New phosphorus dendrimers with chiral ferrocenyl phosphine-thioether ligands on the periphery for asymmetric catalysis

Article abstract of DOI:10.1016/j.jorganchem.2006.10.065

Chiral ferrocenyl phosphine-thioether ligands have been covalently bound on the periphery of 4 phosphorus dendrimers (generations 1-4) having a cyclotriphosphazene core and on one model compound. These new dendrimers proved to be efficient ligands for the palladium-catalyzed asymmetric allylic substitution reaction (ee up to 93%).

Full text of DOI:10.1016/j.jorganchem.2006.10.065

Journal of Organometallic Chemistry 692 (2007) 1064–1073
www.elsevier.com/locate/jorganchem
New phosphorus dendrimers with chiral ferrocenyl
phosphine-thioether ligands on the periphery for asymmetric catalysis
*
´
Lucie Routaboul, Sandrine Vincendeau, Cedric-Olivier Turrin, Anne-Marie Caminade ,
*
*
Jean-Pierre Majoral , Jean-Claude Daran, Eric Manoury
Laboratoire de Chimie de Coordination, CNRS-UPR 8241, 205 route de Narbonne F-31077 Toulouse Cedex, France
Received 21 September 2006; received in revised form 26 October 2006; accepted 26 October 2006
Available online 7 November 2006
Abstract
Chiral ferrocenyl phosphine-thioether ligands have been covalently bound on the periphery of 4 phosphorus dendrimers (generations
1–4) having a cyclotriphosphazene core and on one model compound. These new dendrimers proved to be efficient ligands for the pal-
ladium-catalyzed asymmetric allylic substitution reaction (ee up to 93%).
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Ferrocenes; Phosphorus dendrimers; P,S ligands; Asymmetric catalysis
1. Introduction
mote the palladium catalyzed asymmetric allylic substitu-
tion [8a]. The aim of our project was to graft such
ferrocenyl P,S ligands on the surface of phosphorus den-
drimers and to test them in the asymmetric allylic substitu-
tion reaction.
Dendrimers represent a new and fascinating class of
regular highly branched and well-defined macromolecules
[1] which found numerous promising applications in mate-
rials chemistry, biology, etc. but also as homogenous cat-
alysts with the catalytic sites in the core or at the periphery
of the dendrimers [2]. However, although a very large
number of catalytic systems using dendrimers have already
been described, much less reports on asymmetric catalysis
with chiral dendrimers have been disclosed [3]. We have
been interested since a long time in the synthesis of phos-
phorus-containing dendrimers [4] and more recently in the
synthesis of such dendrimers bearing ferrocene moieties
[5]. In addition, we recently took interest in chiral P,S
ligands. This type of ligands is still uncommonly used in
asymmetric catalysis [6] but had been, however, success-
fully used in various asymmetric catalytic systems [7].
Therefore, we developed new chiral ferrocenyl P,S [8]
ligands ((S)-4R, Scheme 1) which proved to efficiently pro-
2. Results and discussion
2.1. Synthesis of the dendrimers
One step of the synthesis of phosphorus-based dendri-
mers is the quantitative reaction of phenols on PCl bonds
on the periphery of the growing dendrimer [4]. So, we
needed a compound (S)-4R bearing a phenol in order to
covalently bind it to the surface of phosphorus-containing
dendrimers (Schemes 1 and 2). We then decided to used
(S)-1 for this purpose.
Compounds (S)-4R were synthesized by reaction of
alcohol (S)-2 and thiol RSH in presence of fluoroboric acid
[8a]. The same procedure was carried out to obtain the cor-
responding thioether (S)-3 using 4-hydroxythiophenol as
thiol. In this case, only the desired product (S)-3 was
obtained in high yields (Scheme 1): no product of O-alkyl-
ation or from Friedel–Crafts reaction were detected.
Finally, compound (S)-1 was obtained by desulfuration
*
Corresponding authors.
E-mail addresses: caminade@lcc-toulouse.fr (A.-M. Caminade),
majoral@lcc-toulouse.fr (J.-P. Majoral), manoury@lcc-toulouse.fr
(E. Manoury).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.10.065

L. Routaboul et al. / Journal of Organometallic Chemistry 692 (2007) 1064–1073
1065
Fe
Fe
S
i, ii
HO
S
HO
Ph2P
Ph2P
(S)-2
S
(S)-3 (95%)
iii
(S)-4R (92%)
Fe
Ph2P
R = Ar, Alk
Fe
HO
S
S
R
Ph2P
(S)-1 (92%)
Scheme 1. Synthesis of P,S ligand (S)-1. Conditions: (i) HBF4, (ii) p-
HSC6H4OH, (iii) P(NMe2)3.
N
N
N
S
Cl
Cl
[P=N]3
i
O
O
P
6
Fe
Ph2P
N
P
S
O
S
[P=N]3
2
6
Scheme 2. Synthesis of dendrimer G1. Conditions: (i) (S)-1 (12 eq.),
Cs2CO3 or HNa (12 eq.), THF, RT overnight.
of (S)-3 using tris(dimethylamino)phosphine (Scheme 1)
[8a].
The structure of 3 has been confirmed by X-ray diffrac-
tion analysis of the racemic mixture [9] on monocrystals
(Fig. 1) [10]. As observed in related ferrocene derivatives
[11], the S attached to the phosphine group is endo with
Fig. 2. Partial packing view showing the O–Hꢁ ꢁ ꢁS hydrogen bonding and
the formation of infinite chains developping parallel to the (10ꢀ1) plane.
[Symmetry code: (i) 1/2 + x, 1/2 ꢀ y, 1/2 + z.]
˚
respect to the Cp ring (ꢀ0.83(2) A) whereas the S attached
˚
to the phenol group is exo by 1.72(2) A. The two Cp rings
are nearly eclipsed and bond lengths and angles within the
ferrocene moiety are as usual. The most interesting feature
is the occurrence of hydrogen bond between the hydroxyl
group of the phenol and the phosphine sulfur atom of a
The sodium salt of the phenol ferrocene (S)-1 is readily
obtained by reaction with sodium hydride in THF. The
subsequent reaction of 12 equivalents of the sodium salt
of (S)-1 with the first generation dendrimer terminated
with –P(S)Cl2 functions proceeds smoothly at room tem-
perature in THF overnight. The chiral dendrimer G1 is
obtained in nearly quantitative yield after work up
(Scheme 2) as a reddish powder which is sensitive to
oxidation.
˚
˚
neighboring molecule [O–H: 0.82 A; Hꢁ ꢁ ꢁS: 2.356 A;
˚
Oꢁ ꢁ ꢁS: 3.170 A; O–Hꢁ ꢁ ꢁS 172.4ꢁ] resulting in the formation
of an infinite zig-zag like chain (see Fig. 2).
The reaction is monitored by 31P NMR, which shows
first a deshielding of the signal corresponding to the phos-
phorus atoms that undergo the reaction, from d =
66.5 ppm for G1 to d = ca. 72 ppm for the intermediate
mono-arylated –P(S)Cl(O-Ar) terminations. The second
chlorine substitution is accompanied by a shielding of the
P(IV) surface atoms to ca. 66.2 ppm for G1.
The same procedure is applied to the second, third and
fourth generation of P(S)Cl2 terminated dendrimers, lead-
ing to dendrimers Gn (n = 2,3,4) possessing theoretically
24, 48 and 96 ferrocenyl (P,S) ligands, respectively (see
Fig. 3). The completion of all the reactions reported here
has been evidenced by TLC monitoring and multinucleus
NMR.
The compound 0, standing as a model of a monomeric
single dendrimeric ending was obtained in a similar fash-
Fig. 1. X-ray structure of compound ( )-3.

1066
L. Routaboul et al. / Journal of Organometallic Chemistry 692 (2007) 1064–1073
The first attempts to reuse the dendritic catalysts have
Fe
***
** *
* *
*
N
N
*
*
**
*
*
*
*
*
*
*
*
*
=
O
P
O
S
*
*
*
*
*
*
*
been carried out with G4 simply by precipitation with
pentane at the end of the catalytic reaction (Table 1,
entry 8). The catalytic activity and the enantioselectivity
decreased significantly. So, further studies towards an
efficient recycling of these dendrimeric catalysts, for
instance, by screening of solvants for the precipitation
or by more sophisticated methods, like continuous homo-
geneous catalysis with nanofiltration [14], will be
necessary.
*
S
Ph2P
*
*
*
*
*
*
*
*
*
2
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
**
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
* *
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
* *
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
**
*
G2
G3
G4
*
*
*
*
*
*
*
*
*
*
* *
*
**
G1
0
Fig. 3. Gallery of dendrimers and branch termini model.
ion, starting from crystalline PhCH@N–N(Me)P(S)Cl2.
The nucleophilic substitution of the chlorine atoms was
performed in THF using either cesium carbonate or
sodium hydride as a base. Lack of differences in solubility
between (S)-4 and 0 imposed a silica gel chromatography
to obtain pure samples of the accurate branched termini
model.
2.3. Conclusion
In conclusion, chiral ferrocenyl P,S ligands have been
successfully grafted on the surface of phosphorus-contain-
ing dendrimers of various sizes (from model compound 0
with 2 ferrocenyl P,S ligands to generation 4 with 96 ferr-
ocenyl P,S ligands). These new dendrimeric ligands were
successfully used in the asymmetric allylic substitution:
the catalytic properties of the original monomeric ligand
were left almost unaffected after grafting on the different
dendrimeric scaffolds, as shown by comparison of activities
between the monomer itself, the dendrimers G1–4 and the
branch termini model 0. Indeed, these organometallic den-
drimers are efficient soluble polymer-supported catalysts
[15].
2.2. Catalysis
The different dendrimers were used in the allylic substi-
tution reaction [12] under classical conditions (Table 1).
The reaction times for completion were almost the same
for the dendrimers of different sizes and the corresponding
monomeric ligand (S)-4 (Table 1).
In every case, isolated yields were very high and enanti-
oselectivities very close to the one observed for the mono-
meric (S)-4. The dendrimeric structures do not affect very
much the course of the catalytic reaction: no positive or
negative dendritic effects [3,13] were observed in this reac-
tion. Furthermore, we tested the influence of an excess of
ligand G4 related to palladium: as for the monomeric
ligand, the catalytic properties observed with a twofold
excess of P,S ligand on the surface of the dendrimer were
very similar to the ones observed with a 1.05 ligand/metal
ratio (Table 1, entries 6 and 7).
3. Experimental
3.1. General
All reactions were carried out in the absence of air using
standard Schlenk techniques and vacuum-line manipula-
tions. Commercial samples were used as received. All sol-
vents were dried before use. Thin layer chromatography
was carried out on Merck Kieselgel 60F254 precoated silica
Table 1
Palladium-catalyzed asymmetric allylic substitution
Entry
Liganda
Reaction time
Conversion (%)
Yieldb (%)
eec (%)
1
2
3
4
5
6
7
8
a
(S)-4Ph
0
G1
2 h:30 min
2 h:30 min
3 h
3 h
3 h
2 h:30 min
2 h:30 min
6 h
100
100
100
100
100
100
100
100
96
95
89
93
94
92
87
88
93
91
93
92
90
91
92
81
G2
G3
G4
G4
d
e
G4
Reaction run with 0.5 mmol of rac-1,3-diphenylprop-2-enyl acetate, 1 mmol of dimethylmalonate, 1 mmol of BSA, a catalytic amount of LiOAc, the
ligand and 0.01 mol of dimeric palladium precursor (2 mol% in palladium as [PdCl(allyl)]2) in 2 mL of dichloromethane at RT; with a 1.05 P,S ligand/Pd
ratio.
b
Isolated yield.
c
(R) configuration,determined by 1H NMR using Eu-(+)-(hfc)3 as chiral chemical shift reagent.
d
P,S ligand/Pd ratio was 2.
e
Reused catalyst: at the end of a catalytic run, the dendrimer was precipitated and washed with dry pentane under argon. After evaporation under
vacuum, the remaining oil was reused by adding 2 mL of dry dichloromethane, 0.5 mmol of rac-1,3-diphenylprop-2-enyl acetate, 1 mmol of dimethyl-
malonate, 1 mmol of BSA and a catalytic amount of LiOAc.

L. Routaboul et al. / Journal of Organometallic Chemistry 692 (2007) 1064–1073
1067
gel plates. Preparative flash chromatography was per-
formed on Merck Kieselgel. Instrumentation: Bruker
AC200, AM250, ARX250, AMX400 and DPX300 (1H,
13C and 31P NMR), Hewlett–Packard HP MSD 7590
(GC/MS). Elemental analyses were performed by the Ser-
vice d’Analyse du Laboratoire de Chimie de Coordination,
Toulouse (France).
carried out using tris(dimethylamino)phosphine [8a]
(yield = 91%).
C3
C4
C2
C1
S
CH2
Cp
PPh2
OH
Fe
(S)-1
Cp'
3.2. Published procedures
Dendrimers terminated with P(S)Cl2 groups [16] were
synthesized according to published procedures.
(S)-2-Thiodiphenylphosphino-(4-hydroxyphenylthio-
methyl)ferrocene was synthesized from (S)-2-thio-diphenyl-
phosphino-(hydroxymethyl)ferrocene and 4-hydroxythio-
phenol by a published procedure (yield = 95%) [8a].
31P{1H} NMR (202.5 MHz, CDCl3) d = ꢀ21.5 ppm.
1H NMR (500.3 MHz, CDCl3) d = 3.84 (1H, m, Cp-H);
4.03 (5H, s, Cp0-H); 4.06 (2H, br s, CH2); 4.29 (1H, br t,
J = 2.5 Hz, Cp-H); 4.37 (1H, m, Cp-H); 6.74 (2H, m, C2-
H); 7.21 (2H, m, C3-H); 7.3–7.2 (5H, m, PPh2); 7.45–7.40
(3H, m, PPh2); 7.65–7.60 (2H, m, PPh2) ppm.
13C{1H} NMR (125.8 MHz, CDCl3) d = 36.4 (s, CH2);
70.0 (s, Cp); 70.3 (s, Cp0); 71.9 (d, JCP = 3.7 Hz, Cp);
72.2 (d, JCP = 3.6 Hz, Cp); 75.9 (d, JCP = 6.8 Hz, Cpipso);
90.7 (d, JCP = 25.8 Hz, Cpipso); 116.4 (s, C2); 127.4 (s,
C4); 128.3 (s, PPh2); 128.4 (d, JCP = 6.0 Hz, PPh2); 128.6
(d, JCP = 8.0 Hz, PPh2); 129.7 (s, PPh2); 132.9 (d,
JCP = 17.6 Hz, PPh2); 134.4 (s, C3); 135.6 (d,
JCP = 21.1 Hz, PPh2); 137.9 (d, JCP = 7.2 Hz, quat PPh2);
140.1 (d, JCP = 7.9 Hz, quat PPh2); 155.5 (s, C1) ppm.
3.2.1. Synthesis of (S)-2-thiodiphenylphosphino-
(4-hydroxyphenylthiomethyl)ferrocene (S)–(3)
C3
C4
C2
C1
S
CH2
Cp
PPh2
OH
Fe
S
(S)-3
Cp'
3.2.3. Synthesis of model compound 0
To
a suspension of cesium carbonate (609 mg,
31P{1H} NMR (202.5 MHz, CDCl3) d = 44.5 ppm.
1H NMR (500.3 MHz, CDCl3) d = 3.79 (1H, br s, Cp-
H); 4.12 (1H, d (AB), JHH = 13.5 Hz, CH2); 4.27 (1H, m,
Cp-H); 4.31 (5H, s, Cp0-H); 4.39 (1H, m, Cp-H); 4.43
(1H, d (AB), JHH = 13.5 Hz, CH2); 6.73 (2H, br d (AB),
JHH = 8.6 Hz, C2-H); 7.15 (2H, br d (AB), JHH = 8.6 Hz,
C3-H); 7.56–7.39 (6H, m, PPh2); 7.72–7.66 (2H, m, PPh2);
7.8–7.80 (2H, m, PPh2) ppm.
1.86 mmol) in 10 mL of THF was added ferrocene (S)-1
(440 mg, 0.86 mmol). The mixture was stirred for 3 h at
room temperature and then was added dropwise a solution
of PhCH@NN(Me)P(S)Cl2 (112 mg, 0.42 mmol) in 5 mL
of THF at room temperature. The resulting mixture was
stirred overnight at room temperature and then centri-
fuged. The clear solution was then concentrated under
reduced pressure and precipitated with pentane. The result-
ing yellow powder was subjected to column chromatogra-
phy (CH2Cl2) to afford the expected compound 0 as a
yellow powder in 80% yield (774 mg).
13C{1H} NMR (125.8 MHz, CDCl3) d = 35.5 (s, CH2);
69.5 (d, JCP = 10.4 Hz, Cp); 71.3 (s, Cp0); 74.0 (d,
JCP = 95.2 Hz, Cpipso); 74.2 (d, JCP = 9.2 Hz, Cp); 75.0
(d, JCP = 12.5 Hz, Cp); 89.6 (d, JCP = 12.0 Hz, Cpipso);
116.3 (s, C2); 127.3 (s, C4); 128.5 (d, JCP = 14.3 Hz,
PPh2); 128.6 (d, JCP = 14.5 Hz, PPh2); 131.7 (d,
JCP = 2.7 Hz, 2CPPh2); 132.5 (d, JCP = 10.8 Hz, PPh2);
132.6 (d, JCP = 10.7 Hz, PPh2); 133.8 (d, JCP = 90.5 Hz,
quat PPh2); 134.3 (s, C3); 134.8 (d, JCP = 89.5 Hz, quat
PPh2); 155.5 (s, C1) ppm.
Fe
C13
4
C1
C12
1
Co
S
PhP
Ci
Cm
Cp
2
C1
3
C0
C0
C04
O
C01
[a]D = +47.6 (CHCl3, c = 0.6) MS (DCI, NH3) m/e: 541
(M+1, 100%), 415 (M-Ar, 59%).
N
N
P
Elem. Anal. Calc. for C29H25FeOPS2 (540.47 g molꢀ1):
C, 64.55; H, 4.66. Found: C, 64.36; H, 4.53%.
O
S
Fe
S
Ph2P
3.2.2. Synthesis of (S)-2-diphenylphosphino-
(4-hydroxyphenylthiomethyl)ferrocene (S)–(1)
The desulfuration of (S)-2-thiodiphenylphosphino-(4-
31P{1H} NMR (121.5 MHz, CDCl3) d = ꢀ20.7 (s,Cp-
PPh2); 66.1 (s, PS) ppm.
1H
NMR
(300 MHz,
CDCl3)
d = 3.36
(d,
hydroxyphenylthiomethyl)-ferrocene
into
(S)-2-diph-
3JHP = 10.5 Hz, 3H, P-N-Me); 3.83 (br s, 2H, Cp-H);
enylphosphino-(4-hydroxyphenylthiomethyl)ferrocene was

1068
L. Routaboul et al. / Journal of Organometallic Chemistry 692 (2007) 1064–1073
4.03 (br s, 10H, Cp0-H); 4.07 (s, 4H, CH2); 4.26 (s, 2H, Cp-
H); 4.37 (s, 2H, Cp-H); 7.19–7.79 (m, 34H, Harom and
CH@N) ppm.
to a solution of first generation phosphorus dendrimer
capped with 6 P(S)Cl2 end groups (50 mg, 0.027 mmol)
in 20 mL of THF at room temperature. The resulting
mixture was stirred overnight at room temperature and
then centrifuged. The clear solution was then concen-
trated under reduced pressure and precipitated with
ether. The resulting powder was dried and washed twice
with 40 mL of a mixture ether–pentane (1/1) to afford
the expected dendrimer G1 as a yellow powder in 91%
yield (184 mg).
13C{1H} NMR (62.9 MHz, CDCl3) d = 33.37 (d,
3
2JCP = 12.1 Hz, P-N-Me); 34.91 (d, JCP = 12.0 Hz, CH2);
2
70.1 (s, Cp); 70.3 (s, Cp0), 71.91 (d, JCP = 3.0 Hz, Cp);
72.13 (br s, Cp); 75.8 (d, JCP = 7.8 Hz, Cpipso); 89.5 (d,
3
JCP = 26.2 Hz, Cpipso); 122.26 (d, JCP = 6.2 Hz, C2);
1
3
127.5 (s, C2); 128.42 (br d, JCP = 5.9 Hz, Cm); 128.46 (s,
0
Cp); 128.61 (d, JCP = 8.1 Hz, Cm); 129.21 (s, C3); 129.68
3
1
Fe
PPh2
S
Fe
PPh2
Fe
S
PPh2
S
PPh2
O
O
O
Fe
S
S
N
P
N
P
N
S
N
O
Fe
S
Ph2P
O
O
PPh2
N
P
O
S
S
O
P
N
P
N
O
N
N
O
P
Fe
P
N
N
O
S
O
Fe
S
O
O
Ph2P
S
Ph2P
Fe
N
N
S
N
N
P
P
S
O
O
O
O
S
S
Fe
Ph2P
Ph2P
S
S
Fe
Ph2P
Ph2P
Fe
Fe
(s, C30); 129.92 (s, C10); 131.88 (s, C41); 132.86 (d,
31P{1H} NMR (121.5 MHz, CDCl3) d = ꢀ20.8 (s, Cp-
2JCP = 17.7 Hz, Co); 134.08 (s, C40); 135.43 (d,
PPh2); 11.8 (s, N3P3); 66.2 (s, P1) ppm.
1
2JCP = 20.8 Hz, Co); 138.12 (d, JCP = 8.2 Hz, Ci); 140.12
1H
NMR
(300 MHz,
CDCl3)
d = 3.21
(d,
3
1
(d, JCP = 13.8 Hz, CH@N); 140.72 (d, JCP = 8.1 Hz,
3JHP = 10.2 Hz, 18H, P-N-Me); 3.74 (br s, 12H, Cp-H);
3.97 (br s, 60H, Cp0-H); 4.04 (s, 24H, CH2); 4.22 (s, 12H,
Cp-H); 4.33 (s, 12H, Cp-H); 7.09–7.69 (m, 198H, Harom
and CH@N) ppm.
Ci); 150.03 (d, JCP = 6.2 Hz, C1) ppm.
2
1
Elem.
Anal.
Calc.
for
C66H57Fe2N2O2P3S3
(1211 g molꢀ1): C, 65.46; H, 4.74; N, 2.31. Found: C,
65.56; H, 4.85; N, 2.25%.
13C{1H} NMR (62.9 MHz, CDCl3) d = 33.12 (d,
2JCP = 12.2 Hz, P-N-Me); 34.92 (d, JCP = 12.5 Hz, CH2);
3
2
3.3. Synthesis of dendrimers
69.67 (s, Cp); 69.86 (s, Cp0), 71.48 (d, JCP = 3.1 Hz, Cp);
71.66 (br s, Cp); 75.86 (d, JCP = 7.9 Hz, Cpipso); 89.52 (d,
3.3.1. Synthesis of dendrimer G1
JCP = 26.2 Hz, Cpipso); 121.39 (br s, C2); 121.77 (br s,
0
C2); 127.89 (d, JCP = 7.7 Hz, Cm); 128.06 (s, Cp); 128.17
3
To a suspension of 8 mg (0.33 mmol) of sodium
hydride in 20 mL of THF was added 167 mg
(0.33 mmol) of ferrocene (S)-1. The mixture was stirred
for 3 h at room temperature and then added dropwise
1
(d, JCP = 8.2 Hz, Cm); 129.21 (s, C30); 131.27 (s, C13);
3
132.22 (s, C4); 132.35 (d, JCP = 17.7 Hz, Co); 134.05 (s,
2
0
C41); 135.12 (d, 2JCP = 18.7 Hz, Co); 137.06 (d,

L. Routaboul et al. / Journal of Organometallic Chemistry 692 (2007) 1064–1073
1069
3
1JCP = 8.4 Hz, Ci); 139.64 (d, JCP = 13.9 Hz, CH@N);
24H, Cp-H); 4.32 (s, 24H, Cp-H); 7.02–7.72 (m, 426H,
Harom and CH@N) ppm.
1
2
139.71 (d, JCP = 8.0 Hz, Ci); 148.98 (d, JCP = 6.6 Hz,
C11); 148.98 (br s, C10) ppm.
13C{1H} NMR (75.5 MHz, CDCl3) d = 33.46 (d,
3
Elem. Anal. Calc. for
C
396H336Fe12N15O18P21S18
2JCP = 13.3 Hz, P-N-Me); 34.87 (d, JCP = 12.5 Hz, CH2);
(7491 g molꢀ1): C, 63.49; H, 4.52; N, 2.80. Found: C,
63.57; H, 4.60; N, 2.72%.
70.05 (s, Cp); 70.27 (s, Cp0); 71.90 (d, JCP = 3.0 Hz, Cp);
2
72.01 (br s, Cp); 75.29 (d, JCP = 8.0 Hz, Cpipso); 89.98 (d,
JCP = 31.6 Hz, Cpipso); 121.03 (br s, C2); 122.25 (br d,
0
3
3.3.2. Synthesis of dendrimer G2
3JCP = 3.9 Hz, C2 ); 128.29 (d, JCP = 9.1 Hz, Cm); 128.43
1;2
3
To a suspension of 5 mg (0.21 mmol) of sodium hydride
in 20 mL of THF was added 102 mg (0.20 mmol) of ferro-
cene (S)-1. The mixture was stirred for 3 h at room temper-
ature and then added dropwise to a solution of second
generation phosphorus dendrimer capped with 12 P(S)Cl2
end groups (40 mg, 8.3 · 10ꢀ3 mmol) in 20 mL of THF at
room temperature. The resulting mixture was stirred over-
night at room temperature and then centrifuged. The clear
solution was then concentrated under reduced pressure and
precipitated with ether. The resulting powder was dried
and washed twice with 40 mL of a mixture ether–pentane
(1/1) to afford the expected dendrimer G2 as a yellow pow-
der in 89% yield (119 mg).
(s, Cp); 128.56 (d, JCP = 8.0 Hz, Cm); 129.60 (s, C30;1);
131.77 (s, C23); 132.21 (s, C04;1); 132.74 (d, JCP = 17.6 Hz,
2
Co); 134.33 (s, C4); 135.47 (d, JCP = 21.2 Hz, Co); 137.06
2
2
1
3
(d, JCP = 8.4 Hz, Ci); 139.64 (br d, JCP = 13.7 Hz,
1
CH@N); 139.71 (d, JCP = 8.0 Hz, Ci); 149.52 (br d,
2JCP = 6.4 Hz, C1); 151.72 (br s, C01;1) ppm.
2
Elem. Anal. Calc. for
C840H720Fe24N39O42P45S42
(16114 g molꢀ1): C, 62.61; H, 4.50; N, 3.39. Found: C,
62.62; H, 4.59; N, 3.32%.
3.3.3. Synthesis of dendrimer G3
To a suspension of 13 mg (0.52 mmol) of sodium
hydride in 20 mL of THF was added 250 mg (0.49 mmol)
Fe
PPh2
Fe
Fe
S
PPh2
Fe
PPh2
S
PPh2
S
S
Fe
PPh2
Fe
PPh2
O
S
S
PPh2
O
Fe
O
P
S
O
N
S
O
O
S
P
N
N
P
Fe
N
S
N
N
PPh2
O
S
S
PPh2
P
O
N
S
N
O
P
O
Fe
Fe
N
N
O
S
O
S
Ph2
P
O
S
P
N
O
P
S
PPh2
N
N
N
Fe
Fe
S
N
S
O
N
O
Ph2P
P
S
N
O
O
O
S
N
P
O
P
N
O
N
P
N
P
N
N
O
O
P
S
O
PPh2
S
O
P
S
N
O
N
O
O
S
Fe
Fe
S
N
Ph2
P
P
O
N
PPh2
N
S
N
O
N
P
O
Fe
S
S
N
P
O
O
O
Fe
S
N
N
S
O
Ph2P
P
Ph2
P
S
O
Fe
N
S
N
N
P
N
N
O
P
S
O
O
N
S
S
P
S
Fe
Ph2
P
O
O
Ph2P
O
S
Fe
Fe
S
Ph2P
S
Ph2
P
S
S
Fe
Ph2
P
Ph2P
Fe
Ph2P
Fe
Fe
31P{1H} NMR (121.5 MHz, CDCl3) d = ꢀ20.8 (s,Cp-
PPh2); 11.8 (s, N3P3); 66.0 (s, P1); 66.2 (s,P2) ppm.
of ferrocene (S)-1. The mixture was stirred for 3 h at room
temperature and then added dropwise to a solution of third
generation phosphorus dendrimer capped with 24 P(S)Cl2
end groups (100 mg, 9.3 · 10ꢀ3 mmol) in 20 mL of THF
at room temperature. The resulting mixture was stirred
1H NMR (300 MHz, CDCl3) d = 3.21 (br d,
3JHP = 10.5 Hz, 54H, P-N-Me); 3.77 (br s, 24H, Cp-H);
3.95 (br s, 120H, Cp0-H); 4.03 (s, 48H, CH2); 4.21 (s,

1070
L. Routaboul et al. / Journal of Organometallic Chemistry 692 (2007) 1064–1073
3
overnight at room temperature and then centrifuged. The
clear solution was then concentrated under reduced pres-
sure and precipitated with ether. The resulting powder
was dried and washed twice with 40 mL of ether to afford
the expected dendrimer G3 as a yellow powder in 93% yield
(360 mg).
C20); 122.25 (br d, JCP = 3.9 Hz, C21;2;3); 128.29 (d,
3JCP = 9.1 Hz, Cm); 128.43 (s, Cp); 128.56 (d,
3JCP = 8.0 Hz, Cm); 129.60 (s, C03;1;2); 131.77 (s, C33);
132.21 (s, C40;1;2); 132.74 (d, JCP = 17.6 Hz, Co); 134.33
2
(s, C43); 135.47 (d, JCP = 21.2 Hz, Co); 137.06 (d,
2
1JCP = 8.4 Hz, Ci); 139.64 (br d, JCP = 13.7 Hz, CH@N);
3
Fe
Fe
Fe
PPh2
PPh2
PPh2
Fe
PPh2
S
Fe
PPh2
PPh2
S
Fe
S
S
Fe
PPh2
S
PPh2
S
Fe
PPh2
Fe
S
Fe
S
Fe
O
O
PPh2
O
PPh2
O
P
O
P
S
O
S
S
PPh2
N
N
Fe
O
S
N
S
O
P
P
Fe
N
S
N
S
N
PPh2
S
N
N
Fe
PPh2
O
S
Fe
S
O
O
O
S
P
PPh2
P
N
N
PPh2
O
S
Fe
O
S
O
S
O
N
O
N
Fe
P
N
O
P
S
S
P
N
S
N
N
O
N
PPh2
P
O
PPh2
N
N
N
S
Fe
S
S
Fe
O
O
O
O
O
S
P
S
PPh2
O
N
Ph2P
P
S
S
P
N
S
N
O
N
P
O
O
O
N
N
N
Fe
N
P
S
N
N
S
Fe
S
O
PPh2
S
O
N
S
N
S
P
PPh2
Fe
O
P
O
O
O
P
N
O
N
P
O
N
S
N
N
Fe
N
N
N
P
N
O
S
P
O
O
O
S
S
N
S
PPh2
Fe
S
O
Ph2
Fe
P
O
O
N
P
P
O
N
N
PPh2
P
N
S
S
O
N
P
Ph2
P
O
O
O
Fe
N
S
N
N
N
S
S
Fe
P
O
O
O
O
P
S
P
O
S
N
P
S
O
S
N
N
N
O
N
Ph2
P
P
Ph2P
O
O
N
N
O
S
N
N
N
Fe
N
Fe
O
N
S
N
S
S
P
P
N
S
P
O
S
Ph2
P
P
O
S
O
N
O
O
S
PPh2
P
N
O
O
O
O
S
Fe
N
Fe
Ph2
N
S
O
Ph2
P
S
P
N
P
N
O
S
P
N
N
O
S
N
N
S
S
S
Fe
O
N
P
N
Fe
P
N
S
O
O
P
O
S
S
Ph2P
PPh2
O
O
N
P
S
O
O
S
O
Fe
Fe
Ph2
Fe
P
Ph2P
N
N
N
S
N
S
S
N
Fe
Ph2
N
P
P
O
S
N
S
P
O
N
Ph2P
S
S
O
P
O
P
O
Ph2
P
O
Fe
O
Fe
O
S
Ph2
P
Fe
S
Fe
S
Ph2
P
S
Ph2P
S
S
S
S
Fe
Fe
Ph2P
Ph2
P
Ph2
P
Fe
Fe
Ph2P
Ph2
P
Ph2P
Fe
Fe
Fe
1
2
31P{1H} NMR (81 MHz, CDCl3) d = ꢀ20.8 (s, Cp-
PPh2); 11.7 (s, N3P3); 66.2 (br s, P1,2,3) ppm.
139.71 (d, JCP = 8.0 Hz, Ci); 149.52 (br d, JCP = 6.4 Hz,
C13); 151.72 (br s, C01;1;2) ppm.
1H NMR (200 MHz, CDCl3) d = 3.22 (br s, 126H, P-N-
Me); 3.74 (br s, 48H, Cp-H); 3.92 (br s, 240H, Cp0-H); 4.03
(s, 96H, CH2); 4.23 (s, 48H, Cp-H); 4.28 (s, 48H, Cp-H);
7.02–7.72 (m, 882H, Harom and CH@N) ppm.
Elem. Anal. Calc. for C1728H1488Fe48N87O90P93S90
(36360 g molꢀ1): C, 62.22; H, 4.50; N, 3.65. Found: C,
62.38; H, 4.59; N, 3.56%.
13C{1H} NMR (50.3 MHz, CDCl3) d = 33.07 (d,
3.3.4. Synthesis of dendrimer G4
3
2JCP = 12.6 Hz, P-N-Me); 34.47 (d, JCP = 12.2 Hz,
To a suspension of 6 mg (0.25 mmol) of sodium hydride
in 20 mL of THF was added 109 mg (0.21 mmol) of ferro-
cene (S)-1. The mixture was stirred for 3 h at room temper-
ature and then added dropwise to a solution of fourth
2
CH2); 69.66 (s, Cp); 69.84 (s, Cp0); 71.90 (d, JCP
=
3.0 Hz, Cp); 72.01 (br s, Cp); 75.29 (d, JCP = 8.0 Hz,
Cpipso); 89.98 (d, JCP = 31.6 Hz, Cpipso); 121.03 (br s,

L. Routaboul et al. / Journal of Organometallic Chemistry 692 (2007) 1064–1073
1071
generation phosphorus dendrimer capped with 48 P(S)Cl2
end groups (50 mg, 2.21 · 10ꢀ3 mmol) in 20 mL of THF at
room temperature. The resulting mixture was stirred over-
night at room temperature and then centrifuged. The clear
solution was then concentrated under reduced pressure
and precipitated with ether. The resulting powder was dried
and washed twice with 40 mL of ether to afford the expected
dendrimer G4 as a yellow powder in 93% yield (139 mg).
Elem. Anal. Calc. for C3504H3024Fe96N183O186P189S186
(67852 g molꢀ1): C, 62.02; H, 4.49; N, 3.79. Found: C,
62.15, H, 4.55; N, 3.68%.
3.4. Catalytic studies: palladium-catalysed allylic
substitution
In a Schlenk tube, under argon, a mixture of dendrimer
(2.1 mol% of P,S chelate), 1,3-diphenylprop-2-enyl acetate
(0.126 g, 0.5 mmol) and [Pd(C3H5)Cl]2 (1.8 mg, 2 mol% of
palladium) was dissolved in dry dichloromethane (2 mL).
Dimethyl malonate (0.115 mL, 1 mmol), potassium acetate
and N,O-bis(trimethylsilyl)acetamide (BSA) (0.250 mL,
1 mmol) were added to the resulting solution. The reaction
was carried out at room temperature and monitored by
TLC for disappearance of acetate. After complete reaction,
the mixture was quenched with a saturated aqueous solu-
tion of ammonium chloride (20 mL). The aqueous phase
was extracted with dichloromethane, the combined organ-
ics were dried over magnesium sulfate, filtered and the sol-
vents evaporated. The conversion was calculated from the
Fe
PPh2
Fe
S
PPh2
S
S
Fe
PPh2
S
Fe
O
O
S
P
PPh2
N
Fe
PPh2
N
O
S
N
P
O
N
S
Fe
S
O
P
O
Ph2
P
O
N
N
P
S
O
N
N
S
Fe
O
N
S
S
N
O
N
O
P
N
O
Ph2
P
N
P
S
P
O
O
N
S
1
S
crude reaction mixture by H NMR spectroscopy. Subse-
Fe
O
N
N
S
quent purification by chromatography on silica eluting
Ph2
Fe
P
[P3N3
]
O
P
O
N
S
N
Table 2
Ph2P
O
P
S
N
Crystal data and structure refinement
N
O
O
N
O
N
N
P
P
S
Fe
O
S
O
S
Identification code
Empirical formula
Formula weight
Temperature (K)
Wavelength (A)
Crystal system
Space group
S-(3)
N
Ph2
P
P
N
P
C
29H25FeOPS2
[P3N3
]
=
N
O
N
N
N
S
P
O
Fe
P
P
S
540.43
293(2)
0.71073
Monoclinic
P21/n
O
S
Ph2P
O
O
S
N
˚
N
P
Fe
Ph2P
Fe
S
N
O
S
N
P
S
O
Ph2
Fe
P
O
S
Unit cell dimensions
˚
a (A)
15.8446(18)
8.7666(9)
18.108(3)
90
96.456(15)
90
Ph2P
S
˚
b (A)
S
Fe
˚
Ph2
P
c (A)
Ph2
P
Fe
a (ꢁ)
b (ꢁ)
c (ꢁ)
6
3
˚
Volume (A )
2499.3(5)
4
1.436
0.856
31P{1H} NMR (121.5 MHz, CDCl3) d = ꢀ20.8 (s, Cp-
PPh2); 11.8 (s, N3P3); 66.0 (br s, P1,2,3,4) ppm.
Z
Dcalc (Mg/m3)
Absorption coefficient (mmꢀ1
F(000)
Crystal size (mm)
h Range for data collection (ꢁ)
)
1H NMR (300 MHz, CDCl3) d = 3.24 (br s, 270H, P-N-
Me); 3.77 (br s, 96H, Cp-H); 3.98 (br s, 480H, Cp0-H); 4.05
(s, 192H, CH2); 4.22 (s, 96H, Cp-H); 4.33 (s, 96H, Cp-H);
7.01–7.82 (m, 1794H, Harom and CH@N) ppm.
1120
0.33 · 0.23 · 0.2
1.81–20.89
ꢀ15 6 h 6 15, ꢀ8 6 k 6 8,
ꢀ18 6 l 6 18
12698
2604 (0.1454)
98.5
Empirical (DIFABS)
0.6893 and 0.2258
Index ranges
13C{1H} NMR (75.5 MHz, CDCl3) d = 33.49 (d,
Reflections collected
Independent reflections (Rint
Completeness to h = 20.89ꢁ (%)
Absorption correction
Maximum and minimum
transmission
3
2JCP = 12.9 Hz, P-N-Me); 34.93 (d, JCP = 12.2 Hz, CH2);
)
2
69.99 (s, Cp); 70.26 (s, Cp0); 71.97 (d, JCP = 3.0 Hz, Cp);
72.05 (br s, Cp); 75.49 (d, JCP = 8.1 Hz, Cpipso); 90.08 (d,
JCP = 31.4 Hz, Cpipso); 121.03 (br s, C2); 122.21 (br d,
0
3
3JCP = 4.3 Hz, C02;1;2;3;4); 128.29 (d, JCP = 8.4 Hz, Cm);
Refinement method
Full-matrix least-squares on F2
2604/0/308
3
128.43 (s, Cp); 128.56 (d, JCP = 7.9 Hz, Cm); 129.59 (s,
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
C03;1;2;3); 131.86 (s, C43); 132.17 (br s, C40;1;2;3); 132.79 (d,
0.959
2JCP = 17.8 Hz, Co); 134.23 (s, C44); 135.47 (d,
R1 = 0.0767, wR2 = 0.1896
R1 = 0.1221, wR2 = 0.2193
0.408 and ꢀ0.473
1
2JCP = 21.3 Hz, Co); 137.86 (d, JCP = 8.2 Hz, Ci); 139.64
3
1
Largest difference in peak and hole
(br d, JCP = 13.6 Hz, CH@N); 139.71 (d, JCP = 8.0 Hz,
ꢀ3
˚
(e A
)
Ci); 149.52 (br s, C1); 151.72 (br s, C01;1;2;3) ppm.
4

1072
L. Routaboul et al. / Journal of Organometallic Chemistry 692 (2007) 1064–1073
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2009;
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(2002) 2009;
with dichloromethane/pentane (1:1) afforded the product
as colorless oil. The enantiomeric excess was determined
by H NMR spectroscopy using the chiral shift reagent
1
(+) Eu(hfc)3.
(e) A.-M. Caminade, V. Maraval, R. Laurent, J.-P. Majoral, Curr.
Org. Chem. 6 (2002) 739;
3.5. X-ray crystallographic study
(f) R. van Heerbeek, P.C.J. Kamer, P.W.N.M. van Leeuwen, J.N.
Reek, Chem. Rev. 102 (2002) 3717;
Single crystal was mounted under inert perfluoropolye-
ther at the tip of glass fibre and cooled in the cryostream
of the Stoe IPDS diffractometer. Data were collected using
the monochromatic Mo Ka radiation (k = 0.71073). The
final unit cell parameters were obtained by the least-
squares refinement of a large number of selected reflections.
Only statistical fluctuations were observed in the intensity
monitors over the course of the data collections.
(g) O. Bourrier, A.K. Kakkar, J. Mater. Chem. 13 (2003) 1306;
(h) A. Dahan, M. Portnoy, J. Polym. Sci. Part A 43 (2005) 235.
[3] (a) For reviews about the use of dendrimers in asymmetric catalysis,
see: H. Brunner, J. Organomet. Chem. 500 (1995) 39;
(b) B. Romagnoli, W. Hayes, J. Mater. Chem. 12 (2002) 767;
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The structure was solved by direct methods (SIR-97 [17])
and refined by least-squares procedures on F2 with the
SHELXL-97 program [18] using the integrated system
WINGX(1.63) [19]. H atoms were introduced at calculated
positions and treated as riding on their parent atoms
(b) C.-O. Turrin, J. Chiffre, D. de Montauzon, J.-C. Daran, A.-M.
Caminade, E. Manoury, G.G.A. Balavoine, J.-P. Majoral, Tetrahe-
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1891;
˚
˚
[d(CH) = 0.96 A, d(OH) = 0.82 A] with a displacement
parameter equal to 1.2Ueq (C6H5, CH2, OH) times that
of the parent atom. Owing to the poor diffracting ability
of the crystal, refinement was carried out using only the
reflections with a Bragg angle less than 21ꢁ. The Molecular
views were realised with the help of ORTEP-III [20]. Crys-
tal data and refinement parameters are shown in Table 2.
(d) C.-O. Turrin, J. Chiffre, D. de Montauzon, G. Balavoine, E.
Manoury, A.-M. Caminade, J.-P. Majoral, C. R. Chimie 5 (2002) 309.
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(b) A.M. Masdeu-Bulto, M. Dieguez, E. Martin, M. Gomez , Coord.
Chem. Rev. 242 (2003) 159.
[7] (a) Selected examples of successful use of chiral P,S ligands in
asymmetric catalysis: A. Albinati, P.S. Pregosin, K. Wick, Organo-
metallics 15 (1996) 2419;
4. Supplementary material
(b) J. Spencer, V. Gramlich, R. Hausel, A. Togni, Tetrahedron:
¨
Asymmetry 7 (1996) 41;
(c)K.Hiroi,Y.Suzuki,I.Abe,Tetrahedron:Asymmetry10(1999)1173;
(d) D. Enders, R. Peters, R. Lochtman, G. Raabe, J. Runsink, J.W.
Bats, Eur. J. Org. Chem. (2000) 3399;
Crystallographic data (excluding structure factors) for
the structure of compound 3 have been deposited with
the Cambridge Crystallographic Data Centre. CCDC
602136 contains the supplementary crystallographic data
for 3. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from
the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-
033; or e-mail: deposit@ccdc.cam.ac.uk.
`
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(g)T. Kanayama, K. Yoshida, H. Miyabe, T. Kimachi, Y. Takemoto, J.
Org. Chem. 68 (2003) 6197;
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(i) T. Tu, Y.-G. Zhou, X.-L. Hou, L.-X. Dai, X.-C. Dong, Y.-H. Yu, J.
Sun, Organometallics 22 (2003) 1255;
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Acknowledgments
We thank the Centre National de la Recherche Scientif-
ique (CNRS) for financial support and L.R. thanks the
`
Ministere de la Recherche et de la Technologie for a Doc-
toral Fellowship.
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