1,2,3,4-Heterohexatrienes as new tools for Michael-type additions usable for the synthesis of phosphorus dendrimers

Article abstract of DOI:10.1055/s-2003-37356

Linear 1,2,3,4-heterohexatrienes of type H₂C=CHP(R)₂=NP(R′)₂ (X = O, S) are used in Michael-type additions of various primary or secondary amines and hydrazines. The use of functionalized amines allowed the grafting of oth

Full text of DOI:10.1055/s-2003-37356

PAPER
389
1,2,3,4-Heterohexatrienes as New Tools for Michael-Type Additions Usable
for the Synthesis of Phosphorus Dendrimers
1
, 2,3, 4-Heterohexa
a
triene
s
for
l
Michae
é
l-Type Ad
r
ditions in
i
the Sy
e
nthesis of Phosph
M
orus Dendrimers araval, Régis Laurent, Bruno Donnadieu, Anne-Marie Caminade,* Jean-Pierre Majoral*
Laboratoire de Chimie de Coordination, CNRS, 205 route de Narbonne, 31077 Toulouse cedex 4, France
Fax +33(5)61553003; E-mail: caminade@lcc-toulouse.fr; E-mail: majoral@lcc-toulouse.fr
Received 15 November 2002
patibility with the presence of other functional groups. In-
deed, the synthesis of dendrimers being time-consuming,
it is highly desirable to use model compounds easy to syn-
thesize and to characterize, in order to test their reactivity
Abstract: Linear
1,2,3,4-heterohexatrienes
of
type
H2C=CHP(R)2=NP(R′)2=X (X = O, S) are used in Michael-type ad-
ditions of various primary or secondary amines and hydrazines. The
use of functionalized amines allowed the grafting of other func-
tions, such as a double or a triple bond, a sulfide, an imidazole, or a before applying the best results to dendrimers.
phenol, and various types of NH2 groups. These groups were used
The smallest 1,2,3,4-heterohexatriene we studied,
in condensation reactions, leading to the grafting of new functions
H2C=CHP(Ph)2=NP(OPh)2=O (1), is easily obtained by a
such as phenols. Thus, the P(R)2=NP(R′)2=X group appears as a
quantitative Staudinger reaction between two commer-
cially available reagents, diphenylvinylphosphine and
diphenylphosphoryl azide.3 The presence of both an al-
kene and a phosphazene linkage in this compound could
allow interesting comparisons with the structure of
oligoenes8 and oligophosphazenes.9 We obtained crystals
of 1 suitable for an X-ray analysis.10 The structure of com-
pound 1 (Figure 1, Table 1) offers some similarities with
that of oligoenes and oligophosphazenes concerning the
bond lengths. Well separated single and double bonds are
observed for the vinyl group, whereas the lengths of the
theoretically single and double PN bonds are equivalent
(1.58 Å). Compound 1 crystallizes in a cEg conformation
(s-cis for the P–C bond, E for the P=N bond, and gauche
for the P–N bond). The O=PN=P moiety is markedly non
planar (dihedral angle 55.13°), whereas the N=PC=C moi-
ety is almost flat (dihedral angle 4.71°). This behaviour is
different from that reported for oligophosphazenes,9 but
rather similar observations were noted for the structure of
compound 2 [H2C=CHPPh2=NP=S(OC6H4m-NMe2)2]3
even if it crystallized in a different space group (1: triclin-
ic P–1, z = 2; 2: monoclinic P21/n, z = 4). The most im-
portant result deduced from this structure is that the access
to the vinyl group is easy from a steric point of view. This
fact, in addition to the withdrawing influence of the
P=NP=X group, should allow easy Michael-type addi-
tions.
new electron withdrawing group, very easily tunable by changing
the R′ or X substituents.
Key words: Michael additions, alkenes, aminations, dendrimers,
phosphorus
Nucleophilic additions of amines to carbon-carbon double
bonds linked to strong electron withdrawing group(s)
(Michael-type additions) have been extensively investi-
gated.1 The most commonly used electron withdrawing
groups are classical organic unsaturated groups such as
C(O)R, CN, and NO2; a few inorganic groups such as
P(O)R2 were also reported to be able to activate vinyl
groups in Michael-type additions.2 We described recently
alkenes included in the original heterohexatriene linkage
H2C=CHP(R)2=NP(R′)2=X (X = O, S);3–5 to the best of
our knowledge, linear 1,2,3,4-heterohexatrienes of type
H2C=CHZ4=Z3Z2=Z1 (with Zn ≠ CRy), having at least one
phosphorus atom in one of the 1, 2, 3, or 4 position were
unknown before our work. We have shown that the
P(R)2=NP(R′)2=X (X = O, S) linkage connected to a vinyl
group can act as a new electron withdrawing group able to
favour the nucleophilic attack of amines on the alkene. In-
deed, the use of such compounds in Michael-type addi-
tions allowed the synthesis of various dendritic6
compounds possessing unusual architectures.3–5 We have
also shown previously that the P=NP=S group not con-
nected to an alkene reacts with strong electrophiles such
as triflates due to the existence of a mesomeric form
(P+–N=PS–); these reactions led also to dendritic com-
pounds possessing original architectures.7 We wish now
to report a series of experiments carried out with small
model compounds in order to determine the scope and
limitations of the Michael-type additions of amines on
Our first experiments were done with the model 1, and
various functionalized amines. Secondary amines such as
diallylamine (a), or thiomorpholine (b), as well as primary
amines such as propargylamine (c), 1-(3-aminopro-
pyl)imidazole (d), or tyramine (e) react in a few hours, ei-
ther at room temperature or by heating at 50–60 °C. The
excess of amine that is often used to reduce the reaction
time is easily removed by washings. The expected addi-
tion products 3a–e are isolated in very good yields (90–
92% after washings) (Scheme 1). It is interesting to note
that tyramine reacts only by its NH2 group, whereas no re-
action of the OH group is observed. To confirm the spe-
cificity of this reaction, we tried to add 1-butanol to 1: no
1,2,3,4-heterohexatrienes
of
type
H2C=CHP(R)2=NP(R′)2=X, and particularly their com-
Synthesis 2003, No. 3, Print: 28 02 03.
Art Id.1437-210X,E;2003,0,03,0389,0396,ftx,en;Z14402SS.pdf.
© Georg Thieme Verlag Stuttgart · New York
ISSN 0039-7881

390
V. Maraval et al.
PAPER
H2
C
Ph
P
O
P
a: R1 = R2
b: R1R2
=
O-Ph
O-Ph
N
S
Ph
=
N
1
H2
HNR1R2
c: R1 = H, R2
d: R1 = H, R2
e: R1 = H, R2
=
=
=
C
H2
C
H2
C
Ph
P
O
P
O-Ph
O-Ph
N
CH2
N
N
R1R2N
H2
C
Ph
3a-e
C
H2
OH
Scheme 1
reaction was observed, even after prolonged heating. This
behaviour is in contrast to the reactivity of vinylphosphine
oxides, which were reported to react both with amines2a,b
and alcohols.2c,d
Figure 1 ORTEP view of compound 1. Selected bond lengths (Å)
and angles (°): C(2)–C(1) 1.316(3); C(1)–P(2) 1.778(3); P(2)–N
1.5772(19); N–P(1) 1.580(2); P(1)–O(1) 1.4627(17); C(2)–C(1)–P(2)
122.3(2); C(1)–P(2)–N 108.87(11); P(2)–N–P(1) 129.25(12); N–
P(1)–O(1) 122.19(10).
The addition reactions are easily monitored by 31P NMR.
Indeed, the doublet corresponding to the PPh2 group is
deshielded from δ = 9.6 for 1 to ca. δ = 17 for 3a–e. Only
one doublet is observed for this group after the addition,
indicating that the reaction is regiospecific. From a steric
and electronic point of view, the nitrogen of the amine
should add on the CH2 carbon of the vinyl group, as con-
firmed by 1H NMR and 13C Jmod NMR. Indeed, both tech-
niques show the presence of two CH2 groups instead of
one CH3 and one CH group, which would result from the
addition onto the CH= carbon of the vinyl group. Further-
more, we never observed the reaction of the secondary
amino derivatives 3c–e with 1, despite the fact that sec-
ondary amines react easily with 1.
Table 1 Crystallographic Data
Chemical formula
Formula weight
C26H23NO3P2
459.39
Temperature
160(2) K
Wavelength
0.71073 Å
Triclinic, P–1
These addition reactions allow interesting functionaliza-
tions of compound 1 by various groups such as a double
or a triple bond, a sulfide, an imidazole, or a phenol. How-
ever, for further reactions able to lead to original dendritic
architectures, the most interesting function to be grafted is
a primary amine. For this purpose, we reacted a very large
excess (250 to 300 equiv) of 1,2-ethylenediamine or
trans-1,2-diaminocyclohexane at room temperature
(Scheme 2). After washings to eliminate the excess of di-
amine, a single compound is obtained in both cases (5a,b).
The phenomenon of deshielding of the signal correspond-
ing to the PPh2 group in the 31P NMR spectrum, already
observed for compounds 3a–e, is also observed for 5a,b.
The presence of a NH2 group in both cases is shown by the
fact that the starting diamine becomes unsymmetrical. In-
deed, two signals are observed for the CH2CH2 linkage
between both nitrogen atoms for compound 5a (13C
NMR δ = 42.1 for CH2NH2 and 50.9 for CH2NH). Analo-
gously, the unsymmetrical cyclohexane ring of compound
5b gives two signals for the CH α to N (13C δ = 63.6 for
CHNH2 and 55.1 for CHNH), as well as for the CH2 β to
N (13C δ = 35.7 for CH2CHNH2 and 31.2 for CH2CHNH).
The presence of the NH2 group is also demonstrated by
the reaction of 5b with another equivalent of compound 1
(Scheme 2). The cyclohexane ring becomes symmetrical
again, as shown by the presence of only one singlet for the
Crystal system, space group
Unit cell dimensions
a = 9.6921(17) Å α = 87.60(2)°
b = 10.7786(18) Å β = 84.46(2)°
c = 10.9160(18) Å γ = 84.87(2)°
Volume
1129.9(3) Å3
2, 1.350 mgm–3
0.221 mm–1
480
Z, Calculated density
Absorption coefficient
F(000)
Crystal size
(0.62 × 0.12 × 0.05)mm
colorless
Crystal color
Crystal form
platelet
Method of collection
Phi rotation
Reflections collected/unique 9052/3358 [R(int) = 0.0430]
Refinement method
Full-matrix least-squares on F2
R1 = 0.0337, wR2 = 0.0791
R1 = 0.0530, wR2 = 0.0868
(0.269 and –0.293) e.Å–3
Final R indices [I > 2σ(I)]
R indices (all data)
Largest diff. peak and hole
Synthesis 2003, No. 3, 389–396 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
1,2,3,4-Heterohexatrienes for Michael-Type Additions in the Synthesis of Phosphorus Dendrimers
391
Ph
O
P N P
Ph
spectra indicate that the grafted triamine remains symmet-
Ph
P N P
Ph
O
O-Ph
O-Ph
H
O-Ph
O-Ph
rical, since only five CH2 groups are detected for 12a in-
stead of eight if the grafted triamine were unsymmetrical.
Thus only the secondary amine reacted as expected, to af-
ford dendron 12a, which possesses two NH2 groups.
+
H2N
(excess)
NH2
N
1
5a,b
4a,b
NH2
1
H2 H2
C
C
Ph
P N P
Ph
O
O-Ph
O-Ph
a:
b:
N
N
N
N
N
N
N
=
=
H
N
Ph
S
Me
S
C N N P
R
2
P N P O
Ph
O
2
Ph
P N P
Ph
H
a: R = H, b: R = CN
Me
N
H
O-Ph
O-Ph
N
9a,b
H2NNMeH
6b
O
Ph
S
S
C N N P
R
H2N
P N P O
Ph
O
Scheme 2
2
2
N
H
10a,b
Me
H2N(CH2)3Si(OEt)3
CH α to N (13C δ = 54.9) and also for the CH2 β to N
(13C δ = 30.9) in the spectrum of the small dendrimer 6b.
Me
S
C N N P
Ph
S
P N P O
Ph
O
2
2
(EtO)3Si
N
H
H
11a
H-N[(CH2)3NH2]2
Another way to functionalize compound 1 by a NH2 group
should use the Michael-type addition of methylhydrazine.
Indeed, the inductive effect of the methyl on the NH group
should induce an addition of this group in a preferential
way compared to the NH2 group. The addition of methyl-
hydrazine occurs regiospecifically on compounds 1 and 2,
leading to 7 and 8, respectively (Scheme 3), as shown by
the presence of a single product in 1H and 31P NMR spec-
tra. The addition induces a shielding of the signal corre-
Ph
S
Me
S
C N N P
H2N
H2N
O
P N P
Ph
O
2
2
N
H
12a
Scheme 4
The presence of NH2 groups in various compounds ob-
tained by Michael-type additions, and particularly those
resulting from the reaction of methylhydrazine, incited us
to use them in condensation reactions, which should lead
to stable hydrazones. We used functionalized benzalde-
hydes, such as 4-hydroxybenzaldehyde whose reaction
with compounds 7 or 8 affords cleanly the condensation
products 13 or 14 (Scheme 5). This reaction is particularly
characterized in the 1H NMR spectrum by a deshielding of
the signal corresponding to the methyl group (from δ = 2.3
for 7 and 8 to δ = 2.6–2.7 for 13 and 14) and in the 13C
NMR spectrum, which shows an important shielding of
the signal corresponding to the same group (from δ = ca.
50 for 7 and 8 to δ = ca. 38 for 13 and 14). A similar be-
haviour is observed when 3,5-dihydroxybenzaldehyde is
reacted with compound 7 to afford compound 15
(13C NMR δ = 37.5 for CH3).
1
sponding to the methyl group in the H NMR spectrum
(from δ = 2.6 to 2.3) and an important deshielding in the
13C NMR spectrum (from δ = 43.6 to 50.0) indicating a re-
action preference for this side of methylhydrazine. How-
ever, the presence of an NH2 group instead of two NH
groups is mainly shown by the reactivity of compounds 7
and 8 with aldehydes (see later).
Ph
P N P
Ph
Ph
P N P
Ph
X
X
MeNHNH2
O
O
O
O
R
R
H2N
N
Me
7, 8
1, 2
R
1, 7: X = O, R = H
2, 8: X = S, R = NMe2
R
Scheme 3
To apply these Michael-type additions to dendrimers, it is
essential to know if they work also with larger compounds
such as the first generation dendrons 9a4 and 9b
(Scheme 4). Methylhydrazine used in large excess reacts
as expected, to afford dendrons 10a and 10b, character-
ized in the 13C NMR by the deshielding of the signal cor-
responding to the methyl group (δ = 50.4). Then, we
tested the reactivity of other functionalized amines. 3-
(Triethoxysilyl)propylamine reacts cleanly with 9a, af-
fording compound 11a, whose Si(OEt)3 group could be
used in a sol-gel process leading to functionalized silica.11
The case of N-(3-aminopropyl)-1,3-propanediamine
could be more problematic. Indeed, this compound pos-
sesses one secondary amine and two primary amines.
However, according to inductive effects already men-
tioned for methylhydrazine, one may expect a reaction of
the NH group instead of the NH2 groups. NMR spectra of
the reaction between this triamine and dendron 9a show
Ph
P
X
P
O
O
R
N
N
HO
CH
N
Me
Ph
13, 14
13: X = O, R = H
14: X = S, R = NMe2
R
HO
CHO
Ph
P
X
P
O
O
R
N
H2N
N
HO
HO
Ph
7, 8
Me
CHO
R = H
R
HO
Ph
P
O
P
O
O
N
CH N
N
Ph
HO
Me
15
Scheme 5
Analogous condensation reactions are expected to occur
with larger compounds such as dendrons 10a and 10b. In-
deed, dendrons 16a and 16b are easily obtained after reac-
1
that a single compound is obtained. H and 13C NMR
Synthesis 2003, No. 3, 389–396 ISSN 0039-7881 © Thieme Stuttgart · New York

392
V. Maraval et al.
PAPER
dried and distilled prior to use (THF and Et2O over sodium/ben-
zophenone, pentane and CH2Cl2 over phosphorus pentoxide). Com-
pounds 1, 2, 73 and 9a, 10a4 were synthesized as described
previously.
tion with 3,5-dihydroxybenzaldehyde (Scheme 6). They
are also characterized by the same phenomenon of
deshielding of the signal corresponding to the methyl
group in the 1H NMR spectrum (from δ = 2.3 for 10a and
10b to δ = 2.7 for 16a and 16b) and shielding in the 13
C
NMR spectrum (from δ = ca 50 for 10a and 10b to δ =
ca. 38 for 16a and 16b).
Ph
P
S
P
Me
S
P
C
N
N
O
R
2
N
O
H2N
2
N
H
Ph
HO
Me
10a,b
CHO
R
a: R = H
b: R = CN
HO
S
S
P
Me
O
O
N
N
C
H
HO
HO
O
R
R
P
N P
CH N
N
O
C
H
N
O
O
N
16a,b
Me
P
S
Figure 2 Numbering used for NMR
Me
R
Single crystals of 1 suitable for X-ray diffraction were obtained at
r.t. in a very dilute solution of THF–pentane (1:5).
Scheme 6
Phosphoramidic Acid, {[2-(Diallylamino)ethyl]diphenylphos-
phoranylidene}-, Diphenyl Ester (3a)
This paper is a new illustration of the great synthetic inter-
est of the P=NP=X (X = O, S) group, which besides its re-
activity with electrophiles,7 is able to activate vinyl
To a solution of compound 1 (0.200 g, 0.435 mmol) in THF (10 mL)
was added diallylamine (1.87 mL, 15.221 mmol). The resulting so-
lution was stirred for 15 h at 50 °C, then cooled and evaporated to
dryness. The residue was washed with THF–pentane (3 × 30 mL;
1:5) to afford 3a.
groups
when
included
in
heterohexatriene
H2C=CHP(R)2=NP(R′)2=X linkage. We have shown that
this linkage reacts easily and cleanly with variously func-
tionalized primary or secondary amines and methylhydra-
zine. The use of functionalized amines allowed the
grafting of another function, such as a double or a triple
bond, a sulfide, an imidazole, or a phenol, and various
types of NH2 groups. We particularly studied the reaction
of these amines, leading to the grafting of other functional
groups such as phenols. Most of these experiences were
successfully applied to the synthesis of dendrimeric com-
pounds.3–5 However, the electron withdrawing efficiency
of the P=NP=X group is not restricted to Michael-type ad-
ditions of amines usable for the synthesis of dendrimers.
Indeed, even the reactivity of small models can afford in-
teresting compounds, as shown recently by the Michael-
type addition of Ph2PH to compound 1, leading to a new
bidentate ligand.12 Furthermore, the extraordinary versa-
tility of functionalization of the P(R)2=NP(R′)2=X group
Yield: 0.223 g; (92%); white powder.
2
31P{1H}NMR (THF): δ = –7.9 (d, JPP = 35.0 Hz, P0), 16.3 (d,
2JPP = 35.0 Hz, P′0).
1H NMR (CDCl3): δ = 2.6 (m, 4 H, CH2CH2P′0), 2.9 (d, 3JHH = 6.3
Hz, 4 H, =CHCH2N), 5.0 (m, 4 H, CH2=), 5.7 (ddt, 3JHHtrans = 17.2,
3JHHcis = 10.0, 3JHH = 6.5 Hz, 2 H, CH=), 7.0–7.7 (m, 20 H, CHarom).
1
13C{1H}NMR (CDCl3): δ = 26.0 (d, JCP = 66.0 Hz, CH2P′0), 45.9
(s, CH2CH2P′0), 56.2 (s, =CHCH2N), 117.6 (s, CH2=), 120.7 (d,
3JCP = 4.0 Hz, C0 ), 123.7 (s, C0 ), 128.7 (d, JCP = 12.0 Hz, m-
2
4
3
C6H5), 129.2 (s, C0 ), 131.2 (d, 2JCP = 11.4 Hz, o-C6H5), 132.3 (s, p-
3
1
C6H5), 135.2 (s, CH=), 152.4 (d, 2JCP = 8.0 Hz, C0 ).
Anal. Calcd for C32H34N2O3P2: C, 69.06; H, 6.16; N, 5.03. Found:
C, 69.19; H, 6.18; N, 4.98.
Phosphoramidic Acid, {[2-(Thiomorpholino)ethyl]diphenyl-
phosphoranylidene}-, Diphenyl Ester (3b)
To a solution of compound 1 (0.200 g, 0.435 mmol) in THF (10 mL)
must be emphasized. X and R can be modified, and virtu- was added thiomorpholine (2.190 mL, 21.744 mmol). The resulting
solution was stirred for 6 h at r.t., and then evaporated to dryness.
The residue was washed with THF–pentane (2 × 20 mL; 1:5) to af-
ford 3b.
ally any type of substituents can be used as the R′ group.
Thus, the P(R)2=NP(R′)2=X group appears as a new and
versatile tool offered to the imagination of synthetic
Yield: 0.220 g (90%); white powder.
chemists.
2
31P{1H}NMR (THF): δ = –7.8 (d, JPP = 34.5 Hz, P′0), 17.1 (d,
2JPP = 34.5 Hz, P0).
All manipulations were carried out with standard high vacuum and
1H NMR (CDCl3): δ = 2.0–3.0 (m, 12 H, CH2), 7.0–7.8 (m, 20 H,
CHarom).
dry-argon techniques. 1H, 13C, 31P NMR spectra were recorded with
Bruker AC 200, AC 250, DPX 300 or AMX 400 spectrometers.
References for NMR chemical shifts are 85% H3PO4 for 31P NMR,
SiMe4 for 1H and 13C NMR. The attribution of 13C NMR signals has
been done using Jmod, two dimensional HMBC, and HMQC, broad
band or CW 31P decoupling experiments when necessary. However,
the signal for ipso-C6H5 was often partly hidden. The numbering
used for NMR assignments is depicted in Figure 2. Solvents were
1
13C{1H}NMR (CDCl3): δ = 25.8 (d, JCP = 66.0 Hz, CH2P′0), 27.7
(s, CH2S), 51.4 (s, CH2CH2P′0), 54.3 (s, SCH2CH2N), 120.7 (d,
2
4
3
3JCP = 3.5 Hz, C0 ), 123.7 (s, C0 ), 128.7 (d, JCP = 12.4 Hz, m-
C6H5), 129.2 (s, C0 ), 131.1 (d, 2JCP = 10.0 Hz, o-C6H5), 132.3 (s, p-
3
C6H5), 152.3 (d, 2JCP = 7.4 Hz, C0 ).
1
Synthesis 2003, No. 3, 389–396 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
1,2,3,4-Heterohexatrienes for Michael-Type Additions in the Synthesis of Phosphorus Dendrimers
393
Anal. Calcd for C30H32N2O3P2S: C, 64.05; H, 5.73; N, 4.98. Found:
C, 64.21; H, 5.70; N, 4.95.
1H NMR (CDCl3): δ = 2.5–2.8 (m, 9 H, CH2CH2NHCH2CH2P′0),
5.2 (br s, 1 H, OH), 6.7–7.6 (m, 20 H, CHarom).
13C{1H} NMR (CDCl3): δ = 28.6 (d, 1JCP = 66.2 Hz, CH2-P′0), 34.8
(s, CH2C6H4), 42.1 (s, CH2CH2P′0), 50.7 (s, CH2CH2C6H4), 115.6
Phosphoramidic Acid, {[2-(Propargylamino)ethyl]diphenyl-
phosphoranylidene}-, Diphenyl Ester (3c)
3
2
4
(s, C2), 120.5 (d, JCP = 4.7 Hz, C0 ), 123.9 (s, C0 ), 128.7 (d,
To a solution of compound 1 (0.200 g, 0.435 mmol) in THF (10 mL)
was added propargylamine (3.0 mL, 43.5 mmol). The resulting so-
lution was stirred for 2 h at 60 °C, then cooled and evaporated to
dryness. The oily residue was washed with THF–pentane (1:5, 3 ×
30 mL) to afford 3c.
3JCP = 12.7 Hz, m-C6H5), 129.1 (s, C0 ), 129.3 (s, C3), 129.6 (s, C4),
3
2
130.9 (d, JCP = 10.5 Hz, o-C6H5), 132.3 (s, p-C6H5), 151.9 (d,
1
2JCP = 8.1 Hz, C0 ), 155.7 (s, C1).
Anal. Calcd for C34H34N2O4P2: C, 68.45; H, 5.74; N, 4.70. Found:
C, 68.51; H, 5.72; N, 4.71.
Yield: 0.202 g (90%); pale beige powder.
2
31P{1H}NMR (CDCl3): δ = –6.8 (d, JPP = 33.6 Hz, P0), 16.6 (d,
Phosphoramidic Acid, ({2-[(2-aminoethyl)amino]ethyl}diphe-
nylphosphoranylidene)-, Diphenyl Ester (5a)
2JPP = 33.6 Hz, P′0).
To a solution of compound 1 (0.200 g, 0.435 mmol) in THF (10 mL)
was added a large excess of ethylenediamine (8.7 mL, 131 mmol).
The resulting solution was stirred for 3 h at r.t., and then evaporated
to dryness. The residue was washed with THF–pentane (1:5, 3 × 30
mL) to afford 5a.
4
1H NMR (CDCl3): δ = 2.1 (t, JHH = 2.1 Hz, 1 H, HC≡), 2.6 (td,
2JHP = 11.3, JHH = 7.7 Hz, 2 H, CH2P′0), 2.8 (td, JHP = 7.7,
3
3
3JHH = 7.7 Hz, 2 H, CH2CH2P′0), 3.2 (d, JHH = 2.1 Hz, 2 H,
4
CH2C≡), 7.0–7.6 (m, 20 H, CHarom).
13C{1H}NMR (CDCl3): δ = 29.2 (d, JCP = 67.7 Hz, CH2P′0), 37.8
(s, ≡CCH2NH), 41.6 (s, CH2CH2P′0), 71.7 (s, CH≡), 81.5 (s, C≡),
120.7 (d, JCP = 3.4 Hz, C0 ), 123.7 (s, C0 ), 128.8 (d, JCP = 12.8
1
Yield: 0.222 g (98%); pale yellow oil.
3
2
4
3
2
31P{1H} NMR (THF): δ = –7.5 (d, JPP = 33.8 Hz, P0), 16.3 (d,
2JPP = 33.8 Hz, P′0).
3
2
Hz, m-C6H5), 129.2 (s, C0 ), 131.2 (d, JCP = 10.6 Hz, o-C6H5),
132.4 (s, p-C6H5), 152.3 (d, 2JCP = 8.0 Hz, C0 ).
1
1H NMR (CDCl3): δ = 1.7 (br s, 3 H, NH2, NH), 2.5–2.7 (m, 8 H,
CH2CH2NHCH2CH2P′0), 7.0–7.6 (m, 20 H, CHarom).
Anal. Calcd for C29H28N2O3P2: C, 67.70; H, 5.49; N, 5.45. Found:
C, 67.64; H, 5.50; N, 5.42.
13C{1H} NMR (CDCl3): δ = 29.0 (d, 1JCP = 66.0 Hz, CH2P′0), 40.8
(s, CH2CH2P′0), 42.1 (s, H2NCH2), 50.9 (s, H2NCH2CH2NH),
Phosphoramidic Acid, ({2-[1-(3-Aminopropyl)imidazole]eth-
yl}diphenylphosphoranylidene)-, Diphenyl Ester (3d)
To a solution of compound 1 (0.500 g, 1.09 mmol) in THF (2 mL)
was added 1-(3-aminopropyl)imidazole (2.0 mL, 16.35 mmol). The
resulting solution was stirred for 12 h at r.t., and then evaporated to
dryness. H2O was added and the product was extracted with
CH2Cl2. The organic phase was dried (Na2SO4). After filtration and
evaporation to dryness, the product was washed with THF–pentane
(1:10, 3 × 20 mL) to give 3c.
3
2
4
3
120.5 (d, JCP = 5.3 Hz, C0 ), 123.6 (s, C0 ), 128.6 (d, JCP = 12.2
3
Hz, m-C6H5), 129.1 (s, C0 ), 129.2 (dd, 1JCP = 104.6 Hz, 3JCP = 5.8
Hz, i-C6H5), 131.0 (d, 2JCP = 10.9 Hz, o-C6H5), 132.1 (d, 4JCP = 2.3
Hz, p-C6H5), 152.1 (d, 2JCP = 7.8 Hz, C0 ).
1
Anal. Calcd for C28H31N3O3P2: C, 64.73; H, 6.01; N, 8.09. Found:
C, 64.60; H, 6.01; N, 8.07.
Phosphoramidic Acid, ({2-[(2-Aminocyclohexane)-1-amino]-
ethyl}diphenylphosphoranylidene)-, Diphenyl Ester (5b)
To a solution of compound 1 (0.100 g, 0.218 mmol) in THF (10 mL)
was added a large excess of trans-1,2-diaminocyclohexane (6.5 mL,
54.4 mmol). The resulting solution was stirred for 2 h at r.t., and
then evaporated to dryness. The residue was washed with Et2O–
pentane (1:5, 3 × 20 mL) to afford 5b.
Yield: 0.520 g (90%); white powder.
31P{1H}NMR (CDCl3): δ = –6.7 (d, JPP = 34.7 Hz, P0), 16.1 (d,
2
2JPP = 34.7 Hz, P′0).
1H NMR (CDCl3): δ = 1.65 (quint,
2
H, JHH = 6.8 Hz,
3
CH2CH2CH2), 2.3 (t, 2 H, 3JHH = 6.8 Hz, CH2CH2CH2NH), 2.4 (br
3
s, 1 H, NH), 2.6 (m, 4 H, CH2CH2P′0), 3.8 (t, 2 H, JHH = 6.8 Hz,
Yield: 0.097 g (78%); white powder.
ImCH2CH2CH2) 6.7 (s, 1 H, CH=CHIm), 6.9 (s, 1 H, CH=CHIm),
7.1–7.8 (m, 21 H, CHarom, CH=NIm).
2
31P{1H} NMR (CDCl3): δ = –6.8 (d, JPP = 31.9 Hz, P0), 16.5 (d,
2JPP = 31.9 Hz, P′0).
1
13C{1H}NMR (CDCl3): δ = 28.8 (d, JCP = 66.2 Hz, CH2P′0), 30.9
1H NMR (CDCl3): δ = 1.0–2.2 (m, 13 H, CH2cycle, CHcycle, NH2,
NH), 2.6 (m, 2 H, CH2CH2P′0), 2.8 (m, 2 H, CH2P′0), 7.0–7.7 (m,
20 H, CHarom).
(s, CH2CH2CH2), 42.4 (s, CH2CH2P′0), 44.4 (s, CH2CH2CH2NH),
45.7 (s, ImCH2CH2CH2), 118.9 (s, CH=CHIm), 120.5 (d, 3JCP = 5.5
2
4
Hz, C0 ), 123.8 (s, C0 ), 128.7 (s, CH=CHIm), 129.0 (d, 3JCP = 12.8
13C{1H} NMR (CDCl3): δ = 25.1 (s, C4, C5), 30.0 (d, 1JCP = 67.0 Hz,
3
Hz, m-C6H5), 129.2 (s, C0 ), 129.3 (dd, 1JCP = 104, 3JCP = 5.8 Hz, i-
CH2P′0), 31.2 (s, C6), 35.7 (s, C3), 39.8 (s, CH2CH2P′0), 55.1 (s,
C6H5), 131 (d, 2JCP = 11.4 Hz, o-C6H5), 132.4 (s, p-C6H5), 137.1 (s,
C1), 63.6 (s, C2), 120.6 (d, 3JCP = 4.1 Hz, C0 ), 123.7 (s, C0 ), 128.8
2
4
CH=NIm), 151.2 (d, 2JCP = 7.5 Hz, C0 ).
1
(d, 3JCP = 12.1 Hz, m-C6H5), 129.2 (s, C0 ), 131.2 (d, 2JCP = 10.1 Hz,
3
Anal. Calcd for C32H34N4O3P2: C, 65.75; H, 5.86; N, 9.58. Found:
C, 65.82; H, 5.83; N, 9.55
o-C6H5), 132.2 (s, p-C6H5), 152.3 (d, 2JCP = 7.6 Hz, C0 ).
1
Anal. Calcd for C32H37N3O3P2: C, 67.01; H, 6.50; N, 7.33. Found:
C, 66.93; H, 6.48; N, 7.30.
Phosphoramidic Acid, {[2-(Tyramine)ethyl]diphenylphosphor-
anylidene}-, Diphenyl Ester (3e)
Phosphoramidic Acid, Bis-[2-(1,2-aminocyclohexane)ethyl]-
diphenylphosphoranylidene}-, Diphenyl Ester (6b)
To a solution of compound 1 (0.200 g, 0.435 mmol) in THF (15 mL)
was added tyramine (0.179 g, 1.306 mmol). The resulting solution
was stirred for 4 h at 50 °C, then cooled and evaporated to dryness.
The residue was extracted with CH2Cl2, and the solution was evap-
orated to dryness to afford 3e.
To a solution of compound 5b (0.200 g, 0.349 mmol) in THF (10
mL) was added compound 1 (0.080 g, 0.174 mmol). The resulting
solution was stirred for 3 d at 90 °C in a sealed reactor, then cooled
and evaporated to dryness. The residue was washed with THF–pen-
tane (1:5, 3 × 30 mL) to afford 6b.
Yield: 0.241 g (92%); white powder.
2
31P{1H}NMR (CDCl3): δ = –7.5 (d, JPP = 31.5 Hz, P0), 16.6 (d,
Yield: 0.218 g (78%); white powder.
2JPP = 31.5 Hz, P′0).
Synthesis 2003, No. 3, 389–396 ISSN 0039-7881 © Thieme Stuttgart · New York

394
V. Maraval et al.
PAPER
2
4
2
1
2
31P{1H} NMR (THF): δ = –7.8 (d, JPP = 34.9 Hz, P0), 15.8 (d,
C0 CH=N), 153.2 (d, JCP = 8.7 Hz, C0 ), 153.4 (d, JCP = 7.3 Hz,
2JPP = 34.9 Hz, P′0).
C1 ).
1
1H NMR (CDCl3): δ = 1.0–2.0 (m, 12 H, CH2cycle, CHcycle, NH), 2.6
(m, 2 H, CH2CH2P′0), 2.9 (m, 2 H, CH2P′0), 6.9–7.6 (m, 40 H,
CHarom).
Anal. Calcd for C58H45N9O6P4S3: C, 58.83; H, 3.83; N, 10.65.
Found: C, 58.71; H, 3.85; N, 10.60.
Phosphorohydrazidothioic Acid, 2,2′-[({[2-(1-Methylhydrazi-
no)ethyl]diphenylphosphoranyl idene}amino)phosphinothioyl-
idene]bis(oxy-1,4-phenylenemethylidyne)bis-1-methyl,
O,O,O,O-Tetrakis(4-cyanophenyl) Ester, (2E,2E′) (10b)
To a solution of dendron 9b (0.200 g, 0.169 mmol) in THF (10 mL)
was added methylhydrazine (30 equiv of monomethylhydrazine
0.270 mL, 5.067 mmol). The resulting solution was stirred for 3 h
at r.t., and then evaporated to dryness. The residue was washed with
THF–pentane (1:5, 3 × 30 mL) to afford 10b.
13C{1H} NMR (CDCl3): δ = 24.6 (s, C4, C5), 29.5 (d, 1JCP = 66.6 Hz,
CH2P′0), 30.9 (s, C3, C6), 39.4 (s, CH2CH2P′0), 54.9 (s, C1, C2),
3
2
4
3
120.6 (d, JCP = 4.2 Hz, C0 ), 123.7 (s, C0 ), 128.8 (d, JCP = 11.9
3
2
Hz, m-C6H5), 129.2 (s, C0 ), 131.2 (d, JCP = 11.0 Hz, o-C6H5),
132.2 (s, p-C6H5), 152.3 (d, 2JCP = 7.3 Hz, C0 ).
1
Anal. Calcd for C58H60N4O6P4: C, 67.44; H, 5.85; N, 5.42. Found:
C, 67.49; H, 5.82; N, 5.46.
Phosphoramidothioic Acid, {[2-(1-Methylhydrazino)ethyl]-
diphenylphosphoranylidene}-, O,O-Bis-[3-(dimethylami-
no)phenyl] Ester (8)
To a solution of compound 2 (0.221 g, 0.394 mmol) in THF (10 mL)
was added methylhydrazine (0.063 mL, 1.181 mmol). The resulting
solution was stirred for 3 h at r.t., and then evaporated to dryness.
The residue was washed with THF–pentane (3 × 30 mL; 1:5) to af-
ford 8.
Yield: 0.197 g (95%); white powder.
2
31P{1H} NMR (CDCl3): δ = 18.8 (d, JPP = 33.3 Hz, P′0), 52.4 (d,
2JPP = 33.3 Hz, P0), 60.9 (s, P1).
1H NMR (CDCl3): δ = 2.3 (s, 3 H, CH3NNH2), 2.6 (m, 2 H,
3
CH2CH2P′0), 3.0 (m, 2 H, CH2P′0), 3.3 (d, JHP = 11.1 Hz, 6 H,
CH3NP1), 7.2–7.7 (m, 36 H, CHarom, CH=N).
13C{1H} NMR (CDCl3): δ = 25.3 (d, 1JCP = 66.0 Hz, CH2P′0), 32.9
Yield: 0.227 g (95%); colorless oil.
2
(d, JCP = 13.6 Hz, CH3NP1), 50.4 (s, CH3NNH2), 54.4 (s,
2
4
31P{1H} NMR (CDCl3): δ = 16.6 (d, JPP = 33.5 Hz, P′0), 52.3 (d,
CH2CH2P′0), 109.5 (s, C1 ), 118.1 (s, C≡N), 122.1 (d, 3JCP = 5.1 Hz,
2
3
2
3
2JPP = 33.5 Hz, P0).
C0 ), 122.4 (d, JCP = 4.1 Hz, C1 ), 128.1 (s, C0 ), 128.8 (d,
3JCP = 12.1 Hz, m-C6H5), 130.4 (s, C0 ), 131.3 (d, 2JCP = 10.1 Hz, o-
4
1H NMR (CDCl3): δ = 2.3 (s, 3 H, CH3), 2.6 (m, 2 H, CH2CH2P′0),
2.8 (s, 12 H, NMe2), 3.0 (m, 4 H, CH2P′0, NH2), 6.5–7.7 (m, 18 H,
CHarom).
3
3
C6H5), 132.5 (s, p-C6H5), 133.9 (s, C1 ), 140.6 (d, JCP = 13.6 Hz,
4
2
1
2
C0 -CH=N), 153.4 (d, JCP = 9.4 Hz, C0 ), 153.7 (d, JCP = 6.2 Hz,
1
C1 ).
13C{1H} NMR (CDCl3): δ = 25.4 (d, 1JCP = 66.2 Hz, CH2P′0), 40.5
Anal. Calcd for C59H51N11O6P4S3: C, 57.60; H, 4.18; N, 12.52.
Found: C, 57.48; H, 4.17; N, 12.49.
(s, NMe2), 50.0 (s, CH3), 54.6 (s, CH2CH2P′0), 106.4 (d, 3JCP = 5.6
2
4
3
6
Hz, C0 ), 108.5 (s, C0 ), 109.9 (d, JCP = 3.8 Hz, C0 ), 128.7 (d,
5
3JCP = 12.1 Hz, m-C6H5), 129.2 (s, C0 ), 131.4 (d, 2JCP = 11.1 Hz, o-
C6H5), 132.2 (s, p-C6H5), 151.4 (s, C0 ), 153.1 (d, JCP = 9.5 Hz,
Phosphorohydrazidothioic Acid, 2,2′-{[({2-[3-(Triethoxysi-
lyl)propylamine]ethyl}diphenyl phosphoranylidene)amino]-
phosphinothioylidene}bis(oxy-1,4-phenylenemethylidyne)bis-
1-methyl-, O,O,O,O-Tetraphenyl Ester, (2E,2E′) (11a)
To a solution of dendron 9a (0.250 g, 0.231 mmol) in THF (10 mL)
was added 3-(triethoxysilyl)propylamine (5.4 mL, 23.1 mmol). The
resulting solution was stirred overnight at r.t., and then evaporated
to dryness. The residue was washed with THF–pentane (1:5, 3 × 20
mL) to afford dendron 11a.
3
2
1
C0 ).
Anal. Calcd for C31H39N5O2P2S: C, 61.27; H, 6.47; N, 11.52.
Found: C, 61.42; H, 6.44; N, 11.49.
Phosphorohydrazidothioic Acid, 2,2′-({[(Ethenyldiphenylphos-
phoranylidene)amino]phosphinothioylidene}bis(oxy-4,1-phen-
ylenemethylidyne))bis-1-methyl-, O,O,O,O-Tetrakis(4-cyano-
phenyl) Ester, (2E,2E′) (9b)
To a solution of CH2=CHPPh2=NP(S)[OC6H4CH=NNMeP(S)Cl2]2
(0.300 g, 0.351 mmol)4 in THF (10 mL) was added NaOC6H4C≡N
(0.218 g, 1.546 mmol). The resulting mixture was stirred for 12 h at
r.t., and then centrifuged, and the solution was evaporated to dry-
ness. The residue was washed with THF–pentane (1:5, 3 × 50 mL)
to afford dendron 9b.
Yield: 0.283 g (94%); white powder.
2
31P{1H} NMR (CDCl3): δ = 17.1 (d, JPP = 35.0 Hz, P′0), 51.8 (d,
2JPP = 35.0 Hz, P0), 61.9 (s, P1).
3
1H NMR (CDCl3): δ = 0.5 (t, JHH = 8.6 Hz, 2 H, CH2Si), 1.2 (t,
3JHH = 7.1 Hz, 9 H, CH3CH2O), 1.5 (m, 2 H, CH2CH2CH2Si), 2.5 (t,
3JHH = 8.6 Hz, 2 H, CH2CH2CH2Si), 2.9 (m, 4 H, CH2CH2P′0), 3.3
3
Yield: 0.400 g (96%); white powder.
(d, JHP = 10.2 Hz, 6 H, P1NCH3), 3.5 (br s, 1 H, NH), 3.8 (q,
3JHH = 7.1 Hz, 6 H, CH3CH2O), 7.2–7.7 (m, 40 H, CHarom, CH=N).
2
31P{1H} NMR (CDCl3): δ = 12.1 (d, JPP = 29.8 Hz, P′0), 53.1 (d,
2JPP = 29.8 Hz, P0), 60.9 (s, P1).
13C{1H} NMR (CDCl3): δ = 7.7 (s, CH2Si), 18.1 (s, CH3CH2O),
23.0 (s, CH2CH2CH2Si), 28.0 (d, 1JCP = 60.2 Hz, CH2P′0), 33.1 (d,
2JCP = 13.3 Hz, P1NCH3), 42.3 (s, CH2CH2P′0), 52.0 (s,
3
1H NMR (CDCl3): δ = 3.3 (d, JHP = 11.1 Hz, 6 H, CH3NP1), 6.1
3
3
2
(ddd, JHP = 24.2, JHH = 18.3, JHH = 1.0 Hz, 1 H, HC), 6.4 (ddd,
2
CH2CH2CH2Si), 58.2 (s, CH3CH2O), 121.8 (d, 3JCP = 4.8 Hz, C1 ),
3JHP = 45.8, JHH = 12.3, JHH = 1.0 Hz, 1 H, HB), 6.8 (dddd,
2JHP = 25.2, 3JHH = 18.3, 2JHH = 12.3, 2JHH = 1.0 Hz, 1 H, HA), 7.2–
7.7 (m, 36 H, CHarom, CH=N).
3
2
2
4
3
122.5 (d, 3JCP = 4.9 Hz, C0 ), 125.8 (s, C1 ), 128.5 (s, C0 ), 128.9 (d,
3JCP = 12.6 Hz, m-C6H5), 129.9 (s, C1 ), 131.4 (s, C0 ), 131.7 (d,
2JCP = 9.3 Hz, o-C6H5), 132.6 (s, p-C6H5), 139.4 (d, 3JCP = 14.2 Hz,
C0 CH=N), 151.0 (d, JCP = 6.8 Hz, C0 ), 153.6 (d, JCP = 9.1 Hz,
3
4
2
13C{1H} NMR (CDCl3): δ = 32.7 (d, JCP = 13.4 Hz, CH3NP1),
4
2
1
2
4
2
109.3 (s, C1 ), 118.0 (s, CN), 121.9 (d, 3JCP = 5.0 Hz, C0 ), 122.3 (d,
1
C1 ).
3JCP = 5.0 Hz, C1 ), 127.9 (s, C0 ), 128.6 (d, JCP = 13.1 Hz, m-
2
3
3
Anal. Calcd for C63H72N6O9P4S3Si: C, 57.97; H, 5.56; N, 6.44.
Found: C, 57.95; H, 5.53; N, 6.41.
C6H5), 130.2 (s, C0 ), 132.0 (d, 2JCP = 10.9 Hz, o-C6H5), 132.6 (s, p-
4
3
3
C6H5), 133.8 (s, C1 ), 136.7 (s, CH2= ), 140.4 (d, JCP = 13.5 Hz,
Synthesis 2003, No. 3, 389–396 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
1,2,3,4-Heterohexatrienes for Michael-Type Additions in the Synthesis of Phosphorus Dendrimers
395
Phosphorohydrazidothioic Acid, 2,2′-{[({2-[N-(3-aminopropyl)-
1,3-propanediamine]ethyl} diphenylphosphoranylidene)ami-
no]phosphinothioylidene}bis(oxy-1,4-phenylenemethylidyne)
bis-1-methyl-, O,O,O,O-Tetraphenyl Ester, (2E,2E′) (12a)
To a solution of dendron 9a (0.4 g, 0.369 mmol) in THF (2 mL) was
added a large excess of N-(3-aminopropyl)-1,3-propanediamine
(5.2 ml, 37 mmol). The resulting mixture was stirred at r.t. for 12 h.
The solvent was then evaporated under vacuum and the residue was
washed several times with THF–pentane (1:10, 5 × 10 mL) to afford
dendron 12a.
Anal. Calcd for C38H43N5O3P2S: C, 64.12; H, 6.09; N, 9.84. Found:
C, 64.04; H, 6.05; N, 9.81.
Compound 15
To a solution of compound 7 (0.200 g, 0.396 mmol) in THF (10 mL)
was added 3,5-dihydroxybenzaldehyde (1.1 equiv, 0.060 g, 0.435
mmol). The resulting solution was stirred overnight at r.t., and then
evaporated to dryness. The residue was washed several times with
THF–pentane (1:5) to afford compound 15.
Yield: 0.210 g (85%); white powder.
Yield: 0.320 g (80%); white powder.
2
31P{1H} NMR (CDCl3): δ = –7.5 (d, JPP = 33.5 Hz, P0), 17.4 (d,
31P{1H} NMR (CDCl3): δ = 17.7 (d, JPP = 33.8 Hz, P′0), 52.1 (d,
2JPP = 33.5 Hz, P′0).
2
2JPP = 33.8 Hz, P0), 62.6 (s, P1).
1H NMR (CDCl3): δ = 2.4 (s, 3 H, CH3NCH2), 2.7 (m, 2 H,
CH2P′0), 3.3 (m, 2 H, CH2CH2P′0), 6.3 (s, 1 H, HC1), 6.6 (s, 2 H,
HC3), 6.7 (s, 1 H, C4CH=N), 6.9–7.5 (m, 20 H, CHarom), 8.2 (br s, 2
H, OH).
1H NMR (CDCl3): δ = 1.4 (br s, 4 H, NH2), 1.57 (m, 4 H,
CH2CH2CH2), 2.5–3.0 (m, 12 H, NH2CH2, CH2N, CH2CH2P′0), 3.3
(d, 3JHP = 10.5 Hz, 3 H, CH3), 7.1–7.8 (m, 40 H, CHarom, CH=N).
13C{1H} NMR (CDCl3): δ = 27.7 (d, 1JCP = 64.7 Hz, CH2P′0), 32.9
(d, 2JCP = 12.3 Hz, CH3), 33.7 (s, CH2CH2CH2), 40.5 (s, NH2CH2),
47.9 (s, NH2CH2CH2CH2N), 48.2 (s, CH2CH2P′0), 121.4 (d,
13C{1H} NMR (CDCl3): δ = 25.9 (d, 1JCP = 66.0 Hz, CH2P′0), 37.5
(s, CH3NCH2), 51.3 (s, CH2CH2P′0), 102.8 (s, C1), 104.9 (s, C3),
2
4
120.6 (d, 3JCP = 4.4 Hz, C0 ), 123.9 (s, C0 ), 128.5 (dd, 1JCP = 105.2,
2
2
4
3JCP = 3.8 Hz, C1 ), 121.9 (d, 3JCP = 4 Hz, C0 ), 125.2 (s, C1 ), 127.9
3JCP = 5.3 Hz, i-C6H5), 128.6 (d, 3JCP = 12.7 Hz, m-C6H5), 129.2 (s,
(s, C0 ), 128.7 (d, JCP = 12.1 Hz, m-C6H5), 129.1 (dd, JCP = 105,
C0 ), 130.8 (d, 2JCP = 10.6 Hz, o-C6H5), 132.2 (s, p-C6H5), 134.2 (s,
3
3
1
3
3JCP = 5.8 Hz, i-C6H5), 129.4 (s, C1 ), 131.1 (s, C0 ), 131.4 (d,
CH=N), 138.2 (s, C4), 151.8 (d, 2JCP = 7.5 Hz, C0 ), 157.6 (s, C3).
3
4
1
2JCP = 10.0 Hz, o-C6H5), 132.4 (s, p-C6H5), 139.0 (d, 3JCP = 13.7 Hz,
Anal. Calcd for C34H33N3O5P2: C, 65.28; H, 5.32; N, 6.72. Found:
C, 65.14; H, 5.29; N, 6.69.
CH=N), 151 (d, 2JCP = 7.8 Hz, C1 ), 153.3 (d, 2JCP = 9.7 Hz, C0 ).
1
1
Anal. Calcd for C60H66N8O6P4S3: C, 59.30; H, 5.47; N, 9.22. Found:
C, 59.18; H, 5.45; N, 9.18.
Dendrons 16a and 16b; General Procedure
To a solution of dendron 10a (0.4 g, 0.354 mmol) or 10b (0.435 g,
0.354 mmol) in THF (10 mL) was added 3,5-dihydroxybenzalde-
hyde (0.054 g, 0.390 mmol). The resulting mixture was stirred at r.t.
for 24 h, and then evaporated to dryness. The residue was washed
with THF–pentane (1:10) to afford 16a or 16b.
Compounds 13 and 14; General Procedure
To a solution of compound 7 (0.200 g, 0.396 mmol) or 8 (0240 g,
0.396 mmol) in THF (10 mL) was added 4-hydroxybenzaldehyde
(0.048 g, 0.396 mmol). The resulting solution was stirred at r.t. for
24 h, and then evaporated to dryness. The residue was washed with
THF–pentane (1:5, 3 × 30 mL) to afford compound 13 or 14.
Compound 16a
Yield: 0.395g (89%); pale brown powder.
Compound 13
Yield: 0.205 g (85% yield); pale beige powder.
2
31P{1H} NMR (CDCl3): δ = 17.6 (d, JPP = 33.5 Hz, P′0), 52.3 (d,
2JPP = 33.5 Hz, P0), 62.8 (s, P1).
31P{1H} NMR (THF): δ = –8.0 (d, JPP = 33.2 Hz, P0), 16.8 (d,
2
1H NMR (CDCl3): δ = 2.7 (s, 3 H, CH3NCH2), 3.1 (m, 2 H,
2JPP = 33.2 Hz, P′0).
3
CH2P′0), 3.4 (d, JHP = 10.5 Hz, 3 H, CH3NP1), 3.5 (m, 2 H,
1H NMR (CDCl3): δ = 2.6 (s, 3 H, CH3), 2.8 (m, 2 H, CH2P′0), 3.4
(m, 2 H, CH2CH2P′0), 7.0–7.7 (m, 25 H, CHarom, CH=N).
CH2CH2P′0), 6.2 (s, 1 H, HC1), 6.6 (s, 2 H, HC3), 6.9 (s, 1 H,
C4CH=N), 7.1–7.8 (m, 40 H, CHarom, CH=NNP).
13C{1H} NMR (CDCl3): δ = 26.0 (d, 1JCP = 65.8 Hz, CH2P′0), 38.0
13C{1H} NMR (CDCl3): δ = 25.0 (d, 1JCP = 60.5 Hz, CH2P′0), 33.3
3
2
(s, CH3), 51.6 (s, CH2CH2P′0), 115.9 (s, C2), 120.8 (d, JCP = 3.9
(d, JCP = 12.8 Hz, CH3NP1), 38.3 (s, CH3NCH2), 51.9 (s,
2
4
3
Hz, C0 ), 124.3 (s, C0 ), 127.1 (s, C3), 128.9 (d, 3JCP = 13.2 Hz, m-
CH2CH2P′0), 102.7 (s, C1), 105.6 (s, C3), 121.9 (d, JCP = 4.6 Hz,
1
3
2
2
4
3
C6H5), 129.1 (dd, JCP = 104.2, JCP = 5.3 Hz, i-C6H5), 129.4 (s,
C1 ), 122.4 (d, 3JCP = 5 Hz, C0 ), 125.8 (s, C1 ), 128.4 (s, C0 ), 129.3
C0 ), 131.2 (d, 2JCP = 10.2 Hz, o-C6H5), 132.5 (s, p-C6H5, C4), 135.8
(d, 3JCP = 12.8 Hz, m-C6H5), 129.9 (s, C1 ), 131.6 (s, C0 ), 131.8 (d,
3
3
4
1
(s, CH=N), 152.1 (d, 2JCP = 7.7 Hz, C0 ), 157.7 (s, C1).
2JCP = 10.6 Hz, o-C6H5), 132.9 (s, p-C6H5), 133 (s, C4CH=N), 139.3
(d, 3JCP = 13.7 Hz, C0 CH=N), 139.5 (s, C4), 151 (d, 2JCP = 7.2 Hz,
4
Anal. Calcd for C34H33N3O4P2: C, 66.99; H, 5.46; N, 6.89. Found:
C, 66.91; H, 5.43; N, 6.87.
1
1
C1 ), 153.3 (d, 2JCP = 9 Hz, C0 ), 157.5 (s, C2).
Anal. Calcd for C62H59N7O8P4S3: C, 59.56; H, 4.76; N, 7.84. Found:
C, 59.51; H, 4.79; N, 7.81.
Compound 14
Yield: 0.225 g (80%); pale beige powder.
Compound 16b
Yield: 0.454 g (95%); white powder.
2
31P{1H} NMR (CDCl3): δ = 16.4 (d, JPP = 33.5 Hz, P′0), 51.1 (d,
2JPP = 33.5 Hz, P0).
31P{1H} NMR (CDCl3): δ = 18.2 (d, JPP = 33.8 Hz, P′0), 52.6 (d,
2
1H NMR (CDCl3): δ = 2.7 (s, 3 H, CH3NCH2), 2.8 (s, 12 H, NMe2),
3.0 (m, 2 H, CH2P′0), 3.5 (m, 2 H, CH2CH2P′0), 6.4–7.7 (m, 23 H,
CHarom, CH=N).
2JPP = 33.8 Hz, P0), 60.8 (s, P1).
1H NMR (CDCl3): δ = 2.66 (s, 3 H, CH3NCH2), 3.03 (m, 2 H,
CH2P′0), 3.34 (d, JHP = 11.1 Hz, 6 H, CH3NP1), 3.46 (m, 2 H,
CH2CH2P′0), 6.3–7.5 (m, 40 H, CHarom, CH=N).
3
13C{1H} NMR (CDCl3): δ = 24.1 (d, 1JCP = 63.1 Hz, CH2P′0), 37.9
(s, CH3NCH2), 40.4 (s, NMe2), 51.2 (s, CH2CH2P′0), 106.2 (d,
3JCP = 5.3 Hz, C0 ), 108.5 (s, C0 ), 109.7 (d, JCP = 4.4 Hz, C0 ),
13C{1H} NMR (CDCl3): δ = 24.2 (d, 1JCP = 63.4 Hz, CH2P′0), 32.9
2
4
3
6
2
115.4 (s, C2), 126.9 (s, C3), 128.6 (d, 3JCP = 12.7 Hz, m-C6H5), 129.1
(d, JCP = 13.6 Hz, CH3NP1), 37.8 (s, CH3NCH2), 51.3 (s,
(s, C0 ), 131.3 (d, JCP = 10.7 Hz, o-C6H5), 132.0 (s, p-C6H5, C4),
CH2CH2P′0), 102.4 (s, C1), 105.0 (s, C3), 109.4 (s, C1 ), 118.1 (s,
5
2
4
134.4 (s, CH=N), 151.3 (s, C0 ), 152.9 (d, 2JCP = 9.8 Hz, C0 ), 155.9
C≡N), 122.2 (d, JCP = 4.5 Hz, C0 ), 122.4 (d, JCP = 4.2 Hz, C1 ),
3
1
3
2
3
2
3
(s, C1).
128.1 (s, C0 ), 128.6 (dd, 1JCP = 111.1, 3JCP = 5.4 Hz, i-C6H5), 128.9
Synthesis 2003, No. 3, 389–396 ISSN 0039-7881 © Thieme Stuttgart · New York

396
V. Maraval et al.
PAPER
(4) Maraval, V.; Sebastian, R. M.; Ben, F.; Laurent, R.;
Caminade, A. M.; Majoral, J. P. Eur. J. Inorg. Chem. 2001,
1681.
(5) Maraval, V.; Laurent, R.; Merino, S.; Caminade, A. M.;
Majoral, J. P. Eur. J. Org. Chem. 2000, 3555.
(d, 3JCP = 12.3 Hz, m-C6H5), 130.5 (s, C0 ), 131.3 (d, 2JCP = 10.2 Hz,
4
o-C6H5), 132.6 (s, p-C6H5), 133.1 (s, C4), 134.0 (s, C1 ), 138.8 (s,
3
3
4
C1CH=N), 140.5 (d, JCP = 13.6 Hz, C0 CH=N), 153.3 (d,
2JCP = 9.4 Hz, C0 ), 153.7 (d, 2JCP = 7.0 Hz, C1 ), 157.5 (s, C2).
1
1
Anal. Calcd for C66H55N11O8P4S3: C, 58.71; H, 4.11; N, 11.41.
Found: C, 58.59; H, 4.15; N, 11.39.
(6) Majoral, J. P.; Caminade, A. M. Chem. Rev. 1999, 99, 845.
(7) (a) Galliot, C.; Larré, C.; Caminade, A. M.; Majoral, J. P.
Science 1997, 277, 1981. (b) Larré, C.; Caminade, A. M.;
Majoral, J. P. Angew. Chem., Int. Ed. Engl. 1997, 36, 596.
(c) Larré, C.; Donnadieu, B.; Caminade, A. M.; Majoral, J.
P. J. Am. Chem. Soc. 1998, 120, 4029. (d) Larré, C.;
Bressolles, D.; Turrin, C.; Donnadieu, B.; Caminade, A. M.;
Majoral, J. P. J. Am. Chem. Soc. 1998, 120, 13070.
(e) Majoral, J. P.; Larré, C.; Laurent, R.; Caminade, A. M.
Coord. Chem. Rev. 1999, 190-192, 3.
(8) Traetteberg, M. Acta Chem. Scand. 1968, 22, 628.
(9) (a) Allcock, H. R.; Tollefson, N. M.; Arcus, R. A.; Whittle,
R. R. J. Am Chem. Soc. 1985, 107, 5166. (b) Bougeard, D.;
Brémard, C.; de Jaeger, R.; Lemmouchi, Y. Phosphorus,
Sulfur Silicon Relat. Elem. 1993, 79, 147.
(10) CCDC 197221 for 1 contains the supplementary
crystallographic data for this paper. These data can be
obtained free of charge via 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)336033; or deposit@ccdc.cam.ac.uk].
(11) Turrin, C. O.; Maraval, V.; Caminade, A. M.; Majoral, J. P.;
Mehdi, A.; Reyé, C. Chem. Mat. 2000, 12, 3848.
(12) Alijarin, M.; Lopez-Leonardo, C.; Llamas-Lorente, P.
Tetrahedron Lett. 2001, 42, 605.
(13) (a) SIR92 - A Program for Crystal Structure Solution:
Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A.
J. Appl. Crystallogr. 1993, 26, 343. (b) SIR97: Altomare,
A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.;
Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G. G.;
Polidori, G.; Spagna, R. J. Appl. Cryst. 1999, 32, 115.
(14) SHELX97 (Includes SHELXS97, SHELXL97, CIFTAB) -
Programs for Crystal Structure Analysis (Release 97-2);
Sheldrick, G. M., Ed.; Institüt für Anorganische Chemie der
Universität: Göttingen, Germany, 1998.
X-Ray Analysis
Data were collected at low temperature (T = 160 K), on a IPDS
STOE diffractometer equipped with an Oxford Cryosystems Cryos-
tream Cooler Device and using a graphite-monochromated Mo-Kα
radiation (λ = 0.71073 Å). Final unit cell parameters were obtained
by means of a least-squares refinement of a set of well-measured re-
flections, and crystal decay were monitored during data collection;
no significant fluctuations of intensities have been observed. Struc-
tures have been solved by Direct Methods using SIR92,13 refined by
least-squares procedures on a F2 with the aid of SHELXL9714 in-
cluded in the software package WinGX version 1.63;15 atomic scat-
tering factors were taken from International tables for X-Ray
Crystallography.16 All hydrogen atoms were located on a difference
Fourier maps but refined by using an idealized model with isotropic
thermals parameters fixed at 20% higher than those of carbon atoms
to which they were connected. All non-hydrogen atoms were aniso-
tropically refined and in the last cycles of refinement a weighting
scheme was used, where weights are calculated from the following
formula: w = 1/[σ2(Fo2) + (aP)2 + bP] where P = (Fo2 + 2 Fc2)/3.
Criteria for a satisfactory complete analysis was the ratio of RMS
shift to standard deviations being less than 0.1 and also no signifi-
cant residuals electronic densities on finals differences maps. Draw-
ing of molecule was performed with the program ORTEP3217 with
50% probability displacement ellipsoids for non-hydrogen atoms.
References
(1) See for instance: Bernasconi, C. F. Tetrahedron 1989, 45,
4017; and references included therein.
(2) See for instance: (a) Märkl, G.; Merkl, B. Tetrahedron Lett.
1981, 22, 4459. (b) Pietrusiewicz, K. M.; Zablocka, M.
Tetrahedron Lett. 1988, 29, 1991. (c) Märkl, G.; Merkl, B.
Tetrahedron Lett. 1981, 22, 4463. (d) Pietrusiewicz, K. M.;
Zablocka, M. Phosphorus, Sulfur Silicon Relat. Elem. 1988,
40, 47.
(3) Maraval, V.; Laurent, R.; Donnadieu, B.; Mauzac, M.;
Caminade, A. M.; Majoral, J. P. J. Am Chem. Soc. 2000, 122,
2499.
(15) WINGX - 1.63 Integrated System of Windows Programs for
the Solution, Refinement and Analysis of Single Crystal X-
Ray Diffraction Data: Farrugia, L. J. Appl. Crystallogr.
1999, 32, 837.
(16) International Tables for X-Ray Crystallography, Vol IV;
Kynoch Press: Birmingham England, 1974.
(17) ORTEP32 for Windows: Farrugia, L. J. J. Appl. Crystallogr.
1997, 30, 565.
Synthesis 2003, No. 3, 389–396 ISSN 0039-7881 © Thieme Stuttgart · New York