16 was obtained (428
mg).
IR (KBr): w¯ 3421, 2970, 2905, 2817, 2774, 2469, 2370
(B–H), 1635, 1457, 1391, 1158, 1046 (B–N), 799, 696
cm−1. Anal. calcd for C66H159N13PFe4.5Cl11BO13 [M=
2026.15] (%): C, 39.12; H, 7.91; N, 8.99; P, 1.53; Fe,
12.40; Cl, 19.25. Found: C, 39.21; H, 7.71; N, 8.83; P,
1.50; Fe, 12.48; Cl, 19.71.
The study was run under an argon atmosphere in a
conventional three-electrode cell. The potentials were
relative to the Ag/Ag+ 10 mM reference electrode in
CH3CN. The working electrodes were macroporous
carbon (d=12 mm, h=1 cm). The polymerization of a
solution of 1-(N-pent-5-ylpyrrol)-diphenylphosphine
borane 5 (5×10−3 mol l−1) and tetrabutylammonium
perchlorate (10−1 mol l−1) in acetonitrile, was per-
formed by controlled potential oxidation at 0.85 V. The
polymerization was stopped when the quantity of ap-
plied electricity was 15 C, which corresponded to about
25 mg of polymer. The resulting material was kept in
acetonitrile.
4.12. Catalysis applications
4.12.1. Allylation of methylacetoacetate 18 catalyzed
by a palladium (0) complex generated from Pd(OAc)2
and supported phosphine boranes 12–15
4.9. Chemical polymerization of
1-(N-but-4-yl-pyrrol)-1,2-bis(diphenylphosphino)ethane
diborane 8 into the supported diphosphine borane 13
4.12.1.1. Typical procedure. A suspension of supported
phosphine borane 12 (66 mg, 6.4 mol%) and Pd(OAc)2
(7 mg, 3 mol%) in anhydrous THF (1 ml), was stirred
at r.t. for 30 min. Then, allylacetate 17a (108 ml, 1.0
mmol) or allylethylcarbonate 17b (130 mg, 1.0 mmol)
was added, and the mixture was stirred at r.t. for 15
min. In another flask under argon atmosphere, methy-
lacetoacetate (108 ml, 1.0 mmol) was added to a solu-
tion of NaH (26 mg, 1.1 mmol) in anhydrous THF (2
ml), and the mixture was stirred at r.t. for 30 min. The
resulting anion was added dropwise to the solution of
catalyst. The new mixture was stirred at r.t. and the
reaction was monitored by TLC. The ligand was re-
moved by filtration and the solution was concentrated.
The residue was purified by flash chromatography (elu-
ent: cyclohexane/toluene; 8:2), leading to the product
19a. The formation of a minor diallyl product 19b is
also observed.
A solution of anhydrous ferric(III) chloride (700 mg,
4.3 mmol) in dry diethylether (1.6 ml), was added under
argon at 0°C to a solution of 1-(N-but-4-yl-pyrrol)-1,2-
bis(diphenylphosphino)ethane diborane 8 (500 mg, 0.91
mmol) in dry diethylether (1 ml). The previous brown
solution became fastly colorless and a black precipitate
appeared. This suspension was vigourously stirred at
0°C for 1 h, and then filtered. The black powder was
washed with ether (20 ml) and dried under vaccum
overnight (1.04 g). This powder of polypyrrole 13 was
insoluble in classical organic solvents.
IR (KBr): w¯ 2920 (m), 2383(w), 1642 (s), 1610 (s),
1436 (m), 1109 (m), 1024 (m), 739 (m), 691 (m), 592 (m)
1H-NMR (CDCl3): l 5.72 (1H, m, CH2ꢀCH
(2H, m, CH2ꢀCH), 3.72 (3H, s, OCH3), 3.53 (1H, t,
CHCO2Me), 2.60 (1H, m, CH2), 2.27 (3H, s, CH3).
6 ), 5.11
6
6
Scheme 7.
6
6
6

230
N. Riegel et al. / Journal of Organometallic Chemistry 41 (1998) 219–233
Table 4
Results of hydrogenation of 26 catalyzed by rhodium complexes with phosphine boranes grafted on polypyrrole 12–16
a Isolated yield.
b Reference [34].
c Reference [33].

N. Riegel et al. / Journal of Organometallic Chemistry 567 (1998) 219–233
231
1
Minor diallyl product 19b: H-NMR (CDCl3): l 5.70
The reaction was heated at 65°C for 3 h, and the
polymer removed by filtration. The solvent was re-
moved under reduced pressure, and the residue was
poured in a 10% aqueous solution of Na2CO3 (5 ml)
and extracted three times with dichloromethane. The
aqueous layer was then acidified with HCl (0.1M) and
extracted twice with dichloromethane. The organic lay-
ers were dried (MgSO4) and the solvent was removed
under vacuum to give the cinnamic acid 24a (106 mg,
72% yield).
(2H, m, CH2ꢀCH
6
), 5.10 (4H, m, CH2
6
ꢀCH), 3.72 (3H, s,
OCH3), 2.60 (1H, m, CH2
6
6
), 2.20 (3H, s, CH3
6
).
4.12.1.2. Procedure using reco6ered polymer. To a solu-
tion of Pd(dba)2 (1.5 mol%) in dry THF the removed
polymer was added, and the mixture was stirred at r.t.
for 30 min. Allylacetate 17a was added, and the result-
ing mixture was stirred at r.t. for 15 min, generating the
catalyst which was reused for another allylation as
described above.
1H-NMR (CDCl3): l 11.0 (1H, s, CO2H
d, 3JHH=16 Hz, PhCH
), 7.55 (2H, m, H
7.41(3H, m, H
arom), 6.46 (1H, d, 3JHH=16 Hz,
PhCHꢀCH).
6
), 7.81 (1H,
arom),
6
6
4.12.2. Allylation of benzylamine 20 catalyzed by a
palladium (0) complex generated from Pd(OAc)2 and
supported phosphine borane 12
6
6
The reuse of the recovered polymer for another
preparation of catalyst was achieved with Pd(dba)2, as
described in Section 4.12.1.
A suspension of supported phosphine borane 12 (66
mg, 6.4 mol%) and Pd(OAc)2 (7 mg, 3 mol%) in
anhydrous THF (2 ml), was stirred at r.t. for 30 min.
Then allylacetate 17a (216 ml, 2.0 mmol) was added and
the resulting mixture was stirred at r.t. for 15 min. In
another flask under argon atmosphere, benzylamine 20
(109 ml, 1.0 mmol) was added to a solution of NaH (26
mg, 1.1 mmol) in anhydrous THF (3 ml); the mixture
was stirred at r.t. for 30 min and then added dropwise
to the catalyst. The new mixture was heated at 40°C for
60 h. Then, the polymer was removed by filtration and
the solvent was removed under vacuum. The residue is
purified by flash chromatography with a (8:2) mixture
of cyclohexane/ethylacetate as eluent, giving the N,N-
diallylbenzylamine 21 as a colorless oil (139 mg; 74%
yield).
4.12.4. Synthesis of 3-phenylcyclohexan-1-one 24b by a
Heck type reaction, catalyzed by palladium (0)
complexes generated from Pd(OAc)2 and supported
phosphine borane 12
Supported phosphine borane 12 (66 mg, 6.4 mol%)
was added to a solution of Pd(OAc)2 (7 mg, 3 mol%) in
DMF (2 ml), and the mixture was stirred at r.t. for 30
min. Then, a solution of iodobenzene 22a (112 ml, 1.0
mmol), cyclohexenone 23b (290 ml, 3.0 mmol), formic
acid (128 ml, 3.4 mmol) and triethylamine (0.41 ml, 2.9
mmol) in DMF (2 ml), was added and the mixture was
heated at 60°C for 24 h. The polymer was filtered off
and the filtrate was poured in an aqueous HCl solution
and extracted with ether (3×20 ml). The combinated
organic layers were dried (MgSO4) and the solvent was
removed under vacuum. After purification by flash
chromatography with a (9:1) mixture of cyclohexane/
ethyl acetate as eluent, the product 24b was obtained as
a pale yellow oil (50% yield).
1H-NMR (CDCl3) lit. ([31]b): l 7.35–7.15 (5H, m, H
6
arom), 5.82 (2H, dtd, 4J=1.3 Hz, 3Jtrans=17 Hz,
3Jcis=10 Hz, CH2ꢀCH
6
), 5.13 (1H, dq, J=4J=1.5 Hz,
2
3Jtrans=17 Hz, C(H
6
)HꢀCH), 5.07 (1H, dq, J=4J=1.5
2
3
Hz, Jcis=10 Hz, CH(H
3.01 (4H, dt, 3J=6.3 Hz, 4J=1.2 Hz, CH2
NMR (CDCl3): l 139.8 (C1 arom), 136.3 (CH arom),
129.3 (CH arom), 128.6 (CH arom), 127.2 (CHꢀCH2),
117.8 (CHꢀCH2), 57.9 (PhCH2), 56.8 (CH2CHꢀCH2).
6
)ꢀCH), 3.51 (2H, s, PhCH2
6 ),
6
N). 13C-
1
6
3-Phenylcyclohexan-1-one 24b: H-NMR (CDCl3): l
6
6
6
7.20–6.80 (5H, m, H
CH
2). 13C-NMR (CDCl3): l 211 (C
128.7 (C arom), 126.7 (C arom), 126.6 (C
(COCH2CHPh), 44.7 (CHPh), 41.2 (CH2C
(CH2CH2CHPh), 25.5 (CH2CH2CHPh).
6
arom), 2.35–0.90 (9H, m, CH
6 ,
6
6
6
6
6
O), 144 (C arom),
6
The reuse of the recovered polymer for another
preparation of catalyst was realized with Pd(dba)2, as
described in Section 4.12.1.
6
6
6
arom), 48.9
6 H2CO), 32.7
6
6
6
6
4.12.3. Preparation of the cinnamic acid 24a by Heck
reaction catalyzed by a palladium (0) complex
generated from Pd(OAc)2 and supported phosphine
boranes 12–15
4.12.5. Synthesis of 3-(p-methoxyphenyl)cyclohex-1-ene
24c by a Heck type reaction, catalyzed by palladium
(0) complexes generated from Pd(OAc)2 and supported
phosphine borane 12
Supported phosphine borane 12 (66 mg, 6.4 mol%)
was added to a solution of Pd(OAc)2 (7 mg, 3 mol%),
4-iodoanisole 22b (234 mg, 1.0 mmol), cyclohexene 23c
(304 ml, 3.0 mmol), triethylamine (0.41 ml, 2.9 mmol),
NEt4Br (308 mg, 2.0 mmol) and H2O (0.1 ml), in DMF
(3 ml). The reaction was stirred at 70°C for 60 h, and
then the polymer was filtered off. After flash chro-
matography of the residue on silicagel with a (9:1)
4.12.3.1. Typical procedure. Supported phosphine bo-
rane 12 (66 mg, 6.4 mol%) was added to a solution of
Pd(OAc)2 (7 mg, 3 mol%) in anhydrous THF (2 ml),
and stirred at r.t. for 30 min. Then, a solution of
iodobenzene 22a (112 ml, 1.0 mmol), acrylic acid 23a
(103 ml, 1.5 mmol) and triethylamine (0.35 ml, 2.5
mmol) in dry THF (2 ml) was added to the mixture.

232
N. Riegel et al. / Journal of Organometallic Chemistry 41 (1998) 219–233
mixture of cyclohexane/ethyl acetate as eluent, the
product 24c was obtained as a colorless oil (64% yield).
introduced following the procedure described Section
4.12.6, with a reaction time of 48 h.
The recovered catalyst was reused for an hydrogena-
tion under the same conditions, and without addition
of rhodium source.
3
1H-NMR (CDCl3): l 7.07 (2H, d, JHH=9.5 Hz, H
6
3
arom), 6.80 (2H, d, JHH=9.5 Hz, H
m, CHꢀCH), 3.70 (3H, s, CH3O), 2.60 (1H, m, CH
1.70 (6H, m, CH2
). 13C-NMR (CDCl3): l 157.75 (C
arom), 139.51 (C arom), 127.69 (CHꢀCH), 126.92 (C
arom), 126.79 (C arom), 113.69 (CHꢀCH), 55.19
(CH3O), 39.23 (CHPh), 33.58 (CH2CHꢀCH), 29.96
(CH2CHPh), 25.91 (CH2CH2CH2).
6
arom), 5.64 (2H,
6
6
6
6
),
6
6
6
Acknowledgements
6
6
6
6
6
We thank Dr S. Sadki for hepfull discussion on
polypyrrole, Dr G. Dosseh for her help in NMR spec-
tra, Dr L. Le Gendre (Universite´ de Rennes I) for the
surface area measurement, and the Ministry of Re-
search for financial support to EA 1389.
4.12.6. Hydrogenation of h-acetamidocinnamic acid 26
catalyzed by Rh (I) complexes generated from RhCl3,
and the supported phosphine boranes 12–15
4.12.6.1. Typical procedure. The supported phosphine
borane 12 (99 mg, 0.096 mmol, 9.6 mol%) was added to
a solution of RhCl3 (6 mg, 0.029 mmol, 2.9 mol%) in
pure ethanol (1 ml), and the mixture was heated at
reflux under argon for 1 h. The solution of h-acetami-
docinnamic acid 26 (203 mg, 1.0 mmol) and the catalyst
previously prepared in dry methanol (10 ml), was
stirred at r.t. in an autoclave under hydrogen pressure
(10 bars). After 24 h, the polymer bearing the catalyst
was filtered off and washed with methanol. The filtrate
was concentrated under vacuum and the residue was
extracted with NaOH (0.5 M). The aqueous layer was
filtered and acidified with HCl (1 M). The mixture was
extracted with ether (3×25 ml). The recombinated
organic phases were washed with water (5 ml), dried
(MgSO4) and the solvent removed. The reduction rate
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1
was deduced from the H-NMR spectra of the crude
product.
4.12.6.2. h-Acetamidocinnamic acid 26. 1H-NMR
(DMSO D6): l 9.46 (1H, s, CO2H
3J=7Hz, H
arom), 7.50–7.21 (3H, m, H
(1H, s, CHꢀC), 2.89 (1H, sl, NH), 2.50 (3H, s, CH3
6
), 7.62–7.59 (2H, d,
arom), 7.09
CO).
6
6
6
6
6
1
4.12.6.3. N-acetyl phenyl alanine 27. H-NMR (DMSO
D6): l 7.30 (5H, s, H
6
arom), 4.45 (1H, m, CH
6
), 3.08
2
3
(1H, dd, JHH=14 Hz, JHH=4 Hz, PhCH(H
6
)), 2.86
(1H, dd, 2JHH=14 Hz, 3JHH=12 Hz), 2.50 (1H, sl,
NH6 ), 1.78 (3H, s, CH6 3CO).
The hydrogenation of 26 catalyzed with the recov-
ered catalyst was realized under the same conditions
reported above, without addition of rhodium source.
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4.12.7. Hydrogenation of h-acetamidocinnamic acid 26
catalyzed by Rh (I) complexes generated from
[Rh(COD)Cl]2 and supported phosphine 16
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mg, 0.048 mmol, 4.8 mol%). Then, the catalyst was

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