A convenient approach to λ5-phosphinines via interaction of phosphorylated 3-pyrrolidinocrotonitrile with 2-bromoacetophenones

Article abstract of DOI:10.1016/j.tet.2007.03.172

The alkylation of 2-(diphenylphosphino)-3-pyrrolidin-1-ylbut-2-enenitrile with a set of bromoacetophenones has been studied. Cyclization of the phosphonium salts into 6-cyano-3-hydroxy-3-aryl-1,1-diphenyl-5-pyrrolidin-1-yl-1,2,3,4-tetrahydrophosphininium

Full text of DOI:10.1016/j.tet.2007.03.172

Tetrahedron 63 (2007) 5656–5664
5
A convenient approach to l -phosphinines via interaction
of phosphorylated 3-pyrrolidinocrotonitrile with
2
-bromoacetophenones
*
Yurii V. Svyaschenko, Alexandr N. Kostyuk, Bogdan B. Barnych
and Dmitriy M. Volochnyuk
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanskaya 5, Kiev 94, 02094, Ukraine
Received 19 December 2006; revised 9 March 2007; accepted 29 March 2007
Available online 4 April 2007
Abstract—The alkylation of 2-(diphenylphosphino)-3-pyrrolidin-1-ylbut-2-enenitrile with a set of bromoacetophenones has been studied.
Cyclization of the phosphonium salts into 6-cyano-3-hydroxy-3-aryl-1,1-diphenyl-5-pyrrolidin-1-yl-1,2,3,4-tetrahydrophosphininium bro-
mides under heating in the presence of catalytic amount of a base is discussed. Starting both from the acyclic and the cyclic phosphonium
5
salts, new types of l -phosphinines have been synthesized.
Ó 2007 Published by Elsevier Ltd.
1. Introduction
There are few such methods depicted in Figure 1.
The phosphorus-containing heterocycles are a less numerous
and less accessible class of compounds in comparison with
the classical nitrogen or sulfur heterocycles. However, in-
The first synthesis of phosphinine comprises double
alkylation of potassium phosphide with 1,5-bishalogen
derivative II followed by oxidation (Way 1). Later use of
1
7a
7
b,c
terest in this class of compounds, especially toward the
ones with an endocyclic P–C bond, has increased due to their
recent use in a wide variety of areas such as model objects in
unsaturated derivatives, acetylenes IV,
in the reaction
with primary phosphines allowed circumvention of the oxi-
dation stage, an umpolung approach of the reaction was also
studied utilizing dihalogenophosphines (Way 2). In both
2
3
7d
fundamental research, as ligands for new catalysts, for
modifying properties of materials, and as important build-
ing blocks for drug discovery.
4
5
cases, l -phosphinines are formed in the course of 4-
methoxy-1,4-dihydrophosphinine rearrangement. Another
5
5
synthetic approach to l -phosphinines is based on the
recyclization of phosphapyrillium salt IX followed by
Among the most important representatives of the phospho-
rus containing heterocycles l - and l -phosphinines should
3
5
7e
reduction with SiHCl (Way 3). All these approaches are
3
6
be noted. These two classes differ in the coordination state
of the phosphorus atom and confer marked difference in
either multistep syntheses with low total yields or include
steps with unstable, highly reactive or fairly inaccessible
compounds.
5
their chemical properties. For example, unlike l -phosphi-
nines, l -phosphinines are air-sensitive compounds and
3
5
their handling requires special laboratory equipment and
synthetic procedures. At the same time the majority of the
methods for synthesis of l -phosphinines is based on oxida-
Recently we have found a convenient approach to l -phos-
phinines based on the reaction of phosphonium salt XI, a
1,5-bisnucleophile, with the 1,1-biselectrophile, DMFDMA.
In this work we describe that phosphines of type X can act as
1,4-bisnucleophiles with 1,2-biselectrophilic bromoaceto-
phenones.
5
3
5
tion of l -phosphinines so that even l -phosphinines are
fairly inaccessible compounds with limited practical use.
5
Synthetic approaches to l -phosphinines circumventing
the formation of l -phosphinines would certainly solve
many above-mentioned problems.
3
2. Results and discussion
The lack of a convenient synthetic procedure for preparation
of phosphine 1 prompted us to optimize an available proce-
dure. The procedure developed for preparation of the starting
phosphine 1 does not require reducing the corresponding
5
Keywords: l -Phosphinines; Phosphonium salts; Phosphorylated enamines;
2
*
-Bromoacetophenones.
Corresponding author. Tel.: +380 44 5373218; fax: +380 44 5373253;
e-mail: a.kostyuk@enamine.net
0
040–4020/$ - see front matter Ó 2007 Published by Elsevier Ltd.
doi:10.1016/j.tet.2007.03.172

Y. V. Svyaschenko et al. / Tetrahedron 63 (2007) 5656–5664
5657
MeO
OMe
OMe
+
RPH2
RPCl2
R'
IV
MeO
P
R
+
R'
2 steps
Br
Br
P
VI
+
MeO
R
R
Li
Li
II
+
R PK
III
Way 2
V
2
6
steps
R'
Way 1
NAlk2
Way 4
R
EWG
Me
Me
Me
Me
Me
P
+
-
I
P
R
X
R
R
Me C
P
R
R
3
E+
XI
Way 3
steps
VII
5
Way 5
NAlk2
Me
O
R
EWG
This work
Me
Me C
3
+
PR2
+
R
O
P
Br-
Me
P
X
E+
Me C
3
-
Br
VIII
IX
Me
EWG
Alk N
2
5
Figure 1. Available methods for synthesis of l -phosphinines circumventing the formation of l -phosphinines.
3
8
a
phosphine selenide. We have found that neat phosphine 1
prepared by direct phosphorylation of pyrrolidinocrotononi-
that the phosphonium salts of type 2 are easily converted
1
0
into stabilized phosphorane ylides. Indeed, bases such as
aqueous sodium carbonate or triethylamine transformed the
phosphonium salts into stabilized ylides 3a–c. Compounds
of type 3a–c bearing a carbon atom instead of a phosphorus
atom are known to cyclize into benzene derivatives upon
8
trile is quite stable and could be recrystallized from ethanol.
The procedure allows us to prepare it in gram scale batches.
Alkylation of phosphines with alkyl halogens bearing an
electron–acceptor group is known to be a quite complicated
process that in many cases does not lead to phosphonium
salts. Fortunately, in our case phosphine 1 reacts with bro-
moacetophenones in benzene affording phosphonium salts
1
1
treatment with bases. In the case of compounds 3a–c due
to conjugation with the ylide, the electrophilicity of carbonyl
group is markedly decreased compared to the carbon ana-
logues. Various attempts to cyclize these compounds at ele-
vated temperature with and without triethylamine lead to
pronounced resinification of the reaction mixtures that con-
9
2a–c in high yield. Moreover, the phosphonium salts precip-
itate leaving admixture in the solution (Scheme 1).
3
1
tain 10–15% of phosphinines 5 as judged from P NMR and
HPLC–MS spectra. Ylides 3 behave likewise upon treatment
Our main objective was to cyclize the phosphonium salts 2a–
c into the corresponding phosphinines 5a–c. It is well known
ꢀ
with strong bases such as DBU in DMF (100 C) and LDA in
Me
+
Me
Me
CN
CN
PPh2
Ar
N
O
N
O
i
ii
CN
N
PPh2
Br
PPh2
Ar
2a-c
1
3a-c
iii or iv
v
Ar = a: Ph; b: p-MeOPh; c: p-NO Ph
2
Ph
Ph
NC
N
P
N
vi
CN
Ar
+
PPh2 Br
HO
Ar
4
a-c
5a-c
2
, 1 equiv base; (iii) benzene, 80 C, 0.1 equiv base; (iv) benzene, 80 C,
ꢀ
ꢀ
Scheme 1. Reagents and conditions: (i) ArCOCH
ꢀ
2
Br, benzene, 7–10 h; (ii) CH
ꢀ
2
Cl
0
.1 equiv 6; (v) 150 C, 0.03 Torr; (vi) DMF, microwave, 220 C, 5 min.

5658
Y. V. Svyaschenko et al. / Tetrahedron 63 (2007) 5656–5664
ꢀ
product in pure form.
THF (ꢁ78 C) so that it is impossible to separate the target
ylide 7, a strong base, removes a proton from the acyclic
salt 2 turning it into the final cyclic phosphonium salt 4
and liberating ylide 3 so that the whole cycle can be repeated
(Scheme 3). Additional proof supporting the mechanism is
the fact that the reaction proceeds analogously when the cor-
responding ylide (0.1 equiv) is used instead of an organic
base (0.1 equiv).
Analysis of MS spectrum (of ylide 3a) revealed the presence
of a peak that can be ascribed to phosphinine 5a (M¼420).
Thus, it was logical to assume that under analogous condi-
tions ylides 3 could be transformed into phosphinines 5. In-
deed, heating ylides 3 neat at 150 S in vacuo (0.03 Torr) for
5 min afforded the corresponding phosphinines 5 in moder-
ate yields (33–35%). It should be noted that except for phos-
ꢀ
Me
CN
phinines 5, in the course of the reaction the phosphineoxide
of phosphorylated enamine 1 is formed, most probably via
Me
N
O
8
b
CN
3
1
PPh2
thermal intermolecular Wittig reaction as judged by
NMR and HPLC–MS spectra. Thus, we conclude that ylides
undergo thermal cyclization leading to cyclic ylides 7
followed by dehydration thus affording the final phosphinines
(Scheme 2).
P
HO
Ar
PPh2
Ar
3
3
6
2
5
0.1 B:
N
2
N
[
1,7]-
CN
CN
sigmatropic
shift
N
N
+
Br
3
CN
PPh2
CN
PPh2
5
HO
Ar
PPh2
HO
PPh2
-
H O
Ar
2
4
7
HO
HO
Ar
Ar
Scheme 3.
6
7
Scheme 2.
5
The most obvious approach to l -phosphinines is by dehy-
dration and dehydrohalogenation of phosphonium salts
4
Searching to improve yields we tested other procedures.
Thus, heating for 10 h at a temperature of 100 C ylide
a–c. This simple looking transformation was very difficult
ꢀ
a in DMF with 3 equiv of trimethylchlorosilane followed
afforded 2-(diphenylphos-
to accomplish. The reaction in pyridine using thionyl chlo-
ride proceeds with considerable resinification of the reaction
mixture. As in the case of ylide 3 treatment of these salts
with strong bases such as LDA, DBU, dimsyl sodium or
a methanol–water solution of potassium hydroxide resulted
in a mixture of products containing predominantly the phos-
3
by treatment with water
1
2
1
3
phoryl)-1-phenylethanone in 81% yield. Under analogous
conditions the phosphonium salt 2a gave only 63% 2-(di-
phenylphosphoryl)-1-phenylethanone. As cleavage of
aminophosphonium salts is well known in the case of the
salts bearing enamine residue, that is, vinylogous amines,
31
phineoxide of enamine 1 as judged by P NMR and HPLC–
MS spectra.
8b
1
4
one can assume that cleavage proceeds analogously. At
the same time boiling salts 2 in the presence of catalytic
amounts of bases such as triethylamine or Hunig’s base af-
forded cyclic phosphonium salts 4 (Scheme 1). It should be
noted that the reaction was run in nonpolar solvents such as
benzene or toluene where both the starting salts 2 and the
resulting cyclic salts 4 are very poorly soluble. In the course
of the reaction organic by-products remain in solution so
that it is very easy to separate the target products. Monitor-
ing the reaction was conducted by taking P NMR spectra
of the precipitate periodically. Taking into account the fact
that upon treatment with a base, salts 2 are converted into
ylides 3 that thermally cyclize into the phosphinines as
well as the fact that both the starting and the targeted phos-
phonium salts are in precipitate in the course of the reaction
one can assume that this transformation proceeds via
ylide 3.
As the cyclic phosphonium salts 4a–c are high melting com-
pounds, flash vacuum pyrolysis requires high temperatures
so that under these conditions we failed to obtain any indi-
vidual compound. However, under microwave irradiation
at 220 C the salt 4a was transformed into the corresponding
phosphinine 5a.
ꢀ
Quite unexpected results were obtained in the reaction of the
cyclic phosphonium salts with DMFDMA as a base. Thus,
heating the phosphonium salts 4 in DMFDMA results in
a mixture of phosphinines 5 and 8 in various ratios
3
1
(
Scheme 4).
O
Ph
Ph
Ph
Ph
NC
N
P
NC
N
P
i
Ar
4a-c
+
Ar
The following mechanistic pathway was proposed to ratio-
nalize the reaction (Scheme 3). The reaction starts with par-
tial transformation of salt 2 into ylide 3 upon treatment of
a base. Ylide 3 undergoes [1,7]-sigmatropic H-shift afford-
ing cyclic ylide 7 as in the case of the flash vacuum pyrolysis
described above. We have already mentioned that thermal
cyclization of ylide 3 in a solution failed probably due to
low stability of the intermediate cyclic ylide 7. In this case
5
a 30%
b traces
c 85%
8a70%
8b~100%
8c15%
5
5
Ar = a: Ph; b: p-MeOPh; c: p-NO Ph
2
ꢀ
Scheme 4. Reagents and conditions: (i) DMFDMA, 110 C, 2 h. Ratios of
compounds 5 and 8 are given based on chromato-mass spectrometry data
of the reaction mixtures.

Y. V. Svyaschenko et al. / Tetrahedron 63 (2007) 5656–5664
5659
N
N
DMFDMA insertion -
H-shift
N
H
CN
CN - HNMe2
Ph
+
CN
N
PPh2
P
-
PPh2
N
N
O
Ph
Ar
9
Ar 10
O
Ar 11
O
4
+ DMFDMA
8
N +
N
N
CN
PPh2
CN
CN
-
DMFDMA insertion
Ph - HNMe2
O
P
PPh2
O
Ar
N
N
Ph
N
12
Ar 13
Ar 14
O
Scheme 5.
Formation of phosphinines 5 proceeds via dehydrogenation
and dehydrohalogenation of the starting phosphonium
salts. At the same time synthesis of phosphinines 8 could
be rationalized by the following scheme (Scheme 5).
We have synthesized compound 8 by an alternative
method, namely the reaction of the phosphonium salts
8
a
2a–c with DMFDMA under heating. It should be noted
that these l -phosphinines could be prepared under milder
5
DMFDMA can react at both CH groups of the cyclic phos-
2
conditions. Thus, phosphine 16 prepared from its selenide
15 by the reaction with P(NMe ) was treated in situ
2 3
8
a
phonium salts 4 affording intermediates 9 or 12. Both these
intermediates could undergo opening of the cycle giving
acyclic ylides 10 or 13, further cyclization followed by
elimination of dimethylamine in both cases lead to the final
with bromoacetophenones at room temperature affording
l -phosphinines 8a–c. The cyclization proceeds spontane-
ously followed by elimination of dimethylamine (Scheme 6).
5
8
a
phosphinines 8.
Use of Ac O in the presence of AcONa leads to the phosphi-
2
nines 17a–c being acylated at the 6-position of the phosphi-
nine heterocycle (Scheme 7). The reaction proceeds in low
yields; moreover phosphinine 17c was only obtained in trace
amounts.
O
Ph
Ph
NC
N
P
i
Ar
2a-c
It should be noted that in this case unstable ylide 7 formed at
the first stage undergoes acylation at the ylidic carbon atom
followed by dehydration. Alternative compounds of type 18
that can be formed by the recyclization mechanism given
for DMFDMA could not be ruled out. Nevertheless, no evi-
dence for their formation was found. Moreover, the structure
of phosphinine 17 was confirmed by NOE experiment
(Scheme 7).
8
a-c
iii
N
N
ii
CN
CN
N
N
PPh2
PPh2
Se
1
5
16
3. Conclusion
Ar = a: Ph; b: p-MeOPh; c: p-NO Ph
2
ꢀ
In conclusion, we have found a convenient and simple
method for the synthesis of different derivatives of l -
Scheme 6. Reagents and conditions: (i) DMFDMA, 110 C; (ii) benzene,
Br.
5
P(NMe
2
)
3
; (iii) benzene, ArCOCH
2
weak NOE
H
O
O
H O
Ph
Ph
Ph
Ph
Ph
NC
N
P
NC
N
P
NC
N
P
H
strong NOE
Me
Ar
i
4
a-c
H
Ar
17a
1
8
17a-b
CH2
H
Ar = a: Ph; b: p-MeOPh
strong NOE
ꢀ
Scheme 7. Reagents and conditions: (i) Ac
2
O, AcONa, 140 C.

5660
Y. V. Svyaschenko et al. / Tetrahedron 63 (2007) 5656–5664
phosphinines. The starting materials are readily available
enamines and bromoacetophenones. It was shown that the
phosphonium salts prepared by alkylation of 2-(diphenyl-
phosphino)-3-pyrrolidin-1-ylbut-2-enenitrile with bromo-
acetophenones gave stabilized ylides upon treatment with
an equimolar amount of a base, but their treatment with cat-
alytic amounts of a base leads to the cyclic phosphonium
salts. Reaction conditions for transformation of the ylides
and the cyclic phosphonium salts into the corresponding 5-
C H N P requires: C 74.98; H 6.61; N 8.74; P 9.67%];
20 21 2
3
3
dP ꢁ10.2; d (C D ) 7.83 (4H, dd, JHH 7.5 Hz, JPH
H
6 6
7.5 Hz, PPh ), 7.09–7.25 (6H, m, PPh ), 3.04 (4H, br m,
2
2
NCH ), 2.02 (3H, s, CH ), 1.03 (4H, br m, CH ); d
C
2
3
2
2
1
(C D ) 164.5 ( J 40.6 Hz, C(3)), 139.0 ( J 8.2 Hz,
6
6
CP
CP
2
PPh ), 133.4 ( J 20.2 Hz, PPh ), 128.7 (PPh ), 128.7
2
( J 5.1 Hz, PPh ), 121.6 ( J 3.8 Hz, CN), 68.3 ( J
CP
2
CP
2
3
2
1
CP
2
CP
11 Hz, C(2)), 50.9 (NCH ), 25.1 (CH ), 20.8 (C(4)); m/z
2
2
+
(EI): 320 (M , 100), 243 (18), 212 (61), 183 (30), 108
(58), 70 (14), 42 (20%).
5
aryl-2-cyano-3-pyrrolidin-1-yl-1l -phosphinines have been
found. In addition, it was found that dehydration of the
cyclic phosphonium salts with DMFDMAwas accompanied
with formylation and recyclization and the dehydration
4.2. General procedure for acyclic phosphonium salts
with Ac O in the presence of AcONa was accompanied
2
Procedure A. To a stirred solution of phosphine 1 (0.5 g,
1.6 mmol) in benzene (10 mL) under dry argon, a solution
of an appropriate bromoacetophenone (1.7 mmol) was
added. After 4 days the precipitated solid was collected by
filtration and washed with benzene (20 mL) or acetone
with acylation at the 6-position of the phosphinine hetero-
cycle. Plausible mechanisms of these transformations were
discussed.
(20 mL) for 2c.
4. Experimental
4.2.1. (1-Cyano-2-pyrrolidin-1-ylprop-1-enyl)(2-oxo-2-
phenylethyl)diphenylphosphonium bromide (2a). Proce-
4
.1. General
dure A was applied; off-white solid (0.63 g, 77%); mp
195–196 C (benzene); [found: C 64.70; H 5.39; Br
ꢀ
All procedures with compounds sensitive to hydrolysis and
oxidation were carried out in an atmosphere of dry argon.
All solvents were purified and dried by standard methods.
15.29; N 5.43; P 6.01. C H BrN OP requires: C 64.75;
2
8
28
2
H 5.43; Br 15.38; N 5.39; P 5.96%]; nmax (KBr): 3052,
3014, 2875, 2786, 2179, 1675, 1542, 1436, 1403, 1346,
1
31
H and P NMR spectra were recorded on a Varian VXR-
300 spectrometer: H (300 MHz), C D , CDCl or DMSO-
d6 as solvents with TMS as an internal standard;
1
ꢁ1
1263, 1145, 1106, 991, 862, 763, 688, 549 cm ; dP
23.2; dH (CDCl ) 8.30 (2H, d, J
6
6
3
3
1
3
P
121 MHz) with 85% H PO as an external standard, for
7.5 Hz, Ph), 7.85–
HH
3
(
all compounds phosphorus spectra were recorded in the
7.95 (4H, m, PPh ), 7.54–7.73 (7H, m, PPh (6H), Ph
2 2
3
4
3
2
(1H)), 7.46 (2H, t, J
7.5 Hz, Ph), 5.57 (2H, d, J
HH PH
1
same solvent that was used for recording H NMR. NOE cor-
13.5 Hz, PCH ), 4.06 (2H, br m, NCH ), 3.77 (2H, br m,
2 2
NCH ), 2.25 (3H, s, CH ), 2.22 (2H, br m, CH ), 2.05
2 3 2
1
3
relations and C NMR spectra were recorded on a Bruker
Avance DRX 500 spectrometer (500 MHz and 100 MHz, re-
spectively) with C D , CDCl , and DMSO-d as solvents
2
(2H, br m, CH ); d (CDCl ) 191.2 ( J 6.4 Hz, CO);
2
C
3
CP
2
3
169.2 ( J
15.5 Hz, C(2)), 135.5 ( J
134.5 ( J 4 Hz, PPh ), 133.9 (Ph), 133.4 ( J 10.5 Hz,
4.8 Hz, Ph),
6
6
3
6
CP
CP
4
3
with TMS as an internal standard. IR spectra were recorded
on a Nexus-470 spectrometer for samples in KBr discs.
LC/MS (APCI MS) spectra were recorded using chromato-
graphy/mass spectrometric system, Agilent 1100/DAD/
MSD VL G1965a instrument and ‘HEWLETT-PACKARD’
HP GC/MS 5890/5972 instrument (EI, 70 eV) by GC inlet.
Mass spectra were obtained on a VG 70-70EQ, VG ANA-
LYTICAL (FAB) for phosphonium salts or a MX-1321 in-
strument (EI, 70 eV) by direct inlet for other substances.
Column chromatography was performed on silica gel (63–
CP
2
CP
4
2
PPh ), 132.6 ( J
2
3 Hz, Ph), 130.7 (Ph), 130.0 ( J
CP
CP
1
13.0 Hz, PPh ), 120.6 ( J
2
90.6 Hz, PPh ), 118.6
2
( J 11.9 Hz, CN), 54.5 (NCH ), 53.2 (NCH ), 49.7
( J 125.8 Hz, C(1)), 39.7 ( J 61.9 Hz, PCH ), 25.7
CP
2
CP
2
2
1
1
CP
CP
2
3
(CH ), 24.8 (CH ), 24.6 ( J 4.2 Hz, C(3)); m/z (FAB):
2
2
CP
+
439 (M , 100%).
4.2.2. (1-Cyano-2-pyrrolidin-1-ylprop-1-enyl)[2-(4-me-
thoxyphenyl)-2-oxoethyl]diphenylphosphonium bro-
mide (2b). Procedure A was applied; white solid (0.6 g,
2
00 mesh, Merck). Silica gel Merck 60F254 plates were
ꢀ
used for TLC. Microwave irradiation experiments were per-
formed using Emrys Creator EXP. Microanalyses were
performed in the Microanalytical Laboratory of the Institute
of Organic Chemistry, National Academy of Sciences of
Ukraine. Melting points are uncorrected. Yields refer to
pure isolated products.
68%); mp 193–195 C (benzene); [found: C 63.48; H 5.45;
Br 14.65; N 5.11; P 5.68. C H BrN O P requires: C
2
9
30
2 2
63.39; H 5.50; Br 14.54; N 5.10; P 5.64%]; d 28.4; d
P
H
3
(CDCl ) 8.34 (2H, d, J 7.8 Hz, p-MeOPh), 7.85–7.95
3
HH
3
(4H, m, PPh ), 7.55–7.74 (6H, m, PPh ), 6.94 (2H, d, J
HH
7.8 Hz, p-MeOPh), 5.45 (2H, d, J 14 Hz, PCH ), 4.06
PH
2
2
2
2
(2H, br m, NCH ), 3.84 (3H, s, OCH ), 3.79 (2H, br m,
2 3
4.1.1. 2-(Diphenylphosphino)-3-pyrrolidin-1-ylbut-2-
enenitrile (1). To a stirred solution of Ph PCl (3.24 g,
NCH ), 2.27 (3H, s, CH ), 2.15 (2H, br m, CH ), 2.05
2 3 2
2
(2H, br m, CH ); d (CDCl ) 190.2 ( J 6.3 Hz, CO),
2
2
C
3
CP
2
4
1
a solution of enamine 1 (2 g, 14.7 mmol) and Et N
4.7 mmol) in dichloromethane (30 mL) under dry argon,
169.2 ( J 15.1 Hz, C(2)), 164.8 (p-MeOPh), 134.4 ( J
CP CP
3.8 Hz, PPh ), 133.4 ( J
2
MeOPh), 130.0 ( J 12.6 Hz, PPh ), 128.7 ( J 5 Hz, p-
CP 2 CP
MeOPh), 120.8 ( J 90.5 Hz, PPh ), 118.6 ( J 11.3 Hz,
CP 2 CP
3
11.3 Hz, PPh ), 132.5 (p-
2
3
CP
2
3
(
1.93 g, 19 mmol) in dichloromethane (20 mL) was added
1
2
dropwise. After 7 h the reaction mixture was washed with
water (30 mL). The organic layer was separated, dried
CN), 114.2 (p-MeOPh), 55.7 (OCH ), 54.5 (NCH ), 53.2
2
3
1
1
(
lized from i-PrOH; white solid (2.82 g, 60%); mp 115–
Na SO ), and evaporated in vacuo. The residue was crystal-
(NCH ), 50.0 ( J 124.5 Hz, C(1)), 39.3 ( J 61.6 Hz,
2 CP CP
PCH ), 25.7 (CH ), 24.9 (CH ), 24.5 ( J 4 Hz, C(3)); m/z
2 2 2 CP
2
4
3
ꢀ
+
1
16 C; [found: C 74.95; H 6.62; N 8.69; P 9.60.
(FAB): 469 (M , 100%).

Y. V. Svyaschenko et al. / Tetrahedron 63 (2007) 5656–5664
5661
ꢀ
4.2.3. (1-Cyano-2-pyrrolidin-1-ylprop-1-enyl)[2-(4-ni-
trophenyl)-2-oxoethyl]diphenylphosphonium bromide
(0.4 g, 74%); mp 223–225 C (benzene); [found: C 63.40;
H 5.48; Br 14.60; N 5.11; P 5.61. C H BrN O P requires:
C 63.39; H 5.50; Br 14.54; N 5.10; P 5.64%]; d 21.6; dH
2
9
30
2 2
(
2c). Procedure A was applied; pale yellow solid (0.57 g,
ꢀ
P
63%); mp 195–197 C (acetone); [found: C 59.57; H 4.81;
Br 14.22; N 7.43; P 5.51. C H BrN O P requires: C
(DMSO-d ) 7.95–8.06 (2H, m, PPh ), 7.67–7.88 (8H, m,
2
PPh ), 7.53 (2H, d, J 9 Hz, p-MeOPh), 6.95 (2H, d,
HH
JHH 9 Hz, p-MeOPh), 6.20 (1H, s, OH), 4.10–4.22 (1H,
m, C(2)H ), 3.95–4.07 (1H, m, C(2)H ), 3.75 (3H, s,
OCH ), 3.56–3.73 (4H, br m, NCH ), 3.43 (1H, d, J
3 2 HH
6
3
2
8
27
3
3
2
3
5
9.59; H 4.82; Br 14.16; N 7.44; P 5.49%]; d 22.9; d
P
H
3
(
CDCl ) 8.59 (2H, d, J 8.1 Hz, p-NO Ph), 8.25 (2H, d,
2
JHH 8.1 Hz, p-NO Ph), 7.88–7.99 (4H, m, PPh ), 7.61–
3
HH
2
2
3
2
2
2
2
2
7
.73 (6H, m, PPh ), 5.82 (2H, d, J 13.2 Hz, PCH2),
2
16.5 Hz, C(4)H ), 3.01 (1H, d, JHH 16.2 Hz, C(4)H2),
2
PH
4
s, CH ), 2.22 (2H, br m, CH ), 2.06 (2H, br m, CH ); d
.10 (2H, br m, NCH ), 3.76 (2H, br m, NCH ), 2.25 (3H,
1.82–2.09 (4H, br m, CH CH ); d (DMSO-d ) 166.3
6
2
2
2
2
C
2
3
( J
11.3 Hz, p-MeOPh), 134.5 and 134.1 (PPh ), 133.7 and
15.1 Hz, C(5)), 159.2 (p-MeOPh), 138.9 ( J
CP CP
3
2
2
C
2
2
(
C(2)), 150.7 (p-NO Ph), 139.8 ( J 5.3 Hz, p-NO Ph),
CDCl ) 191.3 ( J 5.5 Hz, CO), 168.8 ( J 15.4 Hz,
3
CP
CP
2
3
3
2
133.4 ( J 11.3 Hz, PPh ), 130.0 and 129.7 ( J
12.6 Hz, PPh ), 126.8 (p-MeOPh), 123.1 and 122.6 ( J
91.8 Hz, PPh ), 119.1 ( J 6.3 Hz, CN), 114.0 (p-MeOPh),
2 CP
2
CP
3
2
CP
2
CP
CP
4
1
1
34.7 ( J 3.3 Hz, PPh ), 133.4 ( J 11.3 Hz, PPh2),
CP
131.1 (p-NO Ph), 130.1 ( J 13.5 Hz, PPh ), 123.8 (p-
NO Ph), 120.1 ( J 90.6 Hz, PPh ), 118.4 ( J 11.7 Hz,
2
CP
2
2
2
2
CP
2
1
2
2
71.4 ( J 6.3 Hz, C(3)), 55.7 (OCH ), 53.0 (NCH ), 52.3
CP 3 2
2
CP
2
CP
1
1
3
CN), 54.5 (NCH ), 53.2 (NCH ), 49.5 ( J 126.2 Hz,
CP
(NCH ), 46.0 ( J
2
117 Hz, C(6)), 44.2 ( J
2.5 Hz,
CP
2
2
CP
1
1
C(1)), 40.3 ( J 62.0 Hz, PCH ), 25.7 (CH ), 24.8 (CH ),
CP
C(4)), 32.0 ( J 51.6 Hz, C(2)), 25.7 (CH ), 24.7 (CH );
CP 2 2
2
2
2
3
+
+
2
4.5 ( J 4.2 Hz, C(3)); m/z (FAB): 484 (M , 100%).
CP
m/z (FAB): 469 (M , 100%).
4
.3. General procedures for cyclic phosphonium salts
4.3.3. 6-Cyano-3-hydroxy-3-(4-nitrophenyl)-1,1-di-
phenyl-5-pyrrolidin-1-yl-1,2,3,4-tetrahydrophosphini-
nium bromide (4c). Procedure A was applied; pale yellow
Procedure A. To a stirred suspension of phosphonium salts
a–c (1 mmol) in benzene (15 mL) Et N (0.01 g,
ꢀ
2
0
solid (0.38 g, 68%); mp 230–233 C (benzene); [found: C
59.65; H 4.84; Br 14.20; N 7.48; P 5.40. C H BrN O P re-
3
.1 mmol) was added, and the reaction mixture was heated
2
8
27
3 3
under reflux with stirring for 10 h. After cooling, precipi-
tated solid was collected by filtration and washed with benz-
ene (20 mL).
quires: C 59.59; H 4.82; Br 14.16; N 7.44; P 5.49%]; d 17.7;
P
3
d (DMSO-d ) 8.27 (2H, d, J 9 Hz, p-NO Ph), 7.68–8.10
H
6
HH
2
(12H, m, PPh (10H), p-NO Ph (2H)), 6.62 (1H, s, OH),
2
2
4.10–4.22 (1H, m, C(2)H ), 3.93–4.05 (1H, m, C(2)H ),
3.6–3.83 (4H, br m, NCH ), 3.57 (1H, d, J
2
2
2
Procedure B. To a stirred suspension of phosphonium salt 2a
(
0
with stirring for 10 h. After cooling, the precipitated solid
was collected by filtration and washed with benzene
16.5 Hz,
HH
2
2
0.52 g, 1 mmol) in benzene (15 mL) ylide 3a (0.04 g,
.1 mmol) was added, and the reaction mixture was refluxed
C(4)H ), 3.11 (1H, d, J ¼17.7 Hz, C(4)H ), 1.81–2.08
2
HH
2
2
2 2 C 6 CP
(4H, br m, CH CH ); d (DMSO-d ) 165.6 ( J 15.1 Hz,
C(2)), 153.7 ( J 6.3 Hz, p-NO Ph), 147.5 (p-NO Ph),
CP 2 2
134.6 and 134.2 ( J 2.5 Hz, PPh ), 133.8 and 133.5
CP
3
4
2
3
2
(
20 mL).
( J
PPh ), 127.3 (p-NO Ph), 123.9 (p-NO Ph), 122.8 and
11.3 Hz, PPh ), 130.0 and 129.8 ( J
12.6 Hz,
CP
CP
2
2
2
2
1
2
4
1
.3.1. 6-Cyano-3-hydroxy-1,1,3-triphenyl-5-pyrrolidin-
-yl-1,2,3,4-tetrahydrophosphininium bromide (4a). Pro-
122.4 ( J 93.1 Hz, PPh ), 119.0 ( J 7.5 Hz, CN), 71.8
CP 2 CP
2
1
( J 6.3 Hz, C(3)), 53.0 (NCH ), 52.4 (NCH ), 46.0 ( J
CP 2 2
115.7 Hz, C(6)), 43.2 ( J
CP
CP
3
1
cedure A was applied; white solid (0.42 g, 80%); procedure
B was applied (0.46 g, 88%); mp 218–220 C (benzene);
2.5 Hz, C(4)), 31.5 ( J
CP
ꢀ
found: C 64.71; H 5.39; Br 15.35; N 5.41; P 6.02.
54.1 Hz, C(2)), 25.8 (CH ), 24.6 (CH ); m/z (FAB): 484
2 2
+
[
C H BrN OP requires: C 64.75; H 5.43; Br 15.38; N
(M , 100%).
2
8
28
2
5
2
5
.39; P 5.96%]; nmax (KBr): 3135 (b), 3064, 2977, 2912,
175, 1537, 1436, 1342, 1112, 1062, 943, 856, 744, 705,
20 cm ; dP 20.6; dH (DMSO-d ) 7.95–8.06 (2H, m,
4.4. General procedure for ylides 3
ꢁ
1
To a solution of phosphonium salts 2a–c (1 mmol) in di-
chloromethane (15 mL) a 10% aqueous Na CO (15 mL)
6
PPh ), 7.59–7.90 (10H, m, PPh (8H), Ph (2H)), 7.30–7.45
2
2
2
3
(
3H, m, Ph), 6.28 (1H, s, OH), 4.11–4.23 (1H, m, C(2)H2),
was added, and the reaction mixture was stirred for 5 min.
The organic layer was separated, dried (Na SO ), and evap-
orated in vacuo.
3
3
1
.94–4.06 (1H, m, C(2)H ), 3.59–3.79 (4H, br m, NCH ),
2
2
2
4
2
2
.51 (1H, d, J
6.5 Hz, C(4)H ), 1.81–2.09 (4H, br m, CH CH ); d
16.5 Hz, C(4)H ), 3.05 (1H, d, J
HH
2
HH
2
2
2
C
2
3
(
DMSO-d ) 165.7 ( J
15.1 Hz, C(5)), 146.2 ( J
1.3 Hz, Ph), 133.9 (PPh ), 133.2 and 132.9 ( J 10.5 Hz,
4.4.1. 2-[(2-Oxo-2-phenylethylidene)(diphenyl)phos-
phoranyl]-3-pyrrolidin-1-ylbut-2-enenitrile (3a). Yellow
6
CP
CP
3
1
PPh ), 129.3 and 129.1 ( J 12.6 Hz, PPh ), 128.0 (Ph),
1
PPh ), 118.5 ( J 6.3 Hz, CN), 71.1 ( J 6.3 Hz, C(2)),
5
4
2
2
CP
ꢀ
solid (0.19 g, 43%); mp 124–127 C (CH Cl ); [found: C
2
2
CP
2
2
1
27.5 (Ph), 125.0 (Ph), 122.5 and 122.1 ( J 90.6 Hz,
76.73; H 6.20; N 6.35; P 6.98. C H N OP requires: C
28 27 2
CP
2
2
76.69; H 6.21; N 6.39; P 7.06%]; nmax (KBr): 3054, 2958,
2923, 2171, 1602, 1582, 1525, 1436, 1407, 1390, 1346,
2
CP
CP
1
2.4 (NCH ), 51.7 (NCH ), 45.6 ( J 110.3 Hz, C(6)),
2
3.3 (C(4)), 31.4 ( J 4.2 Hz, C(2)), 25.8 (CH ), 24.1
2
2
CP
1
ꢁ1
1249, 1168, 1105, 1027, 873, 750, 694, 549, 514 cm ; dP
16.8; d (CDCl ) 7.85–7.95 (6H, m, PPh (6H), Ph (2H)),
CP
+
(
(
CH ); m/z (FAB): 439 (M , 100%); m/z (EI): 420
2
M ꢁH O, 12), 235 (17), 85 (70), 83 (100), 47 (28%).
H
3
2
+
7.45–7.59 (6H, m, PPh ), 7.32–7.40 (3H, m, Ph), 4.26 (1H,
2
2
2
d, J 24.6 Hz, PCH), 3.92 (2H, br m, NCH ), 3.59 (2H,
PH
2
4.3.2. 6-Cyano-3-hydroxy-3-(4-methoxyphenyl)-1,1-di-
phenyl-5-pyrrolidin-1-yl-1,2,3,4-tetrahydrophosphini-
nium bromide (4b). Procedure A was applied; white solid
br m, NCH ), 2.26 (3H, s, CH ), 1.99 (4H, br m, CH ); d
2 3 2 C
2
2
(CDCl ) 184.3 ( J 3.8 Hz, CO), 168.3 ( J 11.3 Hz,
3
CP
CP
3
3
C(3)), 142.2 ( J
16.3 Hz, Ph), 132.7 ( J
10.1 Hz,
CP
CP

5662
Y. V. Svyaschenko et al. / Tetrahedron 63 (2007) 5656–5664
4
2
5
PPh ), 131.9 ( J 2.5 Hz, PPh ), 132.6 (Ph), 128.8 ( J
2
4.5.1. 1,1,5-Triphenyl-3-pyrrolidin-1-yl-1l -phosphi-
nine-2-carbonitrile (5a). Procedure A was applied; yellow
2
CP
CP
1
1
3.8 Hz, PPh ), 128.1 ( J 84.3 Hz, PPh ), 127.8 (Ph),
2
CP
2
2
1
1
C(2)), 53.3 ( J
26.8 (Ph), 120.8 ( J 10.1 Hz, CN), 57.0 ( J 117 Hz,
CP
solid (0.074 g, 35%); procedure B was applied (0.065 g,
81%); mp 175–176 C (MeOH); [found: C 76.71; H 6.11;
CP
1
ꢀ
N 8.12; P 8.98. C H N P requires: C 76.73; H 6.15; N
8.13; P 8.99%]; nmax (KBr): 3055, 2968, 2945, 2870, 2159,
114.4 Hz, PCH), 51.5 (NCH ), 52.9
2
CP
3
(NCH ), 25.7 (CH ), 24.9 (CH ), 22.0 ( J 5 Hz, C(4));
m/z (FAB): 439 (MH , 100), 421 (8), 337 (11), 201 (13),
2
2
2
CP
22 21 2
+
1
54 (17), 136 (13), 77 (8%).
1527, 1502, 1477, 1436, 1373, 1346, 1330, 1109, 1099,
9
ꢁ
17, 870, 746, 736, 711, 694, 545, 514, 486 cm ; d 16.4;
P
1
4.4.2. 2-[[2-(4-Methoxyphenyl)-2-oxoethylidene](diphe-
nyl)phosphoranyl]-3-pyrrolidin-1-ylbut-2-enenitrile
dH (CDCl ) 7.67–7.78 (4H, m, PPh ), 7.45–7.61 (8H, m,
3 2
Ph (2H), PPh (6H)), 7.34 (3H, br m, Ph), 4.91 (1H, s,
2
ꢀ
2
(
3b). Pale yellow solid (0.33 g, 70%); mp 114–116 C
CH Cl ); [found: C 74.34; H 6.20; N 5.93; P 6.65.
C(4)H), 4.33 (1H, d, J 18.6 Hz, C(6)H), 3.68 (4H, br m,
PH
2
(
C H N O P requires: C 74.34; H 6.24; N 5.98; P
NCH ), 1.93 (4H, br m, CH ); d (CDCl ) 156.3 ( J
2
2
2
2
C
3
CP
CP
2
3
7.5 Hz, C(3)), 155.3 ( J
11.3 Hz, C(5)), 144.8 ( J
CP
2
9
29
2
2
3
4
6
.61%]; dP 16.6; dH (CDCl ) 7.82–7.94 (6H, m, PPh2
3
16.3 Hz, Ph), 132.0 ( J 11.3 Hz, PPh ), 131.7 ( J 2.5 Hz,
CP 2 CP
1
2
(
d, J
4H), p-MeOPh (2H)), 7.41–7.52 (6H, m, PPh ), 6.85 (2H,
2
PPh ), 131.4 ( J 93.1 Hz, PPh ), 128.7 ( J 11.3 Hz,
2 CP 2 CP
3
2
2
8.7 Hz, p-MeOPh), 4.21 (1H, d, J
24.3 Hz,
PCH), 3.92 (2H, br m, NCH ), 3.81 (3H, s, OCH ), 3.52
PPh ), 128.4 (Ph), 128.2 (Ph), 127.0 (Ph), 123.9 ( J
2
HH
PH
CP
CP
3
1
7.5 Hz, CN), 86.9 ( J
8.8 Hz, C(4)), 61.3 ( J
2
3
CP
1
(
CH ); d (CDCl ) 183.8 ( J 3.8 Hz, CO), 168.3 ( J
2H, br m, NCH ), 2.23 (3H, s, CH ), 1.98 (4H, br m,
101.9 Hz, C(6)), 50.5 (NCH ), 34.1 ( J 118.2 Hz, C(2)),
2
25.7 (CH ); m/z (EI): 420 (M , 32), 236 (48), 235 (100),
2
2
3
CP
2
2
+
2
C
3
CP
CP
3
1
PPh ), 132.0 (p-MeOPh), 131.9 ( J 2.5 Hz, PPh ), 128.9
2.6 Hz, C(3)), 160.6 (p-MeOPh), 132.7 ( J
8.8 Hz,
201 (15), 77 (11), 47 (6%).
CP
4
2
CP
2
1
2
(
(
JCP 94.3 Hz, PPh ), 128.8 ( J 12.6 Hz, PPh ), 128.3
2
p-MeOPh), 120.9 ( J 8.8 Hz, CN), 112.9 (p-MeOPh),
CP
4.5.2. 5-(4-Methoxyphenyl)-1,1-diphenyl-3-pyrrolidin-1-
yl-1l -phosphinine-2-carbonitrile (5b). Procedure A was
CP
2
2
5
1
1
ꢀ
5
7.3 ( J 115.7 Hz, C(2)), 55.8 ( J 122 Hz, PCH), 55.3
CP
applied; yellow solid (0.077 g, 34%); mp 180–183 C
(MeOH); [found: C 77.28; H 6.03; N 6.22; P 6.93.
C H N OP requires: C 77.31; H 6.04; N 6.22; P 6.88%];
CP
(
(
OCH ), 52.9 (NCH ), 51.4 (NCH ), 25.7 (CH ), 25.0
3
CH ), 21.9 ( J 5 Hz, C(3)); m/z (FAB): 469 (MH ,
2 CP
2
2
2
3
+
29 27 2
1
00), 337 (18), 201 (14), 154 (10), 136 (9), 135 (10%).
dP 16.3; dH (CDCl ) 7.66–7.77 (4H, m, PPh ), 7.43–7.58
3 2
3
2 HH
(
8H, m, p-MeOPh (2H), PPh (6H)), 6.89 (2H, d, J
2
4.4.3. 2-[[2-(4-Nitrophenyl)-2-oxoethylidene](diphenyl)-
phosphoranyl]-3-pyrrolidin-1-ylbut-2-enenitrile (3c).
Orange solid (0.25 g, 51%); mp 118–121 C (CH Cl );
2
[found: C 69.51; H 5.43; N 8.60; P 6.37. C H N O P re-
quires: C 69.56; H 5.42; N 8.69; P 6.41%]; d 17.0; d
8.7 Hz, p-MeOPh), 4.90 (1H, s, C(4)H), 4.30 (1H, d, J
PH
17.4 Hz, C(6)H), 3.82 (3H, s, OCH ), 3.68 (4H, br m,
3
ꢀ
NCH ), 1.92 (4H, br m, CH ); d (CDCl ) 159.9 (p-MeOPh),
2
2
2
C
3
2
2
155.3 ( J 12.6 Hz, C(5)), 154.2 ( J 6.3 Hz, C(3)), 137.1
CP CP
( J 18.9 Hz, p-MeOPh), 132.0 ( J 11.3 Hz, PPh ), 131.7
CP CP 2
(PPh ), 131.4 ( J 103.1 Hz, PPh ), 128.7 ( J 11.3 Hz,
2 CP 2 CP
PPh ), 128.1 (p-MeOPh), 124.0 ( J 6.3 Hz, CN), 113.7
2 CP
(p-MeOPh), 86.5 ( J 8.8 Hz, C(4)), 61.7 ( J 110.7 Hz,
CP CP
C(6)), 55.4 (OCH ), 50.5 (NCH ), 34.0 ( J 115.7 Hz,
3 2 CP
C(2)), 25.7 (CH ); m/z (EI): 450 (M , 44), 266 (22), 265
2
2
8
26
3
3
3
3
P
H
3
1
2
(
CDCl ) 8.18 (2H, d, J 8.4 Hz, p-NO Ph), 8.02 (2H, d,
3
JHH 8.4 Hz, p-NO Ph), 7.84–7.95 (4H, m, PPh ), 7.46–
2
HH
2
3
2
2
2
3
1
7
3
.63 (6H, m, PPh ), 4.35 (1H, d, J 23.1 Hz, PCH),
PH
2
1
.99 (2H, br m, NCH ), 3.56 (2H, br m, NCH ), 2.23
2
2
+
(
3H, s, CH ), 2.01 (4H, br m, CH ); d (CDCl3)
C
3
2
2
2
1
81.2 ( J 3.8 Hz, CO), 168.1 ( J 13.8 Hz, C(3)), 148.2
CP
JCP 16.3 Hz, p-NO Ph), 148.1 (p-NO Ph), 132.7 ( J
2 2
(100), 201 (11), 185 (15), 183 (7), 77 (12), 55 (6%).
CP
3
3
(
CP
CP
4
2
1
1
0.1 Hz, PPh ), 132.3 ( J 2.5 Hz, PPh ), 129.0 ( J
2
2.6 Hz, PPh ), 128.0 ( J
2
4.5.3. 5-(4-Nitrophenyl)-1,1-diphenyl-3-pyrrolidin-1-yl-
1l -phosphinine-2-carbonitrile (5c). Procedure A was ap-
CP
1
2
5
93.1 Hz, PPh ), 127.7
2
CP
2
ꢀ
[found: C 72.27; H 5.19; N 9.08; P 6.67. C H N O P re-
(
p-NO Ph), 123.1 (p-NO Ph), 120.4 ( J 11.3 Hz, CN),
CP
plied; red solid (0.077 g, 33%); mp 215–220 C (MeOH);
2
2
1
1
5
6.5 ( J 117 Hz, C(2)), 56.4 ( J 110.7 Hz, PCH), 53.0
CP
CP
28 24 3 2
3
(
NCH ), 51.6 (NCH ), 25.8 (CH ), 24.9 (CH ), 22.3 ( J
2
quires: C 72.25; H 5.20; N 9.03; P 6.65%]; d 16.5; d
P H
2
2
2
CP
+
3
3
(
.8 Hz, C(4)); m/z (FAB): 484 (MH , 95), 319 (47), 201
100), 136 (21), 69 (30), 55 (45), 44 (33%).
(CDCl ) 8.21 (2H, d, J
3
8.7 Hz, p-NO Ph), 7.63–7.77
HH 2
(6H, m, p-NO Ph (2H), PPh (4H)), 7.49–7.61 (6H, m,
2 2
2
PPh ), 4.84 (1H, s, C(4)H), 4.27 (1H, d, J 17.4 Hz,
2
PH
5
4
.5. General procedures for l -phosphinines 5
C(6)H), 3.69 (4H, br m, NCH ), 1.95 (4H, br m, CH ); d
2 2 C
2
3 CP CP
2
(
CDCl ) 155.5 ( J 12.6 Hz, C(5)), 153.6 ( J 7.5 Hz,
3
Procedure A. Finely powdered ylide 3 (0.5 mmol) was
ꢀ
C(3)), 151.4 ( J 17.6 Hz, p-NO Ph), 147.6 (p-NO Ph),
CP 2 2
3
1
heated at 150 S (0.03 Torr) approximately for 5 min (until
132.0 ( J
91.8 Hz, PPh ), 128.9 ( J
10.1 Hz, PPh ), 132.0 (PPh ), 130.9 ( J
CP 2 2 CP
2
gas evolution ceased from the melt). After cooling the resi-
due was crystallized from MeOH.
12.6 Hz, PPh ), 127.8 (p-
CP 2
2
2
NO Ph), 123.6 (p-NO Ph), 123.3 ( J 7.5 Hz, CN), 86.9
2
JCP 8.8 Hz, C(4)), 61.4 ( J
2
CP
3
1
(
103.1 Hz, C(6)), 50.6
CP
1
Procedure B. The phosphonium salt 4a (0.1 g, 0.19 mmol)
was charged into an appropriate argon-flushed Smith micro-
wave process vial and DMF (1.0 mL) was added. The vial
was sealed with a Teflon septum and placed into the micro-
(NCH ), 35.0 ( J 118.2 Hz, C(2)), 25.7 (CH ); m/z (EI):
2 CP 2
+
465 (M , 44), 281 (19), 280 (100), 234 (16), 201 (6), 185
(14), 183 (12), 55 (5%).
ꢀ
5
wave cavity. After irradiation at 220 C for 5 min and subse-
ꢀ
4.6. General procedures for l -phosphinines 8
quent gas jet cooling to 40 C the mixture was diluted with
water (5 mL). The precipitated solid was collected by filtra-
tion and crystallized from MeOH.
Procedure A. A stirred suspension of phosphonium salts 2
ꢀ
(1 mmol) in DMFDMA (15 mL) was boiled at 110 C for

Y. V. Svyaschenko et al. / Tetrahedron 63 (2007) 5656–5664
5663
8
(
h. After cooling the reaction mixture was poured into water
40 mL). The precipitated solid was collected and dried in
70.58; H 4.90; N 8.51; P 6.28%]; d 13.0; d (CDCl ) 8.23
P H 3
(2H, d, J 8.7 Hz, p-NO Ph), 7.85–7.95 (4H, m, PPh ),
HH 2 2
3
3
vacuo. Then the solid was washed with boiling mixture of
EtOAc/hexane (1:2) (60 mL).
7.66 (2H, d, J
PPh ), 7.10 (1H, dd, J
(
8.7 Hz, p-NO Ph), 7.45–7.62 (6H, m,
HH 2
3
3
10.5 Hz, J 32.4 Hz), 5.10
PH
2
HH
4
HH PH
3
1H, dd, J 10.5 Hz, J 1.5 Hz, C(4)H), 3.78 (4H, br
2
Procedure B. To a suspension of dienamine 15 (0.5 g,
1
1
at 80 C until complete dissolution. After cooling the corre-
sponding alkyl halide (1.2 mmol) was added. After 1 h the
reaction mixture was washed with water. The organic layer
was separated, dried (Na SO ), and evaporated in vacuo.
The residue was washed with a boiling mixture of EtOAc/
hexane (1:2) (60 mL).
m, NCH ), 1.97 (4H, br m, CH ); d (CDCl ) 188.0 ( J
2 2 C 3 CP
6.3 Hz, CO), 158.6 ( J 10.1 Hz, C(3)), 148.4 (p-NO Ph),
CP 2
146.0 ( J 8.8 Hz, p-NO Ph), 141.3 ( J 8.8 Hz, C(5)),
CP 2 CP
133.2 ( J 11.3 Hz, PPh ), 132.2 ( J 2.5 Hz, PPh ),
CP 2 CP 2
129.3 (p-NO Ph), 128.6 ( J 12.6 Hz, PPh ), 125.7 ( J
CP
96.8 Hz, PPh ), 123.4 (p-NO Ph), 121.4 ( J 5 Hz, CN),
2
95.9 ( J 8.8 Hz, C(4)), 79.6 ( J 99.4 Hz, C(6)), 51.1
CP
(NCH ), 44.8 ( J 110.7 Hz, C(2)), 25.5 (CH ); m/z (EI):
2 CP 2
2
.1 mmol) in benzene (15 mL) P(NMe2)3 (0.2 g,
.2 mmol) was added, and the reaction mixture was boiled
3
2
ꢀ
3
4
2
1
2
CP
2
2
2
CP
3
1
2
4
CP
1
+
493 (M , 100), 308 (38), 201 (22), 185 (30), 183 (19), 150
11), 104 (5), 77 (5%).
(
5
4.6.1. 6-Benzoyl-1,1-diphenyl-3-pyrrolidin-1-yl-1l -
phosphinine-2-carbonitrile (8a). Procedure Awas applied;
5
4.7. General procedures for l -phosphinines 17
yellow solid (0.30 g, 67%); procedure B was applied (0.36 g,
ꢀ
73%); mp 140–143 C (EtOAc/hexane); [found: C 77.70; H
.63; N 6.22; P 6.97. C H N OP requires: C 77.66; H 5.62;
A stirred suspension of phosphonium salt 4 (1 mmol) and
AcONa (0.25 g, 3 mmol) in Ac O (15 mL) was refluxed
5
N 6.25; P 6.91%]; nmax (KBr): 3056, 2950, 2925, 2871, 2161,
2
9
25
2
2
for 1 day (17a) or 2 days (17b). After cooling the reaction
mixture was poured into water (50 mL). The precipitated
solid was collected and dried in vacuo. The residue was sub-
jected to flash chromatography over silica gel using EtOAc/
cyclohexane 1:1 as an eluent affording 17.
1
5
7
546, 1500, 1442, 1373, 1326, 1270, 1099, 728, 703,
09 cm ; d 13.8; d (CDCl ) 7.85–7.95 (4H, m, PPh ),
ꢁ
1
P
H
3
2
.48–7.57 (8H, m, PPh (6H), Ph (2H)), 7.35–7.40 (3H, m,
2
3
3
Ph), 7.31 (1H, dd, J 9.3 Hz, J 33 Hz), 4.89 (1H, dd,
HH
PH
3
4
3
JHH 10.2 Hz, JPH 1.5 Hz, C(4)H), 3.75 (4H, t, JHH
3
5
6
.6 Hz, NCH ), 1.94 (4H, m, JHH 6.6 Hz, CH ); d
C
4.7.1. 6-Acetyl-1,1,5-triphenyl-3-pyrrolidin-1-yl-1l -
phosphinine-2-carbonitrile (17a). Yellow solid (0.09 g,
2
2
2
2
(CDCl ) 190.9 ( J 6.3 Hz, CO), 158.6 ( J 10.1 Hz,
C(3)), 142.8 ( J 10.1 Hz, C(5)), 139.8 ( J 7.5 Hz, Ph),
1
1
3
CP
CP
2
3
ꢀ
6.63. C H N OP requires: C 77.90; H 5.88; N 6.06; P
19%); mp 198–200 C; [found: C 77.93; H 5.90; N 6.05; P
CP
CP
3
4
33.2 ( J 11.3 Hz, PPh ), 131.9 ( J 2.5 Hz, PPh2),
2
29.9 (Ph), 128.6 (Ph), 128.5 ( J 13.8 Hz, PPh ), 128.0
CP
CP
CP
30 27 2
2
6.70%]; R (EtOAc/hexane 1:1) 0.45; n
f
(KBr): 3052,
max
2
1
2
(
Ph), 126.4 ( J 95.6 Hz, PPh ), 121.9 ( J 6.3 Hz, CN),
CP
2956, 2923, 2865, 2169, 1521, 1477, 1438, 1361, 1294,
1182, 1099, 935, 750, 723, 545, 516, 476 cm ; d 15.5;
2
CP
3
1
ꢁ1
9
4.4 ( J 10.1 Hz, C(4)), 79.5 ( J 99.4 Hz, C(6)), 51.0
CP
CP
P
1
(
NCH ), 44.4 ( J 108.2 Hz, C(2)), 25.5 (CH ); m/z (EI):
2
dH (CDCl ) 7.85–7.95 (4H, m, PPh ), 7.48–7.57 (6H, m,
2
CP
2
3
+
4
(
48 (M , 100), 263 (55), 235 (10), 185 (10), 183 (11), 105
49), 77 (35), 45 (9), 44 (11%).
PPh ), 7.38 (5H, br m, Ph), 4.96 (1H, s, C(4)H), 3.74 (4H,
2
br m, NCH ), 1.93 (4H, br m, CH ), 1.41 (3H, s, COCH );
2
2
3
2
2
dC (CDCl ) 193.6 ( J 5 Hz, CO), 157.4 ( J 10.1 Hz,
3
C(3)), 154.1 ( J 12.6 Hz, C(5)), 144.1 ( J 12.6 Hz, Ph),
CP CP
CP
CP
2
3
4
1
.6.2. 6-(4-Methoxybenzoyl)-1,1-diphenyl-3-pyrrolidin-
-yl-1l -phosphinine-2-carbonitrile (8b). Procedure A
5
3
4
132.9 ( J
PPh ), 128.4 (Ph), 128.3 ( J 11.3 Hz, PPh ), 128.3 (Ph),
10.1 Hz, PPh2), 131.5 ( J
2.5 Hz,
CP
CP
2
was applied; yellow solid (0.19 g, 40%); procedure B was
applied (0.31 g, 59%); mp 178–180 C (EtOAc/hexane);
2
CP
2
ꢀ
found: C 75.35; H 5.69; N 5.80; P 6.54. C H N O P
1
2
128.2 (Ph), 127.8 ( J
6.3 Hz, CN), 99.3 ( J
101.9 Hz, C(6)), 51.0 (NCH ), 46.1 ( J 106.9 Hz, C(2)),
2
29.1 ( J 6.3 Hz, COCH ), 25.5 (CH ); m/z (EI): 462
CP 3 2
(M , 47), 279 (18), 277 (100), 201 (13), 185 (6), 183 (9),
77 (6), 43 (15%).
98.1 Hz, PPh ), 122.2 ( J
2
7.5 Hz, C(4)), 81.1 ( J
CP
CP
CP
3
1
[
requires: C 75.30; H 5.69; N 5.85; P 6.47%]; d 13.9; dH
3
0
27
2
2
CP
1
P
CP
3
(
(
3
CDCl ) 7.83–7.93 (4H, m, PPh ), 7.45–7.57 (8H, m, PPh
3
2
2
3
3
+
6H), p-MeOPh (2H)), 7.36 (1H, dd, J
3 Hz), 6.88 (2H, d, J
10.2 Hz, J
8.7 Hz, p-MeOPh), 5.02 (1H,
HH
HH
PH
3
3
4
dd, JHH 10.2 Hz, JPH 1.5 Hz, C(4)H), 3.82 (3H, s,
OCH ), 3.75 (4H, br m, NCH ), 1.94 (4H, br m, CH ); d
(
(
1
(
1
6
7
4
1
4.7.2. 6-Acetyl-5-(4-methoxyphenyl)-1,1-diphenyl-3-pyr-
rolidin-1-yl-1l -phosphinine-2-carbonitrile (17b). Yel-
3
2
2
C
2
5
CDCl ) 190.9 ( J 6.3 Hz, CO), 161.2 (p-MeOPh), 158.5
3
JCP 8.8 Hz, C(3)), 142.9 ( J 8.8 Hz, C(5)), 133.2 ( J
CP
1.3 Hz, PPh ), 132.3 ( J 10.1 Hz, p-MeOPh), 131.8
2
JCP 2.5 Hz, PPh ), 130.5 (p-MeOPh), 128.4 ( J
2
2.6 Hz, PPh ), 126.6 ( J 95.6 Hz, PPh ), 122.0 ( J
2
.3 Hz, CN), 113.3 (p-MeOPh), 94.0 ( J 10.1 Hz, C(4)),
CP
CP
2
2
3
ꢀ
H 5.91; N 5.66; P 6.33. C H N O P requires: C 75.59; H
low solid (0.09 g, 18%); mp 103–105 C; [found: C 75.64;
CP
3
CP
31 29 2 2
4
2
5.93; N 5.69; P 6.29%]; R (EtOAc/hexane 1:1) 0.35; d
f P
CP
1
2
16.0; d (CDCl ) 7.82–7.93 (4H, m, PPh ), 7.48–7.57 (6H,
H 3 2
2
CP
CP
3
3
m, PPh ), 7.29 (2H, d, J 8.7 Hz, p-MeOPh), 6.91 (2H,
2 HH
1
3
9.3 ( J 100.6 Hz, C(6)), 55.4 (OCH ), 51.0 (NCH ),
CP
d, J 8.7 Hz, p-MeOPh), 4.97 (1H, s, C(4)H), 3.84 (3H,
HH
3
2
1
+
4.4 ( J 108.2 Hz, C(2)), 25.5 (CH ); m/z (EI): 478 (M ,
2
s, OCH ), 3.74 (4H, br m, NCH ), 1.92 (4H, br m, CH ),
2
CP
3
2
2
00), 293 (33), 265 (10), 185 (4), 183(5), 135 (51), 77 (13%).
1.46 (3H, s, COCH ); d (CDCl ) 193.9 ( J 5 Hz, CO),
3 C 3 CP
159.8 (p-MeOPh), 157.4 ( J 10.1 Hz, C(3)), 154.0 ( J
12.6 Hz, C(5)), 136.5 ( J
( J 10.1 Hz, PPh ), 131.5 ( J 3.8 Hz, PPh ), 129.5 (p-
CP 2 CP 2
MeOPh), 128.3 ( J 12.6 Hz, PPh ), 127.8 ( J 98.1 Hz,
CP 2 CP
2
2
CP CP
3
4
1
.6.3. 6-(4-Nitrobenzoyl)-1,1-diphenyl-3-pyrrolidin-1-yl-
l -phosphinine-2-carbonitrile (8c). Procedure A was ap-
13.8 Hz, p-MeOPh), 132.8
CP
5
3
4
2
1
plied; yellow solid (0.21 g, 43%); procedure B was applied
(
ꢀ
0.57; H 4.94; N 8.46; P 6.25. C H N O P requires: C
2
0.35 g, 65%); mp 225–226 C (EtOAc/hexane); [found: C
PPh ), 122.3 ( J 6.3 Hz, CN), 113.7 (p-MeOPh), 99.2
CP
2
3
1
7
( J
7.5 Hz, C(4)), 81.0 ( J
98.1 Hz, C(6)), 55.3
CP
2
9
24
3
3
CP

5664
Y. V. Svyaschenko et al. / Tetrahedron 63 (2007) 5656–5664
1
3
(
5
3
OCH ), 51.0 (NCH ), 45.6 ( J 104.4 Hz, C(2)), 29.2 ( J
3
4. (a) Hirai, Y.; Suzuki, H.; Takeda, Y. JP 2003049051, 2003;
Chem. Abstr. 2003, 138, 154807; (b) Chikamasa, N. JP
2003041473, 2003; Chem. Abstr. 2003, 138, 138749; (c)
Krebs, F. C.; Larsen, P. S.; Larsen, J.; Jacobsen, C. S.;
Boutton, C.; Thorup, N. J. Am. Chem. Soc. 1997, 119, 1208–
2
CP
CP
+
Hz, COCH ), 25.5 (CH ); m/z (EI): 492 (M , 5), 491 (33),
3 2
07 (100), 217 (23), 201 (34), 185 (3), 183 (9), 135 (8), 77
(
20), 57 (32), 43 (39%).
1216; (d) Mizukura, N.; Kita, H. JP 04029237, 1992; Chem.
Abstr. 1992, 117, 17188.
Acknowledgements
5
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Hoffmann, M. G.; Bauer, K.; Bieringer, H.; Rosinger, C.;
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6. Dimroth, K. Fortschr. Chem. Forsch. 1973, 38, 1–147.
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The authors acknowledge Enamine Ltd for technical and
financial support, especially Prof. A.A. Tolmachev, S.V.
Ryabukhin (MW investigation), and V.V. Polovinko (NMR
investigation). Also we thank S.A. Alekseev (Department
of Chemistry of Kyiv National Taras Shevchenko Univer-
sity), A.V. Mazepa (Bogatsky Physico-Chemical Institute,
National Academy of Sciences of Ukraine, Department of
Molecular Structure), and Yu.V. Kuzmenko (Central Cus-
toms Laboratory of National Customs Service of Ukraine)
for spectral measurements.
References and notes
4
45–472.
1
2
3
. (a) Quin, L. D. The Heterocyclic Chemistry of Phosphorus
Systems Based on the Phosphorus–Carbon Bond; Wiley: New
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. (a) Madsen, G. K. H.; Krebs, F. C.; Lebech, B.; Larsen, F. K.
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3
12. For using Me SiCl as a water scavenger, see: (a) Ryabukhin,
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2
002, 137, 201440; (c) Karacar, A.; Freytag, M.; Jones, P. G.;
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1
M.; Kamireddy, B.; Martin, M. T.; Massey, R. J.; Napper, A.
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