Regio- and stereoselective nucleophilic additions of amines, thiols and aminophosphanes to the C{triple bond, long}C bond of P,P-diphenyl-P-(2-phenylethynyl)-λ5-phosphazenes

Article abstract of DOI:10.1016/j.tetlet.2007.07.148

Nitrogen and sulfur nucleophiles, such as amines, thiophenols, and aminophosphanes, add to the triple bond of P-ethynyl-λ⁵-phosphazenes to give regio and diastereoselectively P-ethenyl-λ⁵-phosphazenes. An equally selective substituti

Full text of DOI:10.1016/j.tetlet.2007.07.148

Tetrahedron Letters 48 (2007) 6987–6991
Regio- and stereoselective nucleophilic additions of amines,
thiols and aminophosphanes to the C„C bond of
P,P-diphenyl-P-(2-phenylethynyl)-k5-phosphazenes
*
*
´
´
´
Mateo Alajarın, Carmen Lopez-Leonardo, Pilar Llamas-Lorente and Rosalıa Raja
Departamento de Quı´mica Orga´nica, Facultad de Quı´mica, Campus de Espinardo, 30100 Murcia, Spain
Received 28 June 2007; revised 17 July 2007; accepted 24 July 2007
Available online 27 July 2007
Abstract—Nitrogen and sulfur nucleophiles, such as amines, thiophenols, and aminophosphanes, add to the triple bond of P-ethyn-
yl-k5-phosphazenes to give regio and diastereoselectively P-ethenyl-k5-phosphazenes. An equally selective substitution reaction,
occurring by an addition–elimination pathway, on bis(iminophosphoranyl)ethenes has been also achieved.
Ó 2007 Elsevier Ltd. All rights reserved.
A few examples of nucleophilic addition to the C„C
bond of some classes of P-alkynyl derivatives, such as
phosphane oxides and sulfides, phosphonates and thio-
phosphonates, have been described.1 The results of
these reactions are in agreement with theoretical calcula-
tions showing that these P(V) functionalities are electron
withdrawing and, consequently, play the role of activat-
ing groups in such processes.2 We have previously
disclosed that an iminophosphoranyl function
successfully activate a P-linked C@C bond for Mi-
chael-type addition of a variety of nucleophiles.3 In con-
trast, there is no precedents of similar reactivity over P-
alkynyl-k5-phosphazenes. Moreover, the members of
this class of compounds reported up to now are scarce.4
To our knowledge only their hydrolysis5 and a [3+2]
cycloaddition with diazo compounds6 have been occa-
sionally disclosed.
standard conditions of the Staudinger imination reac-
tion8 (Scheme 1). N-(4-Tolyl) derivative 1a was quite
unstable to be isolated in totally pure form due to the
hydrolytic sensitivity of its P@N bond, but could be
used successfully in crude form in the following reac-
tions. In contrast, the N-acyl and N-sulfonyl derivatives
1b and 1c were isolated in pure state as oils after a simple
work-up and showed to be stable for weeks as far as
they are kept under a nitrogen atmosphere.
The characterization of compounds 1 was straightfor-
ward following their spectral data. Their 31P{1H}
NMR spectra show a singlet appearing between ꢀ16.9
and ꢀ0.5 ppm, remarkably deshielded in relation to
the analogous P-alkenyl-k5-phosphazenes (Dd = 16.7–
18.6 ppm). In their 13C NMR spectra the signals attrib-
uted to the acetylenic carbons appear as doublets, in the
interval 105.6–109.6 ppm for the b-carbon, and in the
Herein, we describe the synthesis of three new P-ethyn-
yl-k5-phosphazenes and the results of the addition reac-
tion of nucleophiles, such as amines, thiophenols, and
aminophosphanes, to their C„C bond.
Ph2P Cl + Ph
H
nBuLi/THF -20 ºC
The P-alkynyl-k5-phosphazenes 1a–c are readily pre-
pared by the stoichiometric reaction of azides and
P,P-diphenyl-P-phenylethynylphosphane7 under the
Ph
R1-N3
Ph2P
Ph2P
Ph
CH2Cl2, rt
N
R1
1a R1= 4-CH3C6H4 (not isolated)
1b R1= 4-CH3C6H4CO (94%)
1c R1= 4-CH3C6H4SO2 (95%)
Keywords: Addition reactions; P-Alkynyl-k5-phosphazenes; Bis(imino-
phosphoranyl)ethenes.
*
Corresponding authors. E-mail addresses: alajarin@um.es; melill@
um.es
Scheme 1. Preparation of P-alkynyl-k5-phosphazenes 1a–c.
0040-4039/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2007.07.148

6988
M. Alajarı´n et al. / Tetrahedron Letters 48 (2007) 6987–6991
range 77.4–81.0 ppm for the a-carbon. In this context, it
is well known that the polarity of a carbon–carbon triple
bond is associated to the difference of the 13C NMR
chemical shifts (Dd) between the signals of their carbon
atoms.2 By comparing these values (for 1a: Dd =
24.66 ppm, 1b: Dd = 28.14 ppm and 1c: Dd =
32.16 ppm) with that of P,P-diphenyl-P-phenylethynyl-
phosphane (Dd = 21.88 ppm)7b and its oxide (Dd =
22.59 ppm)7b it seems clear that the triple bonds of
P-alkynyl-k5-phosphazenes 1a–c are more polar than
those of the precursor P-alkynyl phosphane and its
oxide.
X
Ph2P
R2
N
Ph2P
R1
N
X
R1
R2
E
-2
Z
-2
trans 3
J
CP = 14.1-15.3 Hz
cis 3
JCP = 4.7-8.2 Hz
3
Figure 1. Coupling constants JCP for Z-2 and E-2 isomers.
It is noticeable that for the cases Z-2a and Z-2b, where
X is an NH group, the enamino tautomer, which may
form an intramolecular hydrogen bond with the phos-
phazene N atom, was the only one observed, whereas
in similar compounds where R1 and R2 in structure 2
are 2,6-diisopropylphenyl groups an imino-enamino
equilibrium is clearly established.11
The reaction of P-alkynyl-k5-phosphazenes 1 with a
couple of alkylamines at reflux temperature, and with
4-methoxythiophenol at room temperature, gave rise
to the respective 2-substituted P-alkenyl-k5-phosphaz-
enes 2 (Scheme 2, Table 1).
On the other hand, we have reported that aminophos-
1
2
12
As it has been found in nucleophilic additions to the
C„C bond of other electron-deficient alkynes,9 these
reactions resulted to be totally regioselective, the nucleo-
philic part of the reagents adding to the b-carbon. The
products were isolated as mixtures of Z and E isomers,
except for the case of 2a where the Z isomer is exclu-
sively formed (Table 1). In most cases these two stereo-
isomers could be separated by chromatographic
purification on silica gel deactivated with triethylamine
(5%). The assignment of the double bond geometries
was made on the basis of the coupling constants trans
phanes ðR2P–NH–R Þ
are excellent nucleophilic
species in reactions with activated alkyl halides13 and
carbon–carbon double bonds.3 In such reactions, the
aminophosphanes experience regioselective P-alkyl-
ations and consequently they behave as synthetic equiv-
alents of iminophosphide anions ½R12P@NR2ꢁꢀ. For this
reason they can be considered as iminophosphoranyl
synthons.
When a couple of N-aryl aminophosphanes were reacted
with P-alkynyl phosphazenes 1 the presumed asym-
metrically substituted bis(iminophosphoranes) 3a–d14
derived from 1-phenyl-1,2-bis(diphenylphosphino)ethene,
were obtained in good yields (Scheme 3). These nucleo-
philic additions proceed with total regio- and diastereo-
selectivity, affording exclusively the E-isomers.
3
3JCP (Z isomers) and cis JCP (E isomers) between the
phosphorus atom and the ipso carbon of the 2-phenyl
group in their 13C NMR spectra (Fig. 1). These data
show a clear and simple pattern in which trans
3
3JCP > cis JCP. Furthermore, the ranges are such (trans
3JCP 14.1–15.3 Hz and cis 3JCP 4.7–8.2 Hz) that it is pos-
sible to assign the stereochemistry confidently when only
a single isomer is obtained. These J values are in agree-
ment with other previous reports showing that in P-
alkenyl P(V) compounds the value of both 3JCP coupling
constants are in the ranges: trans 3JCP 16.4–23.7 Hz and
A careful scrutiny of the NMR data of compounds 3,
3
paying particular attention to the values of the JHP
,
3JCP, and 3JPP coupling constants allowed the unambig-
uous assignment of their E-geometries (Fig. 2). For
3
cis JCP 4.0–7.5 Hz.10
R2
N
Ph
Ph
PPh2
C6H6
Ph2P
Ph
Ph2P-NH-R2
C6H6
Ph2P
Ph2P
+
+
R2-XH
Ph2P
N
Ph
reflux, 4 h
R1
N
N
X
rt or reflux
R1
R1
R2
N
R1
R1= 4-CH3C6H4CO R2= 4-CH3C6H4
3a
1
72%
68%
66%
R1= 4-CH3C6H4CO R2= 4-CH3OC6H4 3b
3c
R1= 4-CH3C6H4SO2 R2= 4-CH3OC6H4 3d
2
1
R1= 4-CH3C6H4SO2 R2= 4-CH3C6H4
R1= 4-CH3C6H4, 4-CH3C6H4CO, 4-CH3C6H4SO2
R2= iPr, C6H5CH2, 4-CH3OC6H4
X= NH, S
95%
Scheme 3. Synthesis of E-bis(iminophosphoranyl)ethenes 3 by addi-
tion of N-aryl aminophosphanes to P-alkynyl-k5-phosphazenes 1.
Scheme 2. Nucleophilic addition to P-alkynyl-k5-phosphazenes 1.
Table 1.
Compound
X
R1
R2
Ratio Z/E
Z (%)
E (%)
2a
2b
2c
2d
NH
NH
S
4-CH3C6H4
4-CH3C6H4SO2
4-CH3C6H4
iPr
PhCH2
4-CH3OC6H4
4-CH3OC6H4
100/0
63/37
80/20
80/20
41
44
49
—
22
12
a
a
S
4-CH3C6H4CO
—
—
a Global yield: 76%, E and Z isomers not separated.

M. Alajarı´n et al. / Tetrahedron Letters 48 (2007) 6987–6991
6989
R2
form 7, which may rotate around the central C–C single
bond.
H
N
2JHP
cis 3JCP = 8.2-9.7 Hz
trans 3
PP = 43.6-45.5 Hz
=
cis 3JHP = 20.3-20.7 Hz
PPh2
Ph2P
The most diastereoselective addition reactions on com-
pounds 1 among all presented here are those leading
to 3a–d, which yield exclusively E isomers. This selectiv-
ity can be tentatively interpreted as resulting from a ra-
pid internal proton transfer occurring at intermediate E
zwitterions 5. In these cases, the cis relationship between
the carbanionic sp2 orbital and the proton-releasing
aminophosphonium unit facilitates such proton trans-
fer, via a 5-center transition state (Scheme 5), thus mak-
ing this step particularly rapid when compared with the
alternative, presumably intermolecular proton transfer
collapsing of 4 to Z-2.
J
N
R1
E
-3
Figure 2. Significant coupling constant values of compounds 3.
1
3
example, in their H NMR spectra the value of JHP is
close to 21 Hz, coincident with other reports of cis
3JHP coupling constant in P-vinyl-k5-phosphazenes3a
and analogous bis(sulfides) or bis(oxides).10a,15 In addi-
tion, the quaternary ipso carbon of the C-phenyl group
3
show a JCP = 8–10 Hz, which is in the typical range of
In view of the presumed acceptor properties of the C@C
bond of 1,2-bis(iminophosphoranyl)ethenes 3, bearing
one electron withdrawing group at each carbon, we
decided to test their reactions with thiophenols,
although keeping in mind the possibility that such reac-
tions could not be highly regioselective (as the chemodif-
ferentiation between the two terms of the C@C bonds
seems, a priori, minimal). Rather surprisingly, the prod-
ucts of these reactions were not mixtures of the expected
two regioisomeric addition products but instead k5-
phosphazenes 819 and the corresponding acyl or sulfonyl
aminophosphane 9 were the only isolated products.
Note that the reactions required slightly harsher condi-
tions for completion than others here previously dis-
closed (toluene, reflux) (Scheme 6).
3
cis JCP values of comparable structures.10a,15,16 The
most significant data of their 31P NMR is the 3JPP value,
close to 45 Hz, in agreement with typical values found
for two phosphorus(V) atoms in trans-1,2-positions of
a carbon–carbon double bond.15–17
The stereochemical course of these latter addition reac-
tions is difficult to rationalize on the basis of the well
established general mechanism of the nucleophilic addi-
tions to electron-deficient alkynes.18 Following this gen-
eral mechanism, the attack of a neutral nucleophile
NuH on activated alkyne 1 should initially occur in
an anti fashion to give Z-vinyl zwitterion 4 in preference
to E isomer 5, although both intermediates can isomer-
ize across the linear sp-hybridized zwitterion 6 and its
various resonance contributors. The formation of the
final products (Z-2, of kinetic control, or E-2 and E-3,
of thermodynamic control) will depend on the relative
rates of isomerization versus proton transfer (Scheme
4). In addition, the initially formed Z or E isomers can
directly isomerize, via the intermediacy of zwitterionic
Thus, the R3S group has replaced regio- and stereoselec-
tively one of the two iminophosphoranyl groups at the
R2
R2
N
H
N
Ph
Ph
P
H
PPh2
Ph2P
Ph
Ph2P
Ph
Ph
N
N
R1
R1
Ph2P
N
5
E-3
R1
Scheme 5. Intramolecular proton transfer in intermediate 5 via a 5-
center transition state.
1
NuH
NuH
NuH
Ph
Ph
Ph
R2
N
Ph2P
Ph2P
Ph2P
NuH
NuH
toluene
reflux, 12 h
N
PPh2
+
R3-SH
R1
Ph2P
N
N
R1
R1
N
Ph
4
6
5
R1
3
R2
N
transfer
H
transfer
H
+
Ph2P-NH-R1
PPh2
R3S
H
Ph
Nu
H
Nu
Ph
H
Ph
Nu
Ph
R2 = 4-CH3C6H4, R3 = 4-CH3C6H4
R2 = 4-CH3OC6H4, R3 = 4-CH3OC6H4
R2 = 4-CH3C6H4, R3 = 4-CH3OC6H4
R2 = 4-CH3OC6H4, R3 = 4-CH3OC6H4
8a 75% R1 = 4-CH3C6H4SO2
Ph2P
Ph2P
Ph2P
9a 60%
9a 50%
9b 52%
9b 47%
8b 93% R1 = 4-CH3C6H4CO
N
N
N
R1
R1
R1 = 4-CH3C6H4SO2
R1 = 4-CH3C6H4SO2
R1
8c 83%
8b 80%
Z-2
7
E
-2 and E-3
Scheme 4. Mechanistic proposal for the formation of compounds 2
and 3.
Scheme 6. Selective substitution reaction of one iminophosphoranyl
group of bis(iminophosphoranyl)ethenes 3.

6990
M. Alajarı´n et al. / Tetrahedron Letters 48 (2007) 6987–6991
C@C double bond, more specifically that bearing R1
(ArCO or ArSO2), which is now found in aminophos-
phane 9, whereas the second iminophosphoranyl func-
tion bearing R2 (Ar) remains at its original place.
regioselectivity and high levels of diastereoselectivity.
We have also shown that one iminophosphoranyl group
of 1,2-bis(iminophosphoranyl)ethenes, differently substi-
tuted at their two N atoms, can be replaced by an ArS
residue in a totally controlled way, under thermody-
namic equilibrium conditions, via an addition–elimina-
tion sequence.
These results can be reasonably approximated by
assuming an addition–elimination sequence of events.
First, a regioselective addition of thiol to the C@C bond
takes place,20 incorporating the R3S fragment to the less
substituted carbon of the starting alkene, to give 10
(Scheme 7). Then a b-elimination of aminophosphane
Ph2P–NH–R1 should occur for leading to final products
8 and 9. Note that the N atom of the P@N function,
notably electronegative by virtue of the contribution of
the ylidic +P–Nꢀ resonance form, can reasonably act
as an internal base promoting a 5-center concerted b-
elimination. However, a second alternative b-elimina-
tion is also conceivable involving the other iminophos-
phoranyl group of 10 and leading to the functionalized
alkene 11 and aminophosphane 12 Ph2P–NH–R2. Hav-
ing no doubt the reaction products are exclusively 8 and
9, we interpret the course of these processes as resulting
of a thermodynamic equilibrium between the product
couples 8/9 and 11/12 established across the sterically
congested tetrasubstituted ethane 10 under the reaction
conditions, in which the final composition of the reac-
tion mixture (8 + 9) is determined by the rather irrevers-
ible transformation step 10!8 + 9. The inverse reaction
8 + 9!10 should be quite slow due to the low nucleo-
philicity of N-acyl or sulfonyl aminophosphane 9 as a
result of the delocalization of the N lone pair over the
conjugated C@O or S@O bonds. On the contrary, N-
aryl aminophosphane 12 is able of adding efficiently to
11, thus sustaining their reversible equilibrium with 10.
In support of this last proposal, we have previously
established that N-aryl aminophosphanes add to the
C@C bond of P-alkenyl phosphazenes to yield 1,2-
bis(iminophosphoranyl)ethanes.3b
Acknowledgments
This work was supported by the MEC and FEDER
(Project CTQ2005-02323/BQU) and Fundacio´n Se´neca-
CARM (Project 00458/PI/04). P.L.-L. also thanks Fun-
dacio´n Se´neca-CARM for a fellowship.
References and notes
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In summary the present investigations have explored the
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P-ethynyl-P,P-diphenyl-k5-phosphazenes. The resulting
tri-substituted alkenes have been obtained with total
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R2
R2
N
R3-S
Ph2P
H
N
R3-SH
PPh2
PPh2
Ph2P
N
Ph
H
Ph
N
R1
R1
3
10
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R2
R3-S
N
Ph
Ph P-NH-R1
Ph P-NH-R2
PPh2
Ph2P
+
+
R3-S
2
2
N
R1
Ph
8
9
11
12
R1 = 4-CH3C6H4CO, 4-CH3C6H4SO2
R2 = 4-CH3C6H4, 4-CH3OC6H4
R3 = 4-CH3C6H4, 4-CH3OC6H4
´
´
12. Alajarın, M.; Lopez-Leonardo, C.; Llamas-Lorente, P.
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Synlett 2003, 801–804.

M. Alajarı´n et al. / Tetrahedron Letters 48 (2007) 6987–6991
6991
14. Bis(iminophosphoranyl)ethene 3a: Yield: 72%; mp 76–
78 °C (yellow prisms from dichloromethane/diethyl ether);
1H NMR (200 MHz, CDCl3): d 2.29 (s, 3H, CH3), 2.43 (s,
3H, CH3), 6.49 (d, 2H, 3JHH = 8.0 Hz, Harom), 6.64 (t, 2H,
C.; Steigelmann, O.; Wilkinson, D. L.; Muller, G. Chem.
¨
Ber. 1989, 1857–1861; (c) Kawaguchi, S.; Nagata, S.;
Shirai, T.; Tsuchii, K.; Nomoto, A.; Ogawa, A. Tetrahe-
dron Lett. 2006, 47, 3919–3922.
3
3JHH = 7.6 Hz, Harom), 6.84 (d, 2H, JHH = 8.0 Hz,
18. Semmelhack, M. F. In Comprehensive Organic Synthesis;
Trost, B. M., Fleming, I., Eds.; Oxford, 1991; Vol. 4, pp
47–53.
3
H
arom), 6.85–6.89 (m, 1H, Harom), 6.98 (d, 2H, JHH
=
8.0 Hz, Harom), 7.14–7.52 (m, 18H, 2Harom + Ph2), 7.69–
2
7.79 (m, 4H, Ph2), 8.06 (t, 1H, JHP = 3JHP = 20.4 Hz,
19. Iminophosphorane 8c: Yield: 87%; mp 124–126 °C (yellow
prisms from chloroform/pentane); 1H NMR (400 MHz,
CDCl3): d 2.22 (s, 3H, CH3), 3.77 (s, 3H, OCH3), 6.74 (d,
3
CH@C), 8.20 (d, 2H, JHH = 8.0 Hz, HHarom); 13C{1H}
NMR (50 MHz, CDCl3): d 20.76 (CH3), 21.63 (CH3),
3
3
3
124.21 (d, JCP = 16.1 Hz), 126.95, 127.24 (q), 127.39
2H, JHH = 8.0 Hz, Harom), 6.79 (d, 2H, JHH = 8.8 Hz,
3
3
(dright, Ci), 127.59, 128.44 (d, JCP = 11.2 Hz, 2 Cm),
H
H
arom), 6.87 (d, 2H, JHH = 8.0 Hz, Harom), 7.01 (m, 2H,
arom), 7.19 (d, 2H, JHH = 8.8 Hz, Harom), 7.20–7.25 (m,
3
128.56, 129.35–129.47 (aromatics), 129.67 (d, JCP
=
=
2
1.7 Hz), 131.70–131.88 (Co + 2Cp), 133.13 (d, JCP
3H, Harom), 7.31–7.36 (m, 4H, Ph2), 7.41–7.45 (m, 2H,
Ph2), 7.59–7.64 (m, 4H, Ph2), 7.79 (d, 1H, 3JHP = 16.5 Hz,
CHS) 13C{1H} NMR (100 MHz, CDCl3): d 20.64 (CH3),
2
9.0 Hz, Co), 133.47 (d, JCP = 3JCP = 8.4 Hz, q), 135.83
3
1
(d, JCP = 18.7 Hz, q), 136.33 (dd, JCP = 66.9 Hz,
2JCP = 12.2 Hz, PCH@CP), 140.95 (q), 148.18 (d,
3
55.42 (OCH3), 114.90, 123.44 (d, JCP = 17.7 Hz), 124.93
2JCP = 2.0 Hz, q), 150.38 (d, JCP = 61.8 Hz, PCH@CP),
(q), 126.35 (q), 126.69 (d, JCP = 89.7 Hz, CH=CP),
1
1
176.82 (d, JCP = 17.7 Hz, CO); 31P{1H} NMR (81 MHz,
128.02 (d, JCP = 1.5 Hz), 128.34 (d, JCP = 11.9 Hz,
2
5
3
3
3
3
CDCl3): d 6.77 (d, JPP = 44.1 Hz), 7.98 (d, JPP
=
Cm), 128.60, 129.33, 129.76 (d, JCP = 4.0 Hz), 130.00 (d,
4
44.1 Hz); IR (Nujol): m = 1540, 1505, 1439, 1337, 1176,
1114 cmꢀ1; MS (FAB+): m/z (%) = 712 (45) [M++2], 711
(95) [M++1], 710 (48)[M+], 303 (100); Anal. Calcd for
C47H40N2OP2 (710.78): C, 79.42; H, 5.67; N, 3.94. Found:
C, 79.59; H, 5.76; N, 3.82.
1JCP = 100.3 Hz, Ci), 131.58 (d, JCP = 2.6 Hz, Cp),
2
132.62, 132.88 (d, JCP = 9.3 Hz, Co), 135.56 (d,
2JCP = 8.8 Hz, q), 148.40 (q), 148.58 (d, JCP = 12.6 Hz,
2
CHS), 159.67 (q); 31P{1H} NMR (161 MHz, CDCl3): d
2.43; IR (Nujol): m = 1505, 1439, 1335, 1172, 1110 cmꢀ1
;
15. Sato, A.; Yorimitsu, H.; Oshima, K. Angew. Chem., Int.
Ed. 2005, 44, 1694–1696.
16. Banert, K.; Fendel, W.; Schlott, J. Angew. Chem., Int. Ed.
1998, 37, 3289–3292.
17. (a) Colquhoun, I. J.; McFarlane, W. J. Chem. Soc., Dalton
Trans. 1982, 1915–1921; (b) Schmidbaur, H.; Paschalidis,
MS (EI): m/z (%) = 532 (22) [M++1], 531 (54) [M+], 291
(100); Anal. Calcd for C34H30NOPS (531.65): C, 76.81, H,
5.69, N, 2.63. Found: C, 76.75, H, 5.77, N, 2.71.
20. The basicity of the phosphazene functions may contribute
to promote the addition of relatively acidic neutral
nucleophiles such as thiols.