An efficient synthesis combining phosphorus dendrimers and 15-membered triolefinic azamacrocycles: Towards the stabilization of platinum nanoparticles

Article abstract of DOI:10.1039/b9nj00568d

The synthesis of a new series of phosphorus-containing dendrimers bearing as terminal groups triazatriolefinic macrocycles is reported, from generation 1 (6 macrocycles) to generation 4 (48 macrocycles). These macrocycles are linked to the dendrimers through diazaphospholane moieties (5-membered rings). The complexation ability of these dendrimers and of a compound possessing a single macrocycle was tested towards Pt₂(dba)₃. A discrete complex could be isolated only in the case of the model compound, whereas the dendrimers afford highly branched networks of Pt(0) nanoparticles interweaved with the dendrimers. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2010.

Full text of DOI:10.1039/b9nj00568d

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PAPER
www.rsc.org/njc | New Journal of Chemistry
An efficient synthesis combining phosphorus dendrimers and
15-membered triolefinic azamacrocycles: towards the
stabilization of platinum nanoparticlesw
ab
Gregory Franc, Elena Badetti,c Carine Duhayon,ab Yannick Coppel,ab
´
ab
c
Cedric-Olivier Turrin, Jean-Pierre Majoral,*ab Rosa-Marıa Sebastian* and
´
´
´
Anne-Marie Caminade*ab
Received (in Montpellier, France) 15th October 2009, Accepted 19th November 2009
First published as an Advance Article on the web 3rd February 2010
DOI: 10.1039/b9nj00568d
The synthesis of a new series of phosphorus-containing dendrimers bearing as terminal groups
triazatriolefinic macrocycles is reported, from generation 1 (6 macrocycles) to generation 4
(48 macrocycles). These macrocycles are linked to the dendrimers through diazaphospholane
moieties (5-membered rings). The complexation ability of these dendrimers and of a compound
possessing a single macrocycle was tested towards Pt2(dba)3. A discrete complex could be isolated
only in the case of the model compound, whereas the dendrimers afford highly branched
networks of Pt(0) nanoparticles interweaved with the dendrimers.
synthesis based on a multistep process with 3 different
Introduction
available routes.16 These macrocycles are known to complex
different metals such as Pd(0), Pt(0) or more moderately
Ag(I).17 In order to graft them onto dendrimers, they must
be selectively functionalized. The possibility to have one, two
or three different types of aryl substituents to confer specific
properties has been recently largely reviewed.18 The aim of
this article is to demonstrate the ability, through an
efficient method, to combine phosphorus dendrimers and
15-membered azamacrocycles on the outer shell, and to
demonstrate the interest of these dendrimers functionalized
with macrocycles in the field of organometallic chemistry.
Macromolecules with special three-dimensional architectures
such as macrocycles1 and dendrimers2 have attracted the
attention of researchers for several decades due to their
properties in numerous fields such as complexation, catalysis,
medicine, etc. Combination of both types of macromolecules
can increase the level of pre-organization and induce cooperative
effects affording specific properties different from those
produced by the separated parts.3 The association of dendrimers
and macrocycles started to develop approximately fifteen years
ago, by the use of azacrown ether macrocycles as constituents of
the branches of a dendrimer.4 However, in most cases,
macrocycles are used as core of dendrimers: porphyrins,5
phthalocyanines,6 cyclam,7 crown ethers,8 or phosphorus
macrocycles9 among other macrocycles were used for this
purpose. On the contrary and surprisingly, dendrimers bearing
macrocycles at the periphery are still relatively rare, despite the
fact that increasing the number of macrocyclic units could
enhance the properties of such assemblies. Examples with
porphyrins,10 phthalocyanines,11 and crown ethers12 as peripheral
substituents are known. More particular substituents such as
tetraazamacrocycles13 and TTF-semicrown ethers14 were also
grafted as end groups of phosphorus-containing dendrimers.15
In the present study, the macrocycles used are 15-membered
triazamacrocycles containing 3 olefins obtained through a
Results and discussion
Synthesis of the macrocycles and their grafting to phosphorus
dendrimers
The macrocycle that we used contains three nitrogen atoms
linked to aromatic rings, two of them are 2,4,6-triisopropylaryl
group chosen to increase the solubility, and the last one is a
fluoroaryl group, to be used later for the grafting to dendri-
mers through a linker. During the course of the known
synthesis (Scheme 1),16 we could isolate a single crystal of 1
(crystallization from hexane–AcOEt) and obtain an
X-ray structure, showing that both bromine atoms are in
anti-position as depicted on Fig. 1.
After cyclisation of compound 1 affording the azamacrocycle
2,19 the latter could be easily functionalized with diamine chains
via an aromatic nucleophilic substitution of the fluoride atom.
In presence of ethylene diamine or 1,3-diaminopropane as a
solvent (T = 95 1C) compounds 319 and 4 were obtained in
excellent yield (91 and 92% after work-up, respectively). 19F
NMR allowed us to determine if reaction had gone to comple-
tion by disappearance of the initial signal at d = ꢀ105 ppm.
We have already reported the condensation of compound 3
on aldehyde terminal groups of dendrimers;20 the reduction of
a CNRS, LCC (Laboratoire de Chimie de Coordination), 205,
route de Narbonne, F-31077 Toulouse, France.
E-mail: majoral@lcc-toulouse.fr, caminade@lcc-toulouse.fr;
Fax: +33 56155 3003
b Universite´ de Toulouse, UPS, INPT, LCC,
F-31077 Toulouse, France
Department of Chemistry, Universitat Autonoma de Barcelona,
Cerdanyola, 08193-Barcelona, Spain.
c
`
E-mail: rosamaria.sebastian@uab.es; Fax: +34 93581 1265
w CCDC reference number 751820. For crystallographic data in CIF
or other electronic format see DOI: 10.1039/b9nj00568d
ꢁc
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Scheme 2 Attempts to synthesise the model compounds.
final compound 6 at d = 68.57 ppm. This shift was in good
agreement with previous surface modification of phosphorus
dendrimers with two amine substituents;13,21 a monosubstitution
with a single amine on P(S)Cl2 would lead to a signal at
d ca. 73 ppm,22 which is never observed here. Both nucleo-
philic substitutions took place simultaneously; the stability of
the newly formed 5-membered adduct allowed isolation of
compound 6 in excellent yield (91%). The phosphorus atom
was a stereogenic center and diastereotopic protons could be
identified through a 2D experiment. In fact, two signals for
each proton of the methylene of the newly formed heterocycle
were clearly visible: signals of the protons attached to
the carbon Ca (see Fig. 7 for numbering) appeared as two
multiplets at d = 3.65 and 3.85 ppm, while signals for the ones
attached to Cb appeared equally as two multiplets at d = 3.94
and 3.99 ppm. Another proof of the appropriate achievement
of the reaction was the chemical shift of C1 at d = 145.74 ppm
(d, 2JCP = 7.3 Hz) compared to the initial value of 151.8 ppm.
Mass spectrometry (FAB, m/z: 1132 [M]+) also gave a positive
result.
Scheme 1 Synthesis of 15-membered azamacrocycles functionalized
with two different diamine chains (compounds 3 and 4).
Fig.
1 ORTEP view of 1 after crystallization in a mixture
AcOEt–hexane (H atoms are omitted for clarity).
the imine linkages was required to stabilize these compounds.
In the present paper, we report a more straightforward way to
graft these macrocycles to phosphorus dendrimers, by using
the diamine chain for a cyclization reaction with P(S)Cl2
terminal groups; formation of a 5-membered (diazaphospholane)
ring with macrocycle 3 or 6-membered (diazaphosphorinane)
ring with macrocycle 4 is expected to occur. However,
before starting the peripheral modification of phosphorus
dendrimers, we decided to synthesize a model compound
to determine the feasibility of our concept (Scheme 2). The
phosphorhydrazone 5 (easily obtained by condensation of
N-methyldichlorothiophosphorhydrazone on benzaldehyde)
was elected as it mimicks one arm of a dendrimer. By reacting
one equivalent of compounds 3 and 5 in presence of a base
(Cs2CO3), we could form the expected 5-membered ring
adduct. The reaction went fast and while the signal corres-
ponding to starting material at d = 62.5 ppm disappeared in
31P NMR, we could distinguish the formation of the desired
With the first attempt of our model compound to form a
5-membered ring being successful, we followed the same
methodology to try to obtain the 6-membered ring adduct
from compounds 4 and 5. By using the same conditions
(Cs2CO3 and THF), we unfortunately could not obtain the
desired compound: in fact, the presence of an additional
carbon between the two amines seemed to give more flexibility
to the system. For this reason, we suspected that a non-
aromatic amine coming from another macrocycle could react
before the cyclization took place and hampered the formation
of our desired target. To determine if this undesired effect
could be due to the hindrance of the macrocycle, we easily
synthesized compound 7 (yield 89%) following a previously
published procedure23 in order to perform the expected reac-
tion. The result of the reaction of 7 with 5 was unfortunately
analogous to the reaction of 4 with 5 with a major peak at d =
58 ppm in the 31P NMR. Attempted purification by silica
gel chromatography afforded multiple new peaks in the
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starting materials even if a major modification of the topology
is induced by the presence of the dendrimer. Reaction between
one equivalent of the first generation phosphorus dendrimers
8-G1 and 6 equivalents of macrocycle 3 in presence of a base
(Cs2CO3, 24 eq) led to the desired compound 9-G1 in good
yield after classical purification by precipitation with pentane
(81% yield). In fact, as shown by the presence of only one
signal (singlet at d = 68.44 ppm) for the phosphorus attached
to the macrocycle, no side reactions occurred. The presence of
a stereogenic center for each phosphorus at the periphery
induced the appearance of a multiplet for the phosphorus
located at the core (d = 7.70 ppm). Such a phenomenon was
previously observed at the (n ꢀ 1) generation for dendrimers
bearing uncontrolled chiral entities as end groups of the n
generation.26 The presence of signals at similar shifts for Ca
(m, d = 40.39 ppm) and Cb (s, d = 47.56 ppm) compared to 6
strongly supported the achievement of the reaction on all
reactive sites.
Scheme 3 Failure to obtain a diazaphosphorinane heterocycle even
in the absence of the macrocycle.
31P NMR, demonstrating the dead-end of this route to obtain
such a 6-membered ring heterocycle (Scheme 3). We may
presume that the difference in the reactivity of the alkylamine
compared to the aromatic amine was compensated for by the
close proximity between this aromatic amine and the P–Cl
bond after reaction of the alkylamine in the case of the
5-membered ring, but not in the case of the 6-membered ring.
In the latter case, the second H of the alkylamine may react
with another P–Cl function, to afford presumably a kind of
dimer possessing a diazadiphosphetidine 4-membered ring.24
Our model compound demonstrated the viability of a
5-membered ring adduct by reacting a P(S)Cl2 extremity and
a diamine, the amino groups being linked through a CH2–CH2
spacer; we could then move on to the first generation
Following the same procedure, we carried out the reaction
at the periphery of the second generation dendrimer (8-G2),
which possesses 12 P(S)Cl2 end-groups. The reaction
proceeded readily and could be monitored by 31P NMR:
signal of the P(S) groups of the second generation shifted to
d = 67.99 ppm (singlet) as expected, while signal of the first
generation appeared as a multiplet between d = 61.90–63.00,
confirming the assumption made for 9-G1; signal of the core
(d = 8.37 ppm) remained a singlet (see Fig. 2 for the 31P NMR
spectrum). After a similar purification process to the one used
with the first generation, final compound 9-G2 (see Fig. 3 for
an extended structure) was isolated with a yield of 83%.
In order to confirm the ability of our dendrimers to be
functionalized with this macrocycle even for a high generation,
we decided to test directly on the fourth generation 8-G4. We
proceeded as before: no side reaction took place and 9-G4 was
isolated with a yield of 74%. 31P NMR could allow us to
discern a singlet for the P(S) of the fourth generation (d =
67.92 ppm), a large singlet containing the signals of genera-
tions one to three (d = 62.27 ppm) and a singlet for the signal
dendrimer, built from
a
cyclotriphosphazene core25
(Scheme 4). We hoped to conserve the same reactivity
(no intra- or intermolecular side reactions) between the two
Fig. 2 31P-{1H} NMR spectrum of dendrimers 9-G2 bearing 12
macrocycles on the periphery. Effect of chirality is clearly visible on
the phosphorus of the first generation (B).
Scheme 4 Synthesis of 9-G1, 9-G2 and 9-G4 with 6, 12 and 48
macrocycles, respectively, at the periphery.
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Scheme 5 Preparation of the Pt(0)-metallated macrocycles 10 and 11.
chromatography was needed to afford the desired compound
10, with a yield of 67%. A splitting of the signals of the three
CH2–CHQCH–CH2 linkages of the macrocycle was observed,
1
both by H and 13C NMR, as previously described.29 This is
due to the fact that the 3 olefins are not involved in the same
manner in the complexation with Pt, and this is complicated
by the presence of two different aryl substituents on the
macrocycle.
Having this metallated macrocycle in hand, we thought that
an alternative route to the direct complexation of Pt by the
dendrimers 9-Gn could be the grafting of complexed macro-
cycles to dendrimers 8-Gn. For this purpose, we tried to
functionalize compound 10 for further grafting on P(S)Cl2
extremities. Addition of ethylene diamine had to be handled
with care to avoid decomplexation, Pt being really sensitive to
the presence of nitrogen atoms. Indeed, the direct complexa-
tion of macrocycle 3 failed to afford the expected macrocyclic
complex. Following previous methodology with free
macrocycle 2, ethylenediamine was reacted with the complex
10 at 95 1C but only for 3 h and the reaction was monitored
with 19F NMR. We obtained pure compound 11 in
excellent yield (97%). It must be emphasized that no
decomplexation occurred at this step. Indeed, uncomplexed
CHQCH as in compound 3 should give a singlet at
5.7–5.8 ppm in 1H NMR, which is not detected in the
spectrum of compound 11.
Fig. 3 Extended structure of 9-G2.
of the core (d = 8.03 ppm). A suitably integrated 31P NMR
spectrum corresponded to expected theoretical values indicating
the complete modification of the periphery. The pattern of 1H
NMR spectrum demonstrated that no degradation had
occurred. In addition, integrations of all signals suited well
with theoretical values. 13C NMR also displayed all the
expected signals, in particular those corresponding to Ca
(40.43 ppm) and Cb (47.69 ppm) (see Fig. 7 for numbering).
Complexation of platinum and obtaining of Pt nanoparticle
networks
Regarding our initial goal of using these compounds in
organometallic chemistry, we intended to complex a metal
inside the triolefinic macrocycle to obtain nanoassemblies
combining dendrimers, macrocycles and metals. We have
previously reported in the case of the macrocycles grafted to
the dendrimers by condensation/reduction and having twice
the number of macrocycles at the same generation compared
to 9-Gn, that these compounds were able to complex Pd(0),
Pd(dba)2 being the best precursor for such a purpose.20 On the
other hand, a previous report mentioned the possibility to
complex Pt(0) with Pt(PPh3)4 as a precursor, but reaction time
was long (4 days) and the yield quite moderate (52%).27 For
this reason, and by analogy with the reaction of Pd(dba)2 with
this azamacrocycle (reaction overnight with high yield), we
decided to move on to Pt2(dba)3 as a new precursor
(Scheme 5). The latter was synthesized according to a
previously reported procedure.28 First, complexation experi-
ments were carried out with the macrocycle 2. Indeed,
this simple compound would allow us to determine all the
characteristic data of the complexation, and help us later to
determine if the same reaction would occur with dendrimers.
After only one night in refluxing DMF complexation of
macrocycle 2 was fully accomplished. Disappearance of the
At this step, we decided to perform a complete characteri-
zation of the metallated macrocycle 11 by NMR, to be able to
later compare its behaviour before and after grafting at the
periphery of dendrimers. Firstly, two signals appeared in the
195Pt NMR at d = ꢀ6165 and ꢀ6163 ppm; a previous report
demonstrated that all three olefins were not involved in the
same manner in the complexation process, two of them
binding more strongly to the metal than the third.17b Thus,
due to the wide scale of platinum in NMR and the fact that 11
has two types of aryl substituents, it easily explains the
presence of two peaks, which should correspond to structures
110 and 110 0, approximately in a 1 : 2 ratio as expected for a
statistical reaction. Secondly, original HMQC experiments
195Pt-1H NMR (Fig. 4) allowed us as well to clearly distinguish
the signals coming from both adducts in 1H NMR; both
CHQCH and CH2 groups inside the macrocycle correlate
1
1
with Pt. With the help of COSY H–1H and HSQC H–13C
NMR experiments, we could detect very different
chemical shift for each of the CH2 groups inside
a
H
1
olefin signals at d = 5.7–5.8 ppm on the H NMR spectrum
was the key element to assert total complexation. However,
the macrocycle, for instance 1.45 and 4.62 ppm (see the
experimental section for the other couples of chemical shifts
1
for CH2 in H NMR).
a
black precipitate was also observed; thus, column
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Fig. 5 High resolution TEM image of the result of the reaction of
9-G1 with Pt2(dba)3, showing the Pt network.
Fig. 4 Two dimensional HMQC 195Pt–1H experiments display the
presence of two different forms for complex 11 (110 minor, 110 0 major).
Fig. 6 TEM image of the result of the reaction of 9-G4 with
Following the same procedure as before, we intended to
graft 11 at the periphery of 8-G1: in the same conditions
decomplexation unfortunately took place after 2 days, as we
could distinguish easily in 1H NMR the presence of the signals
corresponding to the free olefins (d = 5.7 ppm). A second
attempt with a more concentrated solution was carried out but
the same result was obtained. We have to point out that the
stability of the complex 11 in solution was not excellent, the
solution moving from slightly to strongly yellow after 2 days in
the NMR tube.
Pt2(dba)3.
not only composed of Pt but also of dendrimers.30 High
resolution TEM images display a continuous network of Pt
nanoparticles (Fig. 5); thus, we deduced that the dendrimers
wrap the ribbons of nanoparticles to ensure their cohesion,
and can also probably connect the ribbons to induce either an
almost linear continuation of the network, or the branching
points.
Fig. 6 displays one of the TEM images obtained for the
reaction of 9-G4 with Pt2(dba)3. An astonishing observation
could be made for these experiments: when the generation
(the size) of the dendrimer increases, the branches of the Pt
networks lengthen, while the monomer does not create any
network. The ability of dendrimers to create large dendritic-
like assemblies (more precisely dendron-like assemblies) with
nanoparticles is unprecedented, but in the very first paper by
Tomalia et al., PAMAM dendrimers reacted with sodium
hydroxide self-assembled in dendritic ‘‘snow-flakes’’,31
illustrating the potential of dendrimers for supramolecular
superstructures.
To circumvent the problem of the instability of compound
11, we tried to implement complexation directly at the
periphery of the dendrimers. For this purpose, we reacted
Pt2(dba)3 with dendrimers 9-G1, 9-G2 and 9-G4 overnight in
refluxing THF and under air, using a stoichiometry of 1.2 Pt
atoms per macrocycle. With this stoichiometry, we expected to
obtain discrete complexes, as in the case of the reaction with
macrocycle 2, and also when using palladium previously.
However, deep black solutions were obtained in all cases,
which afforded only very broad signals in NMR. In order to
understand what happened, a drop of the crude solutions of
the reaction of dendrimers 9-Gn with Pt2(dba)3, and also of the
black precipitate obtained in the synthesis of 10, was diluted in
THF then analyzed by transmission electron microscopy
(TEM). Totally unexpected results were obtained: despite the
low amount of Pt used and the very mild conditions applied,
oriented dendritic superstructures of Pt were observed in all
cases, as shown by low resolution TEM. We recently reported
detailed investigations about these ‘‘dendritic structures within
dendritic structures’’, in which the branches of the network are
Conclusion
The reaction of a P(S)Cl2 extremities of dendrimers with
15-membered azamacrocycle functionalized with a 1,2-diamine
led to the formation of one 5-membered ring (diazaphospholane)
on each phosphorus terminal group. Such reaction was carried
out with a monomeric model compound and with first, second
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and fourth generations of phosphorus dendrimers (1, 6, 12, 48
macrocycles as terminal groups, respectively). Such reaction
generates stereogenic centers on the external layer, which
induce the splitting of the signal of the previous generation
on 31P NMR spectra, demonstrating the sensitivity of 31P
NMR to subtle structural changes. The monomeric species of
these macrocycles is able to complex one Pt(0) atom obtained
from Pt2(dba)3. A 195Pt NMR study displays the presence of
two different forms due to the different complexation of Pt by
essentially two of the three olefinic bonds of the macrocycle.
This phenomenon has no consequence when the macrocycle
has 3 identical aryl groups, but in our case the presence of two
different aryl substituents in a 1 : 2 ratio induces two different
forms for the Pt complexes. This discrete complexation could
not been obtained when the macrocycles are connected to the
dendrimers whatever the generation. Instead, unprecedented
organic/inorganic hyperbranched superstructures, in which
the dendrimers wrap and organize ribbons of Pt nano-
particules, creating ‘‘dendritic structures (the dendrimers)
within dendritic structures (the inorganic network of Pt)’’ were
obtained.30
Syntheses
Compound 4. compound 2 (263 mg, 0.292 mmol) was
dissolved in 1,3-diaminopropane (3.15 mL, 37.73 mmol) in
presence of catalytic amount of Cs2CO3 at 95 1C overnight.
When reaction was over, water was added to the reaction
mixture, followed by a filtration on a Buchner. The solution
¨
was evaporated to dryness under reduced pressure, and final
compound 4 was obtained as a white powder with a yield of
92%. 1H NMR (CDCl3, 500.33 MHz): d = 1.24–1.29
= 6.5 Hz, 2H,
3
(m, 36H, CH(CH3)2), 1.82 (q, JHH
NH2–CH2–CH2), 2.92 (m, 4H, CH(CH3)2, NH–CH2), 3.28
3
(t, JHH = 6.5 Hz, 2H, NH2–CH2), 3.77 (m, 12H, CH2–CH),
4.10 (sept, 3JHH = 7.5 Hz, 4H, CH(CH3)2), 5.73–5.77 (m, 6H,
3
CH2–CHQ), 6.58 (d, JHH = 8.9 Hz, 2H, HC2), 7.17 (s, 4H,
HC13), 7.57 (d, JHH = 8.9 Hz, 2H, HC3); 13C-{1H} NMR
3
(CDCl3, 125.80 MHz): d = 23.59 (s, C16), 24.84 (s, C18), 29.25
(s, C17), 31.59 (s, NH2–CH2–CH2), 34.17 (s, C15), 40.33
(s, NH–CH2), 41.98 (s, NH2–CH2), 48.78, 48.79 (2 s, C8,
C9), 51.28 (s, C5), 111.64 (s, C2), 123.95 (s, C13), 125.06
(s, C4), 128.96, 129.87 (2 s, C7, C10), 129.23 (s, C3), 130.77
(s, C11), 131.02 (s, C6), 151.49 (s, C1), 151.85 (s, C12), 153.18
(s, C14) ppm. IR (neat): 3389 (N–H), 2958 (C–H), 2928 (C–H),
2868 (QC–H), 1600 (CQC), 1462 (SO2), 1150 (SO2) cmꢀ1. MS
(DCI): m/z = 952.4 [M]+. MP: 90–92 1C.
Experimental section
General
Compound 5. At 0 1C (ice bath) a solution of N-methyl-
dichlorothiophosphorhydrazide (c = 0.19 mol Lꢀ1 in CHCl3,
37 mL) was added slowly on benzaldehyde (0.478 mL, 4.71
mmol) under good stirring, then the reaction mixture was left
to react for 3 h at room temperature (r.t.). When the reaction
was over, a filtration on a pad of silica (DCM–pentane 1 : 9)
was accomplished to remove the excess of phosphorhydrazide.
Final compound 5 was obtained as a white powder with a yield
of 95%. 31P–{1H} NMR (CDCl3, 81.0 MHz): d = 62.5
Macrocycles 2 and 3,19 dendrimers 8-Gn and Pt2(dba)3
25
28
were synthesized using published procedures. All manipula-
tions were carried out with standard high-vacuum techniques
under a dry argon atmosphere. The solvents were freshly dried
and distilled (THF over sodium/benzophenone, pentane and
CH2Cl2 over phosphorus pentoxide). Melting points were
uncorrected and obtained with an Electrothermal melting
point apparatus. Mass spectrometry was carried out with
Finniganmat TSQ 7000. 1H, 13C, 31P, 19F and 195Pt NMR
spectra were recorded on Bruker ARX250, DPX300, AV300
and AV500 spectrometers.
1
3
(s, PQS); H NMR (CDCl3, 200.13 MHz): 3.50 (d, JHH
=
13.5 Hz, 3H, N–Me), 7.39–7.77 (m, 6H, CHQN, Har);
=
2
13C–{1H} NMR (CDCl3, 50.32 MHz): d = 31.77 (d, JCP
13.7 Hz, N–Me), 127.41 (s, C0 ). 128.84 (s, C0 ), 130.20
References for NMR chemical shifts are 85% H3PO4 for 31
P
2
3
NMR, SiMe4 for 1H and 13C NMR, Na2PtCl6 in D2O for 195Pt
NMR and trifluoroacetic acid for 19F NMR. The attribution
1
4
3
(s, C0 ), 134.06 (s, C0 ), 141.82 (d, JCP = 18.6 Hz, CHQN)
ppm. IR (neat): 2963 (QC–H), 1571 (CQN) cmꢀ1. MP: 61–62 1C.
1
of H and 13C NMR signals has been done using Jmod, two-
dimensional COSY, HMBC and HMQC, broad band or CW
31P decoupling experiments when necessary. The numbering
used for NMR is shown on Fig. 7.
Compound 6. Compound
5 (13.6 mg, 0.05 mmol)
was dissolved in THF, then caesium carbonate (68.4 mg,
0.209 mmol) and compound 3 (47.8 mg, 0.05 mmol) were
added to the reaction mixture and left to react at r.t. overnight.
After centrifugation for removal of the salts, residual solvents
were removed under low pressure. Final compound 6 was
obtained as a white powder with a yield of 91%. 31P–{1H}
1
NMR (CDCl3, 202.53 MHz): d = 68.57 (s, PQS); H NMR
3
(CDCl3, 500.33 MHz): d = 1.25 (d, JHH = 7.2 Hz, 12H,
CH(CH3)2), 1.27 (d, JHH = 7.1 Hz, 24H, CH(CH3)2), 2.84
3
2
(m, 2H, CH15H(CH3)2), 3.07 (d, JHP = 14.5 Hz, 1H, NH),
3
3.51 (d, JHP = 10.1 Hz, 3H, N–Me), 3.65–3.85 (m, 14H,
CH2–CH, Ca–H), 3.94, 3.99 (2 m, 2H, Cb–H), 4.11
(m, 4H, CH17H(CH3)2), 5.67–5.80 (m, 6H, CHQCH), 7.17
(s, 4H, HC13), 7.23–7.70 (m, 10H, CHQN, HAr); 13C–{1H}
NMR (CDCl3, 125.80 MHz): d = 23.57 (s, C16), 24.83 (s, C18),
29.24 (s, C17), 32.44 (d, 2JCP = 13.8 Hz, N–Me), 34.15 (s, C15),
2
Fig. 7 Numbering scheme used for NMR assignments.
40.44 (s, Ca), 47.79 (d, JCP = 12.6 Hz, Cb); 48.72, 48.79
ꢁc
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3
(2 s, C8, C9), 51.32 (s, C5), 116.00 (d, JCP = 6.3 Hz, C2),
reduced pressure. The residue was then dissolved in the
minimum amount of THF (ca. 1 mL) and precipitated
with pentane. The resulting powder was filtered off and the
procedure was repeated once to afford 9-G2 as a brownish
powder with a yield of 83%. 31P–{1H} NMR (CDCl3,
121.49 MHz): d = 8.37 (s, PQN), 61.90–63.00 (m, P1QS), 67.99
(s, P2QS); 1H NMR (CDCl3, 300.13 MHz): d = 1.18–1.30
(m, 432H, CH(CH3)2), 2.90 (m, 24H, CH15H(CH3)2), 3.22
(m, 12H, NH), 3.30 (m, 18H, N(Me)–P1), 3.45 (m, 36H,
N(Me)-P2), 3.55–3.95 (m, 192H, CH2–CH, Ca–H, Cb–H),
4.06 (m, 48H, C17H(CH3)2), 5.55–5.75 (m, 72H, CHQCH),
6.90–7.70 (m, 192H, CHQN, HAr) ppm. 13C–{1H} NMR
(CDCl3, 75.46 MHz): d = 23.57 (s, C16), 24.84 (s, C18),
2
123.94 (s, C13), 126.60 (s, C4, C0 ), 128.39 (s, C0 ), 129.16,
3
1
129.24 (2 s, C7, C10), 129.86 (s, C6), 130.46 (s, C0 ), 130.69,
4
3
130.86 (2 s, C3, C11), 135.06 (s, C0 ), 138.87 (d, JCP
=
2
13.4 Hz, CHQN), 145.74 (d, JCP = 7.3 Hz, C1), 151.50
(s, C12), 153.16 (s, C14) ppm. MS (FAB) m/z: 1132 [M]+.
Compound 7. 4-Fluorodiethylsulfonamide (500 mg, 2.16 mmol)
was dissolved in 1,3-diaminopropane (3.6 mL, 42.73 mmol)
at 100 1C overnight. When reaction was over, water (20 mL)
was added to the reaction mixture, followed by two extrac-
tions with DCM (2 ꢂ 80 mL). Organic phase was then dried
over MgSO4 and after removal of the residual solvents final
compound 7 was obtained as a white powder with a yield
2
29.23 (s, C17), 32.49 (d, JCP = 13.2 Hz, N(Me)-P2), 32.53
2
(d, JCP = 11.2 Hz, N(Me)-P1), 34.14 (s, C15), 40.39 (s, Ca),
of 89%. 1H NMR (CDCl3, 300.13 MHz): d = 1.10 (t, 3JHH
=
7.0 Hz, 6H, CH3), 1.31 (s, 2H, NH2), 1.76 (q, 3JHH = 6.5 Hz,
2H, NH2–CH2–CH2), 2.86 (t, 3JHH = 6.5 Hz, 2H, NH–CH2),
47.56 (m, Cb), 48.69, 48.83 (2 s, C8, C9), 51.35 (s, C5), 115.97
2
(br s, C2), 121.30 (br s, C0 ), 121.69 (br s, C1 ), 123.95 (s, C13),
2
3
3.18 (pseudo q, JHH = 7 Hz, 6H, NH2–CH2, CH2), 5.28
3
127.80 (s, C4, C0 ), 128.35 (s, C1 ), 129.30, 129.82 (2 s, C7, C10),
3
3
(s, 1H, NH), 6.55 (d, JHH = 8.8 Hz, 2H, HC2), 7.55
4
130.63 (s, C6), 130.82, 131.60 (2 s, C3, C11), 132.28 (s, C0 )
3
(d, JHH = 8.8 Hz, 2H, HC3); 13C–{1H} NMR (CDCl3,
4
132.68 (s, C1 ), 137.46 (m, CHQN–N–P2) 139.00
2
75.45 MHz): d = 14.12 (s, CH3), 31.96 (s, NH2–CH2–CH2),
40.36 (s, NH2–CH2), 41.87 (s, CH2CH3), 41.95 (s, NH–CH2),
111.46 (s, C2), 126.42 (s, C4), 128.99 (s, C3), 151.52 (s, C1) ppm.
MS (DCI): m/z = 286.2 [M + H]+. Anal Calcd (%): C 54.71,
H 8.12, N, 14.72. Found: C 54.38, H 7.98, N 14.52.
(br d, CHQN–N–P1), 145.54 (d, JCP = 7.0 Hz, C1), 150.88
(br s, C1 ), 151.14 (s, C0 ), 151.46 (s, C12), 153.19 (s, C14) ppm.
1
1
IR (neat): 3369 (N–H), 2956 (C–H), 2867 (Q C–H), 1596
(CQC), 1461 (SO2), 1148 (SO2) cmꢀ1
.
Compound 9-G4. Dendrimer 8-G4 (36 mg, 1.60 10ꢀ3 mmol)
was dissolved in THF, then caesium carbonate (104.17 mg,
0.319 mol) and compound 3 (75 mg, 0.08 mmol) were added to
the reaction mixture and left overnight under good stirring.
After reaction completion, salts were removed by centrifuga-
tion and the clear solution was evaporated under reduced
pressure. The residue was then dissolved in the minimum
amount of THF (ca. 1 mL) and precipitated with pentane.
The resulting powder was filtered off and the procedure was
repeated once to afford 9-G4 as a brownish powder in 74%
yield. 31P–{1H} NMR (CDCl3, 202.53 MHz): d = 8.03 (br s,
PQN), 62.27 (br s, P1QS, P2QS, P3QS), 67.92 (s, P4QS); 1H
Compound 9-G1. Dendrimer 8-G1 (22.5 mg, 0.0123 mmol)
was dissolved in THF, then caesium carbonate (104.13 mg,
0.319 mmol) and compound 3 (75 mg, 0.08 mmol) were added
to the reaction mixture and left overnight under good stirring.
After reaction completion, salts were removed by centrifuga-
tion and the clear solution was evaporated under reduced
pressure. The residue was then dissolved in the minimum
amount of THF (ca. 0.5 mL) and precipitated with pentane.
The resulting powder was filtered off and the procedure was
repeated once to afford 9-G1 as a brownish powder in 81%
yield. 31P–{1H} NMR (CDCl3, 121.49 MHz): d = 7.70
1
(m, PQN), 68.44 (s, P1QS); H NMR (CDCl3, 300.13 MHz):
NMR (CDCl3, 500.33 MHz):
d = 1.28 (m, 1728H,
d
= 1.22–1.28 (m, 216H, CH(CH3)2), 2.84 (m, 12H,
CH(CH3)2), 2.89 (m, 96H, CH15H(CH3)2), 3.15 (br s, 48H,
NH), 3.27 (br s, 126H, N(Me)-P1,2,3), 3.38 (br s, 144H,
N(Me)-P4), 3.60–3.95 (m, 768H, CH2–CH, Ca–H2, Cb–H2),
4.09 (m, 192H, CH17H(CH3)2), 5.55–5.75 (m, 288H,
CH15H(CH3)2), 3.25 (br s, 6H, NH), 3.45 (br m, 18H,
N–Me), 3.55–3.98 (m, 96H, CH2–CH, Ca–H, Cb–H), 4.09
(m, 24H, CH17H(CH3)2), 5.60–5.78 (m, 36H, CHQCH),
6.90–7.78 (m, 78H, CHQN, HAr); 13C–{1H} NMR (CDCl3,
75.46 MHz): d = 23.57 (s, C16), 24.83 (s, C18), 29.23 (s, C17),
32.53 (d, 2JCP = 12.7 Hz, N–Me), 34.14 (s, C15), 40.33 (s, Ca),
47.73 (m, Cb), 48.72, 48.84 (2 s, C8, C9), 51.30 (s, C5), 115.96
CHQCH), 7.10–7.80 (m, 834H, CHQN, HAr
) ppm.
13C–{1H} NMR (CDCl3, 125.80 MHz): d = 23.58 (s, C16),
24.85 (s, C18), 29.23 (s, C17), 32.49 (d, JCP = 12.9 Hz,
2
2
N(Me)-P4), 33.01 (br s, N(Me)–P1,2,3), 34.12 (s, C15), 40.43
(s, Ca), 47.69 (br s, Cb), 48.67, 48.82 (2 s, C8, C9), 51.34 (s, C5),
115.99 (br s, C2), 121.76 (br s, C0,1,2,32), 123.94 (s, C13), 127.81
(s, C4), 128.37 (s, C0,1,2,33), 129.25, 129.80 (2 s, C7, C10), 130.69
(br s, C2), 121.01 (br s, C0 ), 123.94 (s, C13), 127.69 (s, C4),
3
128.37 (s, C0 ), 129.36, 129.85 (2 s, C7, C10), 130.34 (s, C6),
3
130.57, 130.83 (2 s, C3, C11), 132.30 (s, C0 ), 137.62 (d, 3JCP
=
2
13.6 Hz, CHQN), 145.74 (d, JCP = 6.0 Hz, C1), 150.88
(br s, C0 ), 151.47 (s, C12), 153.18 (s, C14) ppm. IR (neat): 3356
4
(s, C6), 130.85 (s, C3, C11), 132.41 (s, C0,1,24) 132.64 (s, C3 ),
1
137.66 (m, CHQN–N–P4) 139.15 (br m, CHQN–N–P1,2,3),
145.65 (br s, C1), 150.88 (br s, C0,1,2,31), 151.44 (s, C12), 153.18
(s, C14) ppm. IR (neat): 3369 (N–H), 2956 (C–H), 2867
(N–H), 2955 (C–H), 2867 (QC–H), 1596 (CQC), 1461 (SO2),
1149 (SO2) cmꢀ1
.
Compound 9-G2. Dendrimer 8-G2 (31 mg, 6.62
ꢂ
(QC–H), 1596 (CQC), 1461 (SO2), 1148 (SO2) cmꢀ1
.
10ꢀ3 mmol) was dissolved in THF, then caesium carbonate
(104.17 mg, 0.319 mol) and compound 3 (75 mg, 0.08 mmol)
were added to the reaction mixture and left overnight under
good stirring. After reaction completion, salts were removed
by centrifugation and the clear solution was evaporated under
Compound 10. Compound 2 (100 mg, 0.111 mmol) was
dissolved in DMF, then Pt2(dba3)28 (106 mg, 0.133 mmol)
was added to the reaction mixture and left to react at 130 1C
overnight. When reaction was over (TLC monitoring), after
ꢁc
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New J. Chem., 2010, 34, 547–555 | 553

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removal of the solvents, the residue was subjected to flash
chromatography (pentane–AcOEt: 1 : 0 - 9 : 1) to afford the
PhD grant to G.F. (Fond Social Europe
´
en), from the
‘‘Ramon y Cajal’’ foundation (MCyT-FEDER/FSE) for a
grant to R.M.S., from the Ministry of Education and Science
of Spain for pre-doctoral scholarships to E.B, from the
PICASSO exchange program, from the LEA-368 (LTPMM)
and from the CNRS.
1
desired compound 10 as a brownish powder in 67% yield. H
NMR (CDCl3, 250 MHz): d = 1.27 (m, 36H, CH(CH3)2),
1.39–1.90 (m, 4H, CH2), 2.12–2.60 (m, 2H, CH), 2.9 (sept,
3JHH = 7.0 Hz, 2H, CH(CH3)2), 3.00–3.25 (q, 3JHH = 7.1 Hz,
4H, CH2), 3.30–3.70 (m, 4H, CH), 4.21 (sept, 3JHH = 7.0 Hz,
2H, CH(CH3)2), 4.35–5.20 (m, 6H, CH2), 7.16 (m, 2H, Har),
7.20 (s, 4H, Har), 7.75–7.95 (m, 2H, Har) ppm. 13C–{1H} NMR
(CDCl3, 62.5 MHz): d = 24.0 (s, C16), 25.2 (s, C18), 25.3
(s, C18), 29.6 (s, C17), 29.7 (s, C17), 34.6 (s, C15), 43.4, 45.0,
45.8, 45.9, 47.2, 47.3, 47.9, 49.3 (s, CH2–CH), 62.8, 63.1, 63.3,
63.6, 63.7, 64.2, 69.0, 70.2, 70.5 (s, CHQCH), 116.9
Notes and references
1 For reviews and concept articles concerning macrocycles, see e.g.:
(a) C. J. Pedersen, J. Am. Chem. Soc., 1967, 89, 7017; (b) Top. Curr.
Chem., ed. E. Weber and F. Vogtle, 1992, vol. 161;
¨
(c) A.-M. Caminade and J.-P. Majoral, Chem. Rev., 1994, 94, 1183.
2 (a) Dendrimers and other dendritic polymers, ed. J. M. J. Frechet
´
and D. A. Tomalia, John Wiley and Sons, Chichester, 2001;
(b) Dendrimers and dendrons. Concepts, syntheses, applications,
ed. G. R. Newkome, C. N. Moorefield and F. Vogtle, Wiley
¨
VCH, Weinheim, 2001; (c) J.-P. Majoral and A.-M. Caminade,
Chem. Rev., 1999, 99, 845.
3 (a) D. Soto-Castro and P. Guadarrama, J. Comput. Chem., 2004,
25, 1215; (b) A.-M. Caminade, Y. Wei and J.-P. Majoral,
C. R. Chimie, 2009, 12, 105; (c) A.-M. Caminade and
J.-P. Majoral, Top. Heterocycl. Chem., 2009, 20, 275.
2
2
(d, JCF = 21.7 Hz, C2), 117.0 (d, JCF = 21.7 Hz, C2),
124.4 (s, C13), 129.5–130.5 (m, C3, C11), 131.5–131.9 (m, C11),
4
4
134.6 (d, JCF = 4.0 Hz, C4), 135.5 (d, JCF = 4.0 Hz, C4),
151.70 (m, C12), 153.72 (s, C14), 165.46 (d, 1JCF = 251.87 Hz,
C1) ppm. IR (neat): 2956 (C–H), 2867 (QC–H), 1593 (CQC),
1148 (SO2) cmꢀ1. MP: 135–137 1C. Anal Calcd (%): C 52.73,
H 6.27, N 3.84. Found: C 52.51, H 6.44, N 3.94.
4 T. Nagasaki, M. Ukon, S. Arimori and S. Shinkai, J. Chem. Soc.,
Chem. Commun., 1992, 608.
Compound 11. Compound 10 (52 mg, 0.047 mmol) was
dissolved in ethylenediamine (100 mL, 1.49 mmol) at 95 1C
for 3 h. When reaction was over, 10 mL of water were added to
the reaction mixture, followed by two extractions with DCM
(80 mL). Organic phase was then dried over Na2SO4 and after
removal of the residual solvents, final compound 11 was
obtained as a brownish powder with a yield of 97%. 1H
NMR (CDCl3, 500.33 MHz): d = 1.26 (m, 36H, CH(CH3)2),
1.45 and 4.62 (2 m, C5,8,9H2-110 0), 1.85 and 4.38–4.53
5 See e.g.: (a) R.-H. Jin, T. Aida and S. Inoue, J. Chem. Soc., Chem.
Commun., 1993, 1260; (b) R. Sadamoto, N. Tomioka and T. Aida,
J. Am. Chem. Soc., 1996, 118, 3978; (c) D.-L. Jiang and T. Aida,
J. Am. Chem. Soc., 1998, 120, 10895; (d) K. W. Pollak, J. W. Leon,
J. M. J. Frechet, M. Maskus and H. D. Abruna, Chem. Mater.,
´
1998, 10, 30; (e) K. Yamamoto, M. Higuchi, S. Shiki, M. Tsuruta
and H. Chiba, Nature, 2002, 415, 509; (f) O. Finikova, A. Galkis,
V. Rozkov, H. Cordero, C. Hagerhall and S. Vinogradov, J. Am.
Chem. Soc., 2003, 125, 4882; (g) W. R. Dichtel, S. Hecht and
J. M. J. Frechet, Org. Lett., 2005, 7, 4451.
´
6 See e.g.: (a) M. Kimura, K. Nadaka, Y. Yamaguchi, K. Hanabusa,
H. Shirai and N. Kobayashi, Chem. Commun., 1997, 1215;
(b) M. Brewis, G. J. Clarkson, V. Goddard, M. Helliwell,
A. M. Holder and N. B. McKeown, Angew. Chem., Int. Ed.,
1998, 37, 1092; (c) C. A. Kernag and D. V. McGrath, Chem.
Commun., 2003, 1048; (d) J. Leclaire, Y. Coppel, A.-M. Caminade
and J.-P. Majoral, J. Am. Chem. Soc., 2004, 126, 2304;
(e) J. Leclaire, R. Dagiral, S. Fery-Forgues, Y. Coppel,
B. Donnadieu, A.-M. Caminade and J.-P. Majoral, J. Am. Chem.
Soc., 2005, 127, 15762; (f) J. Leclaire, R. Dagiral, A. Pla-Quintana,
A.-M. Caminade and J.-P. Majoral, Eur. J. Org. Chem., 2007,
2890.
3
(2 m, C5,8,9H2), 2.18 (br t, JHH = 12 Hz, C6,7,10H-110), 2.45
3
(br t, JHH = 12 Hz, C6,7,10H-110 0), 2.93 (m, 2H, C15H), 3.00
(m, 2H, CaH2), 3.06 and 5.03 (2 m, C5,8,9H2-110), 3.14 and 4.85
(2 m, C5,8,9H2-110 0), 3.25 (m, 2H, CbH2), 3.36 (m, C6,7,10H),
3.57 (m, C6,7,10H), 4.21 (m, 4H, C17H), 4.91 (br s, NH, NH2),
3
3
6.60 (d, JHH = 8.7 Hz, C2H-110 0), 6.61 (d, JHH = 8.7 Hz,
3
C2H-110), 7.20 (s, 4H, C13H), 7.53 (d, JHH = 8.7 Hz,
C3H-110 0), 7.61 (d, JHH = 8.7 Hz, C2H-110) ppm. 13C-{1H}
3
NMR (CDCl3, 125.8 MHz): d = 23.52 (s, C16), 24.79, 24.86
(2 s, C18), 29.21, 29.26 (2 s, C17), 34.15 (s, C15), 40.39 (s, Ca),
43.04 (s, C5,8,9-1100), 44.46 (s, C5,8,9-110), 44.66 (s, Cb), 45.60,
46.87, 47.03 (3 s, C5,8,9), 47.45, 48.88 (2 s, C5,8,9-110), 62.69,
63.08, 63.13, 63.23, 63.47 (5 s, C6,7,10), 69.45 (s, C6,7,10-110 0),
69.67 (s, C6,7,10-110), 111.91 (s, C2-110 0), 112.01 (s, C2-110),
123.94 (s, C13), 129.07 (s, C3-110), 129.29 (s, C3-110 0), 131.19,
131.38, 131.44 (3 s, C4,11), 151.30, 151.38 (2 s, C12), 151.71
(s, C1), 153.24 (s, C14) ppm. 195Pt-{1H} NMR (CDCl3, 107.55
MHz): d = ꢀ6163.08 (s, 1100), ꢀ6165.77 (s, 110) ppm. IR
(neat): 3375 (N–H), 2956 (C–H), 2867 (QC–H), 1597 (CQC),
1147 (SO2) cmꢀ1. MP: 123–126 1C.
¨
7 See e.g.: (a) K. Kadei, R. Moors and F. Vogtle, Chem. Ber., 1994,
127, 897; (b) C. Saudan, V. Balzani, M. Gorka, S.-K. Lee,
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¨
125, 4424; (c) C. Saudan, V. Balzani, M. Gorka, S.-K. Lee, J. van
Heyst, M. Maestri, P. Ceroni, V. Vicinelli and F. Vogtle,
¨
Chem.–Eur. J., 2004, 10, 899; (d) B. Branchi, P. Ceroni,
G. Bergamini, V. Balzani, M. Maestri, J. van Heyst, S.-K. Lee,
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¨
(e) C. Larpent, C. Genies, A. P. De Sousa Delgado,
A. M. Caminade, J. P. Majoral, J. F. Sassi and F. Leising, Chem.
Commun., 2004, 1816.
8 See e.g.: (a) Y. Pan, M. Lu, Z. Peng and J. S. Melinger, Org.
Biomol. Chem., 2003, 1, 4465; (b) D. Alivertis, V. Theodorou,
G. Paraskevopoulos and K. Skobridis, Tetrahedron Lett., 2007, 48,
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9 (a) J. Mitjaville, A.-M. Caminade, J.-C. Daran, B. Donnadieu and
J.-P. Majoral, J. Am. Chem. Soc., 1995, 117, 1712; (b) C.-O. Turrin,
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J.-P. Majoral, Eur. J. Inorg. Chem., 2006, 2556.
10 See e.g.: (a) J. C. Roberts, Y. E. Adams, D. A. Tomalia,
J. A. Mercer-Smith and D. K. Lavallee, Bioconjugate Chem.,
1990, 1, 305; (b) E. K. L. Yeow, K. P. Ghiggino, J. N. H. Reck,
M. J. Crossleyn, A. W. Bosman, A. P. H. J. Schenning and
E. W. Meijer, J. Phys. Chem. B, 2000, 104, 2596;
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Acknowledgements
We acknowledge financial support from the Ministerio de
´
Ciencia e Innovacion of Spain (Projects CTQ2008-05409-
C02-01, CTQ2005-04968-C02-01, HF2004-0212, Consolider
INGENIO 2010: CSD2007-00006), Generalitat de Catalunya
(Projects SGR 2009-1441 and 2005SGR00305). We also
acknowledge support from the European Community for a
ꢁc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2010
554 | New J. Chem., 2010, 34, 547–555

View Article Online
11 G. A. Kraus and S. V. Louw, J. Org. Chem., 1998, 63, 7520.
12 (a) N. Launay, M. Slany, A.-M. Caminade and J.-P. Majoral,
J. Org. Chem., 1996, 61, 3799; (b) C. Larre, D. Bresolles, C. Turrin,
´
19 B. Blanco, A. Mehdi, M. Moreno-Manas, R. Pleixats and C. Reye
Tetrahedron Lett., 2004, 45, 8789.
20 E. Badetti, A.-M. Caminade, J.-P. Majoral, M. Moreno-Manas
and R.-M. Sebastian, Langmuir, 2008, 24, 2090.
´
,
B. Donnadieu, A.-M. Caminade and J.-P. Majoral, J. Am. Chem.
Soc., 1998, 120, 13070.
´
21 (a) M. Slany, A.-M. Caminade and J.-P. Majoral, Tetrahedron
Lett., 1996, 37, 9053; (b) C. Loup, M.-A. Zanta, A.-M. Caminade,
J.-P. Majoral and B. Meunier, Chem.–Eur. J., 1999, 5, 3644.
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Chem.–Eur. J., 1996, 2, 1417.
13 D. Pre
and J.-P. Majoral, Eur. J. Org. Chem., 1999, 1701.
14 F. Le Derf, E. Levillain, G. Trippe, A. Gorgues, M. Salle
R.-M. Sebastian, A.-M. Caminade and J.-P. Majoral, Angew.
vote, B. Donnadieu, M. Moreno-Manas, A.-M. Caminade
´ ´
´
´
,
´
Chem., Int. Ed., 2001, 40, 224.
23 E. Badetti, M. Moreno-Manas, R. Pleixats, R.-M. Sebastia
A. Serra-Muns, R. Soler and A. Vallribera, Synlett., 2005, 449.
´
n,
15 (a) N. Launay, A.-M. Caminade, R. Lahana and J.-P. Majoral,
Angew. Chem., Int. Ed. Engl., 1994, 33, 1589; (b) N. Launay,
A.-M. Caminade and J.-P. Majoral, J. Am. Chem. Soc., 1995,
117, 3282; (c) M.-L. Lartigue, B. Donnadieu, C. Galliot,
A.-M. Caminade, J.-P. Majoral and J.-P. Fayet, Macromolecules,
1997, 30, 7335.
24 F. Gonce, A.-M. Caminade, F. Boutonnet and J.-P. Majoral,
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25 N. Launay, A.-M. Caminade and J.-P. Majoral, J. Organomet.
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