One-pot process in phosphonium-iodonium ylides: Nucleophilic substitution and the Wittig reaction

Article abstract of DOI:10.1007/s11172-008-0061-4

The nucleophilic substitution in mixed phosphonium-iodonium ylides was investigated. The iodonium group is replaced by such S-containing nucleophiles as the thiocyanate anion or thiourea, as well as by halide ions. The structure of the reaction product with the thiocyanate ion was established by X-ray diffraction. A one-pot process involving the nucleophilic substitution and the Wittig reaction was developed.

Full text of DOI:10.1007/s11172-008-0061-4

Russian Chemical Bulletin, International Edition, Vol. 57, No. 2, pp. 400—405, February, 2008
400
Oneꢀpot process in phosphoniumꢀiodonium ylides:
nucleophilic substitution and the Wittig reaction
E. D. Matveeva,ꢀ T. A. Podrugina, A. S. Pavlova, A. V. Mironov, and N. S. Zefirov
Department of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 939 0290. Eꢀmail: matveeva@org.chem.msu.ru
The nucleophilic substitution in mixed phosphoniumꢀiodonium ylides was investigated.
The iodonium group is replaced by such Sꢀcontaining nucleophiles as the thiocyanate anion or
thiourea, as well as by halide ions. The structure of the reaction product with the thiocyanate
ion was established by Xꢀray diffraction. A oneꢀpot process involving the nucleophilic substituꢀ
tion and the Wittig reaction was developed.
Key words: mixed phosphoniumꢀiodonium ylides, phenyliodonium group, nucleophilic
substitution, α,βꢀunsaturated acids, Xꢀray diffraction.
Iodonium salts and ylides belong to an important class
in reactions with potassium salts.7 An analogous substituꢀ
tion is observed also with tetraalkylammonium salts.8
The nucleophilic substitution of the iodonium fragꢀ
ment occurs also in the reaction of ylide 1 with trimethylꢀ
silyl halides.6 The silylation is accompanied by the
replacement of the iodonium fragment by the halide anion
that is released in the course of the reaction (Scheme 2).
of organic compounds, which can be used for the syntheꢀ
sis of new reagents and in fine organic synthesis.1—3 Due
to considerable synthetic potential, particularly in the nuꢀ
cleophilic substitution of the phenyliodonium group,4
aryliodonium salts belong to the most wellꢀstudied and
widely used class of such compounds.
Earlier,5 using ylide 1 as an example, we have demonꢀ
strated that mixed phosphoniumꢀiodonium ylides are well
described by resonance structures with a considerable conꢀ
tribution of the structure 1C (Scheme 1).
Scheme 2
Scheme 1
X = Cl (a), Br (b), I (c)
Using the silylation reaction, we succeeded
in performing the nucleophilic substitution, the silyl
deprotection, and the Wittig reaction as a oneꢀpot process
for various aldehydes. As a result, we prepared the correꢀ
sponding derivatives of αꢀsubstituted acrylic acids 3a—n
(Scheme 3). This procedure allows the synthesis of
αꢀhalogenꢀsubstituted acrylic acids, which are difficult to
prepare by other methods,9,10 in reproducible high yields
(see Scheme 3).
It should be noted that silylꢀcontaining chloro derivaꢀ
tive 2a is the most stable compound and can be prepared
at room temperature, whereas it is necessary to perform
the silylation with trimethylbromosilane and iodosilane at
It can be seen that the molecule of mixed phosphoꢀ
niumꢀiodonium ylide 1 contains several reaction centers,
due to which such compounds can be used in nucleoꢀ
philic substitution reactions. Earlier, we have shown that
ylide 1 can be used as the Oꢀnucleophile in alkylation,
acylation, and silylation reactions,6 as well as for the reꢀ
placement of the iodonium fragment with halide anions
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 391—395, February, 2008.
1066ꢀ5285/08/5702ꢀ0400 © 2008 Springer Science+Business Media, Inc.

Oneꢀpot process for phosphoniumꢀiodonium ylides Russ.Chem.Bull., Int.Ed., Vol. 57, No. 2, February, 2008
401
Scheme 3
Scheme 4
In the 1H NMR spectrum of compound 4, the signals
of the ethoxy group are substantially broadened, which is
attributed to an equilibrium between the Z and E isomers
of ylide (4B and 4C) in solution and is indicative of a weak
contribution of the resonance structure 4A (Scheme 5).
An analogous equilibrium is characteristic of the NMR
spectra of ylide 1 (see Ref. 5).
3
R
X
Z/E
Yield (%)
а
b
c
d
e
f
g
h
i
j
k
l
m
n
4ꢀCF3C6H4
4ꢀCF3C6H4
4ꢀCF3C6H4
4ꢀBrC6H4
4ꢀBrC6H4
4ꢀBrC6H4
4ꢀFC6H4
4ꢀFC6H4
4ꢀFC6H4
4ꢀMeOC6H4
4ꢀMeOC6H4
Bu
Cl
Br
I
Cl
Br
I
Cl
Br
I
Cl
Br
Cl
Br
I
80/20
89/11
88/12
84/16
90/10
55/45
89/11
55/45
84/16
86/14
85/15
88/12
70/30
72/28
90
80
50
75
75
60
90
50
60
80
35
50
60
40
Scheme 5
Bu
Bu
–35 and –65 °C, respectively. In addition, the synthesis
of iodoꢀsubstituted compound 2c is complicated by the
release of molecular iodine, which is apparently associꢀ
ated with reduction of the C—I bond. This results in a
slight decrease in the yield of iodocinnamic acids.
The ratio of the Z/E isomers of αꢀhalocinnamic acids
was determined by 1H NMR spectroscopy. This ratio
varies from 90 : 10 to 55 : 45 (see Scheme 3). The Z
isomer is generated as the major product because the
reaction is performed with stabilized ylide. For the Z
isomer, the signals of the ethyl group and the vinyl proton
are shifted downfield compared to the corresponding
signals for the E isomer. For example, the 1H NMR
spectrum of the Z isomer of chloroꢀsubstituted cinnamic
acid ester 3a shows the signals of the Et group at δ 1.39
(CH3) and 4.30 (OCH2), whereas the corresponding sigꢀ
nals for the E isomer are observed at δ 1.16 and 4.19.
Analogously, the signal of the vinyl proton for the Z
isomer is observed at δ 7.91, whereas the corresponding
signal for the E isomer is observed at δ 7.23.
The structure of ylide 4 was established by singleꢀ
crystal Xꢀray diffraction. The Xꢀray diffraction data for
the crystalline E isomer of 4B provide unambiguous
evidence for the nucleophilic substitution and the
C—SCN bond formation, as well as for the considerable
double bond character of the C=C bond.
The overall molecular structure is shown in Fig. 1.
The P, C(1), C(2), S, O(1), and O(2) atoms lie in a single
C(25)
C(24)
C(12)
C(35)
C(13)
C(26)
C(14)
C(15)
C(36)
C(31)
C(34)
C(33)
C(21)
P
C(16)
C(11)
C(23)
C(32)
C(22)
O(2)
In addition, ylides 1 are involved in the nucleophilic
displacement of the iodonium group with Sꢀnucleophiles.
In the present study, we used the thiocyanate anion and
thiourea as Sꢀnucleophiles. For example, the reaction of
ylide 1 with ammonium thiocyanate in acetonitrile perꢀ
formed at room temperature for 6 h afforded thiocyanated
ylide 4 (Scheme 4).
C(1)
C(2)
O(1)
S
C(4)
C(3)
C(5)
N(1)
Fig. 1. Xꢀray diffraction structure of compound 4.

402
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 2, February, 2008
Matveeva et al.
Table 1. Interatomic distances (d) in compound 4
Experimental
The H, 31P, and 13C NMR spectra were recorded on a
Bruker Avance 400 instrument operating at 400 MHz in CDCl3
with Me4Si as the internal standard. The IR spectra were meaꢀ
sured on a URꢀ20 instrument in CCl4. The elemental analysis
was carried out on a VarioꢀII CHN analyzer. The mass spectra
were obtained on a Finnigan Mat Incos50 quadrupole mass
spectrometer (EI, 70 eV, direct inlet). The progress of the reactions
was monitored and the purity after chromatographic separation
was checked by TLC on Silufol plates.
1
Distance
d/Å
Distance
d/Å
P—C(11)
P—C(21)
P—C(31)
P—C(1)
S—C(1)
S—C(5)
1.801(3)
1.806(2)
1.817(2)
1.741(3)
1.718(3)
1.691(4)
C(1)—C(2)
C(2)—O(1)
C(2)—O(2)
O(2)—C(3)
C(3)—C(4)
C(5)—N(1)
1.429(4)
1.216(4)
1.375(4)
1.449(4)
1.470(8)
1.134(5)
Reaction of ylide 1 with Me3SiCl. Synthesis of αꢀhalogenꢀ
substituted acrylic acid esters 3a,d,g,j,l (general procedure).
Trimethylsilyl chloride (0.06 mL, 0.46 mmol) was added to a
solution of ylide 1 (0.2 g, 0.314 mmol) in anhydrous acetonitrile
at room temperature. The reaction mixture was stirred under
argon until ylide 1 was consumed (TLC monitoring). The correꢀ
sponding aldehyde (0.36 mmol) and Bu4NF•xH2O (x = 1—3)
(120 mg, 0.46 mmol) were added to the mixture. The reaction
mixture was stirred for 8 h (TLC monitoring) and concentrated
in vacuo. The residue was chromatographed on a column with
elution using benzene, CH2Cl2, and a CH2Cl2—MeOH mixture
in a ratio from 100 : 1 to 20 : 1.
plane within 0.1 Å (∆/Å: 0 (P), –0.001(1) (S), 0.025(3)
(C(1)), –0.012(4) (C(2)), –0.086(4) (O(1)), 0.060(4)
(O(2))). This fact, as well as the considerable double bond
character of the C(1)—C(2) bond (1.429(4) Å) (Table 1),
confirm a considerable contribution of the structure 4B.
On the contrary, the C(1)—P bond length is 1.741(3) Å.
The C(1)—C(2) and C(1)—P bond lengths are in good
agreement with the data published in the literature11—13
for phosphonium ylides stabilized by CORꢀtype acceptor
groups. The P—C(1)—C(2) (120.4(2)°), S—C(1)—C(2)
(118.2(2)°), and C(1)—C(2)—O(1) (127.6(3)°) bond
angles are additional arguments in favor of the structure
4B. It should be noted that the O(2)—C(2)—C(1) angle is
110.0(2)°. The distortion of this angle is most likely assoꢀ
ciated with the steric repulsion between the hydrogen
atom of the CH2 group and the O(1) atom. This is also
evident from the rather short distance between the H and
O(1) atoms (2.35(4) Å) and the C(3)—O(2)—C(2) angle
(118.5(3)°).
Ethyl 2ꢀchloroꢀ3ꢀ[4ꢀ(trifluoromethyl)phenyl]propꢀ2ꢀenoate
(3a). The yield was 90%. Z isomer (80%). 1H NMR (CDCl3), δ:
1.39 (t, 3 H, Me, J = 7.0 Hz); 4.36 (q, 2 H, CH2, J = 7.0 Hz);
7.67 and 7.90 (both d, 2 H each, H arom., 3JH,H = 8.2 Hz, 3JH,H
= 8.0 Hz); 7.91 (s, 1 H, CH). 13C NMR (CDCl3), δ: 14.18 (s,
Me); 62.89 (s, OCH2); 123.8 (d, CF3, 1JC,F = 278.1 Hz); 125.42
3
(q, mꢀC arom., JC,F = 3.7 Hz); 128.68 (s, CCl); 130.62 (s,
CH); 131.11 (d, CCF3, 2JC,F = 42.4 Hz); 135.21 (s, oꢀC arom.);
1
135.65 (s, ipsoꢀC); 162.90 (s, C=O). E isomer (20%). H NMR
(CDCl3), δ: 1.16 (t, 3 H, Me, J = 7.2 Hz); 4.19 (q, 2 H, CH2, J
= 7.2 Hz); 7.23 (s, 1 H, CH); 7.39 and 7.59 (both d, 2 H each, H
The reaction of thiourea with ylide 1 in anhydrous
acetone affords product 5 (Scheme 6). The 1H NMR
spectrum of ylide 5 is not contradictory to this structure.
The signals of the ethoxy group are also strongly broadꢀ
ened, which is characteristic of ylides.5
3
3
arom., JH,H = 8.6 Hz, JH,H = 8.3 Hz). IR, ν/cm–1: 1620
(C=C); 1725 (C=O). Found (%): C, 51.77; H, 3.70. C12H10ClF3O2.
Calculated (%): C, 51.71; H, 3.59.
Ethyl 3ꢀ(4ꢀbromophenyl)ꢀ2ꢀchloropropꢀ2ꢀenoate (3d). The
1
yield was 75%. H NMR (CDCl3), δ: 1.40 (t, 3 H, Me, J = 7.1
Hz); 4.36 (q, 2 H, CH2, J = 7.1 Hz); 7.57 and 7.72 (both d, 2 H
3
3
each, H arom., JH,H = 8.6 Hz, JH,H = 8.3 Hz); 7.84 (s, 1 H,
CH). 13C NMR (CDCl3), δ: 14.20 (s, Me); 62.68 (s, OCH2);
124.51 (s, CBr); 130.08 (s, CCl); 131.47 (s, ipsoꢀC); 131.81 (s,
oꢀC arom.); 131.97 (s, mꢀC arom.); 135.56 (s, CH); 163.13 (s,
C=O). IR, ν/cm–1: 1620 (C=C); 1730 (C=O). Found (%): C,
45.79; H, 3.64. C11H10BrClO2. Calculated (%): C, 45.60; H, 3.45.
Ethyl 2ꢀchloroꢀ3ꢀ(4ꢀfluorophenyl)propꢀ2ꢀenoate (3g). The
Scheme 6
1
yield was 90%. H NMR (CDCl3), δ: 1.40 (t, 3 H, Me, J = 7.0
Hz); 4.36 (q, 2 H, CH2, J = 7.1 Hz); 7.12 (dd, 2 H, H arom.,
3JH,H = 3JH,F = 8.6 Hz, 3JH,H = 3JH,F = 8.9 Hz); 7.85—7.89 (m,
3 H, 2 H arom. + CH). 13C NMR (CDCl3), δ: 14.21 (s, Me);
2
62.61 (s, OCH2); 115.73 (d, mꢀC arom., JC,F = 21.1 Hz);
129.16 (s, CCl); 130.26 (s, ipsoꢀC); 132.76 (d, oꢀC arom.,
1
3JC,F = 7.6 Hz); 135.59 (s, CH); 163.44 (d, CF, JC,F = 253.6
Hz); 163.30 (s, C=O). IR, ν/cm–1: 1610 (C=C); 1730 (C=O).
Found (%): C, 58.05; H, 4.29. C11H10ClFO2. Calculated (%):
C, 57.77; H, 4.38.
Ethyl 2ꢀchloroꢀ3ꢀ(4ꢀmethoxyphenyl)propꢀ2ꢀenoate (3j).9 The
yield was 80%. 1H NMR (CDCl3), δ: 1.40 (t, 3 H, Me, J = 7.0 Hz);
3.87 (s, 3 H, OMe); 4.36 (q, 2 H, CH2, J = 7.0 Hz); 6.96 (d, 2 H,
To summarize, we demonstrated that mixed phosphoꢀ
niumꢀiodonium ylides are readily involved in the nucleoꢀ
philic displacement of the iodonium fragment by halide
anions and S nucleophiles.

Oneꢀpot process for phosphoniumꢀiodonium ylides Russ.Chem.Bull., Int.Ed., Vol. 57, No. 2, February, 2008
403
3
H arom., JH,H = 8.9 Hz); 7.87 (t, 3 H, 2 H arom. + CH,
3JH,H = 8.5 Hz).
1.30—1.52 (m, 7 H, 2 CH2, Me); 2.36 and 4.28 (both q, 2 H
each, CH2, OCH2, J = 7.1 Hz); 7.30 (t, 1 H, CH). 13C NMR
(CDCl3), δ: 13.78 (s, Me); 14.17 (s, Me); 22.39 (s, CH2); 29.65
(s, CH2); 31.82 (s, CH2); 62.31 (s, OCH2); 116.29 (s, CBr);
146.22 (s, CH); 162.54 (s, C=O). MS, m/z: 236 [M + 2]+, 234
[M]+, 155 [M – Br]+. IR, ν/cm–1: 1620 (C=C); 1720 (C=O).
Reaction of ylide 1 with trimethylsilyl iodide. Synthesis of
αꢀhalogenꢀsubstituted acrylic acid esters 3c,f,i,n (general proceꢀ
dure). Trimethylsilyl iodide (0.065 mL, 0.46 mmol) was added
to a solution of ylide 1 (0.2 g, 0.314 mmol) in anhydrous CH2Cl2
at –65 °ꢁC. The reaction mixture was stirred under argon until
ylide 1 was consumed (TLC monitoring). The corresponding
aldehyde (0.36 mmol) and Bu4NF (120 mg, 0.46 mmol) were
added to the reaction solution. The reaction mixture was stirred
at –65 °C for 1 h, warmed to room temperature, stirred for
8—12 h (TLC monitoring), and concentrated in vacuo. The
residue was chromatographed on a column with elution using
benzene, CH2Cl2, and a CH2Cl2—MeOH mixture in a ratio
from 100 : 1 to 20 : 1.
Ethyl 2ꢀchloroheptꢀ2ꢀenoate (3l).14 The yield was 50%. 1H NMR
(CDCl3), δ: 0.94 (t, 3 H, Me, J = 7.3 Hz); 1.33—1.50 (m, 7 H, 2 CH2,
Me); 2.37 and 4.29 (both q, 2 H each, CH2, OCH2, J = 7.3 Hz);
7.10 (t, 1 H, CH).
Reaction of ylide 1 with trimethylsilyl bromide. Synthesis of
αꢀhalogenꢀsubstituted acrylic acid esters 3b,e,h,k,m (general proꢀ
cedure). Trimethylsilyl bromide (0.06 mL, 0.46 mmol) was added
to a solution of ylide 1 (0.2 g, 0.314 mmol) in anhydrous acetoꢀ
nitrile at –35 °C. The reaction mixture was stirred under argon
until ylide 1 was consumed (TLC monitoring). The correspondꢀ
ing aldehyde (0.36 mmol) and Bu4NF (120 mg, 0.46 mmol)
were added to the reaction solution. The mixture was stirred at
–35 °C for 1 h, warmed to room temperature, stirred for 8—12 h
(TLC monitoring), and concentrated in vacuo. The residue was
chromatographed on a column with elution using benzene,
CH2Cl2, and a CH2Cl2—MeOH mixture in a ratio from 100 : 1
to 20 : 1.
Ethyl 2ꢀbromoꢀ3ꢀ[4ꢀ(trifluoromethyl)phenyl]propꢀ2ꢀenoate
(3b). The yield was 80%. 1H NMR (CDCl3), δ: 1.41 (t, 3 H, Me,
J = 7.0 Hz); 4.38 (q, 2 H, CH2, J = 7.0 Hz); 7.70 and 7.92 (both
d, 2 H each, H arom., 3JH,H = 8.1 Hz, 3JH,H = 7.8 Hz); 8.24 (s,
1 H, CH). 13C NMR (CDCl3), δ: 14.14 (s, Me); 63.04 (s, OCH2);
Ethyl 2ꢀiodoꢀ3ꢀ[4ꢀ(trifluoromethyl)phenyl]propꢀ2ꢀenoate
(3c). The yield was 50%. 1H NMR (CDCl3), δ: 1.39 (t, 3 H, Me,
J = 7.0 Hz); 4.36 (q, 2 H, CH2, J = 7.0 Hz); 7.69 and 7.82 (both
d, 2 H each, H arom., 3JH,H = 7.9 Hz, 3JH,H = 8.1 Hz); 8.26 (s,
1 H, CH). 13C NMR (CDCl3), δ: 14.17 (s, Me); 63.29 (s, OCH2);
1
1
115.85 (s, CBr); 123.8 (d, CF3, JC,F = 271.5 Hz); 125.30 (d,
94.22 (s, CI); 121.14 (d, CF3, JC,F = 273 Hz); 125.30 (d, mꢀC
3
mꢀC arom., JC,F = 3.7 Hz); 130.23 (s, oꢀC arom.); 130.94
arom., 3JC,F = 2.9 Hz); 129.50 (s, oꢀC arom.); 131.33 (d, CCF3,
2JC,F = 32.2 Hz); 139.32 (s, ipsoꢀC); 146.40 (s, CH); 163.36 (s,
C=O). IR, ν/cm–1: 1610 (C=C); 1720 (C=O). Found (%): C,
38.54; H, 2.36. C12H10F3IO2. Calculated (%): C, 38.92; H, 2.70.
Ethyl 3ꢀ(4ꢀbromophenyl)ꢀ2ꢀiodopropꢀ2ꢀenoate (3f). The yield
(d, CCF3, 2JC,F = 32.2 Hz); 139.12 (s, CH); 139.48 (s, ipsoꢀC);
162.83 (s, C=O). IR, ν/cm–1: 1620 (C=C); 1730 (C=O). Found
(%): C, 44.62; H, 2.98. C12H10BrF3O2. Calculated (%): C, 44.58;
H, 3.096.
1
Ethyl 2ꢀbromoꢀ3ꢀ(4ꢀbromophenyl)propꢀ2ꢀenoate (3e). The
yield was 75%. 1H NMR (CDCl3), δ: 1.40 (t, 3 H, Me, J = 7.0 Hz);
4.37 (q, 2 H, CH2, J = 7.0 Hz); 7.57 and 7.74 (both d, 2 H each,
was 60%. Z isomer (55%). H NMR (CDCl3), δ: 1.40 (t, 3 H,
Me, J = 7.0 Hz); 4.36 (q, 2 H, CH2, J = 7.0 Hz); 7.58 and 7.67
3
3
(both d, 2 H each, H arom., JH,H = 8.6 Hz, JH,H = 8.5 Hz);
8.21 (s, 1 H, CH). 13C NMR (CDCl3), δ: 14.20 (s, Me); 63.16
(s, OCH2); 92.03 (s, CI); 124.32 (s, CBr); 130.24 (s, oꢀC arom.);
131.59 (s, mꢀC arom.); 134.43 (s, ipsoꢀC); 137.49 (s, CH); 163.59
3
3
H arom., JH,H = 8.6 Hz, JH,H = 8.9 Hz); 8.15 (s, 1 H, CH).
13C NMR (CDCl3), δ: 14.23 (s, Me); 62.93 (s, OCH2); 114.00
(s, CBr); 124.52 (s, pꢀCBr); 131.69 (s, oꢀC, mꢀC arom.); 132.62
(s, ipsoꢀC); 139.47 (s, CH); 163.10 (s, C=O). IR, ν/cm–1: 1620
(C=C); 1730 (C=O). Found (%): C, 39.43; H, 3.05. C11H10Br2O2.
Calculated (%): C, 39.52; H, 2.99.
1
(s, C=O). E isomer (45%). H NMR (CDCl3), δ: 1.33 (t, 3 H,
Me, J = 7.3 Hz); 4.30 (q, 2 H, CH2, J = 7.3 Hz); 7.14 (s, 1 H,
CH); 7.72 and 7.73 (both d, 2 H each, H arom., 3JH,H = 8.3 Hz,
3JH,H = 8.0 Hz). IR, ν/cm–1: 1720 (C=O). MS, m/z: 382 [M + 2]+,
380 [M]+, 253 [M – I]+, 180 [M – I – COOC2H5]+.
Ethyl 2ꢀbromoꢀ3ꢀ(4ꢀfluorophenyl)propꢀ2ꢀenoate (3h). The
yield was 50%. Z isomer (55%). 1H NMR (CDCl3), δ: 1.40 (t, 3 H,
Me, J = 7.1 Hz); 4.37 (q, 2 H, CH2, J = 7.1 Hz); 7.14 (dd, 2 H,
H arom., 3JH,H = 3JH,F = 8.8 Hz, 3JH,H = 3JH,F = 8.6 Hz); 7.90
(q, 2 H, H arom., 3JH,H = 8.3 Hz, 4JH,F = 5.3 Hz, 3JH,H = 8.6 Hz,
4JH,F = 5.6 Hz); 8.20 (s, 1 H, CH). 13C NMR (CDCl3), δ: 14.23
(s, Me); 62.86 (s, OCH2); 112.89 (s, CBr); 115.66 (d, mꢀC
Ethyl 3ꢀ(4ꢀfluorophenyl)ꢀ2ꢀiodopropꢀ2ꢀenoate (3i)7. The yield
1
was 60%. H NMR (CDCl3), δ: 1.39 (t, 3 H, Me, J = 7.1 Hz);
4.36 (q, 2 H, CH2, J = 7.1 Hz); 7.14 (dd, 2 H, H arom., 3JH,H
=
3JH,F = 8.6 Hz, 3JH,H = 3JH,F = 8.6 Hz); 7.82 (q, 2 H, H arom.,
3JH,H = 8.8 Hz, 4JH,F = 5.3 Hz, 3JH,H = 8.8 Hz, 4JH,F = 5.3 Hz);
8.24 (s, 1 H, CH).
2
arom., JC,F = 22.0 Hz); 132.11 (s, ipsoꢀC); 132.47 (d, oꢀC
arom., 3JC,F = 8.0 Hz); 139.50 (s, CH); 163.27 (s, C=O); 163.50
Ethyl 2ꢀiodoheptꢀ2ꢀenoate (3n). The yield was 40%. 1H NMR
(CDCl3), δ: 0.95 (t, 3 H, Me, J = 7.1 Hz); 1.27—1.53 (m, 7 H,
2 CH2, Me); 2.33 and 4.28 (both q, 2 H each, CH2, OCH2,
J = 7.1 Hz); 7.21 (t, 1 H, CH). 13C NMR (CDCl3), δ: 13.84 and
14.18 (both s, Me); 22.38, 29.58, and 36.75 (all s, CH2); 62.57
(s, OCH2); 95.13 (s, CI); 153.24 (s, CH); 162.96 (s, C=O). MS,
1
1
(d, CF arom., JC,F = 252.5 Hz). E isomer (45%). H NMR
(CDCl3), δ: 1.36 (t, 3 H, Me, J = 7.1 Hz); 4.34 (q, 2 H, CH2,
J = 7.3 Hz); 7.12 (s, 1 H, CH); 7.35 (dd, 2 H, H arom., 3JH,H
=
3JH,F = 7.3 Hz, 3JH,H = 3JH,F = 7.6 Hz); 7.72 (d, 2 H, H arom.,
3JH,H = 7.3 Hz). IR, ν/cm–1: 1720 (C=O). MS, m/z: 274 [M + 2]+,
272 [M]+, 193 [M – Br]+, 120 [M – Br – COOC2H5]+.
Ethyl 2ꢀbromoꢀ3ꢀ(4ꢀmethoxyphenyl)propꢀ2ꢀenoate (3k).9
m/z: 282 [M]+, 253 [M – C2H5]+, 155 [M – I]+. IR, ν/cm–1
:
1618 (C=C); 1725 (C=O).
1
The yield was 35%. H NMR (CDCl3), δ: 1.37 (t, 3 H, Me,
Ethyl thiocyanato(triphenylphospharanylidene)acetate (4).
Ammonium thiocyanate (0.03 g, 0.395 mmol) was added to a
solution of ylide 1 (0.2 g, 0.314 mmol) in anhydrous acetonitrile
(3 mL). The reaction mixture was stirred under argon for 6 h.
The completion of the reaction was determined by TLC based
on the disappearance of ylide 1. Ammonium fluoroborate was
J = 7.0 Hz); 3.82 (s, 3 H, OMe); 4.33 (q, 2 H, CH2, J = 7.0 Hz);
3
6.94 and 7.90 (both d, 2 H each, H arom., JH,H = 8.9 Hz,
3JH,H = 8.8 Hz); 8.16 (s, 1 H, CH).
Ethyl 2ꢀbromoheptꢀ2ꢀenoate (3m). The total yield was 45 mg
1
(60%). H NMR (CDCl3), δ: 0.94 (t, 3 H, Me, J = 7.1 Hz);

404
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 2, February, 2008
Matveeva et al.
Table 2. Crystallographic characteristics and the Xꢀray data colꢀ
lection and refinement statistics for compound 4
resulting oil was dissolved in CH2Cl2, and excess thiourea was
filtered off. The residue was chromatographed on a column with
elution using CH2Cl2 and then a CH2Cl2—MeOH mixture with
an increasing amount of methanol. Compound 5 was obtained
as an oil. The yield was 50%. 31P NMR (CDCl3), δ: 28.77. 1H NMR
(CDCl3), δ: 0.58 (br.s, 3 H, Me); 3.85 (br.s, 2 H, CH2);
7.58—7.71 (m, 15 H, H arom.); 8.08 and 8.70 (both br.s, 2 H
each, 2 NH2). 13C NMR (CDCl3), δ: 13.66 (s, Me); 30.79
Parameter
Characteristics
Molecular formula
М
C23H20NO2PS
405.45
Crystal system
Space group
a/Å
b/Å
c/Å
β/deg
Z
dcalc/g cm–3
Radiation (λ/Å)
T/K
Monoclinic
P21/n
1
(d, JC,P = 125.9 Hz); 60.71 (s, OCH2); 124.19 (d, ipsoꢀC,
1JC,P = 92.2 Hz); 129.24 (d, mꢀC arom., JC,P = 12.4 Hz); 133.22
(s, pꢀC arom.); 133.79 (d, oꢀC arom., JC,P = 9.5 Hz); 172.21 (s,
CN); 173.99 (s, C=O). IR, ν/cm–1: 1730 (C=O); 2860—2980
(NH2). MS, m/z: 347 [M – HBF4 – SC(NH2)2]+, 160 [M –
HBF4 – Ph3P]+. Found (%): C, 53.95; H, 4.49; N, 5.42.
C23H24BF4N2O2PS. Calculated (%): C, 54.12; H, 4.71; N, 5.49.
Xꢀray diffraction study. Xꢀray diffraction data were collected
from transparent crystals of compound 4. The unit cell paramꢀ
eters were refined based on 23 reflections. The absorption corꢀ
rection was applied based on the crystal shape. The structure
was solved by direct methods (SIR2002).15 All nonhydrogen
atoms were located in sequential Fourier and difference Fourier
maps and refined first isotropically and then with anisotropic
atomic displacement parameters using the JANA2000 program
package.16 The hydrogen atoms (except for the methyl groups)
were positioned geometrically and refined first with fixed bond
lengths and bond angles and then independently. Their atomic
displacement parameters were taken equal to 1.2Uiso of the
parent carbon atoms. The Xꢀray data collection and refinement
statistics are given in Table 2.
9.3944(22)
16.2603(18)
13.9574(21)
96.071(16)
4
1.282
MoꢀKα (0.71069)
293
Crystal shape
Crystal dimensions/mm
Diffractometer
Scanning mode
Absorption correction
Rod
0.18×0.18×0.59
CADꢀ4
ω/1.33θ
Analytical
(based on crystal shape)
7150
Number of measured
reflections
Number of independent
reflections
Number of observed reflections
3845
3350
with I > 3σ(I )
θꢀScan range/deg
Ranges of indices h, k, l
2—30
0 ≤ h ≤ 13,
–1 ≤ k ≤ 22,
–19 ≤ l ≤ 19
0.021
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 05ꢀ03ꢀ33054),
the Council on Grants of the President of the Russian
Federation (Program for State Support of Leading Scienꢀ
tific Schools, Grant NShꢀ2552.2006.3), the Ministry of
Education and Science of the Russian Federation (Target
Program “Development of the Research Potential of
Higher Education,” Grant RNP.2.1.1.7779), and the Diꢀ
vision of Chemistry and Materials Science of the Russian
Academy of Sciences (Program No. 1 for Basic Research).
Rint
R/Rw (I > 3σ(I ))
Goodnessꢀofꢀfit
Number of refinement
parameters
Weighting scheme
∆rmax/eÅ–3
0.048/0.064
2.00
304
2
w = [σ (F ) + (0.015F )2]–1
+0.33/–0.23
filtered off, and the filtrate was concentrated in vacuo. The
residue was washed with petroleum ether. Compound 4 was
obtained as an oil. The yield was 90%. 31P NMR (CDCl3), δ:
29.07. 1H NMR (CDCl3), δ: 1.29 and 1.67 (both br.s, 3 H, Me);
3.47 and 3.89 (both br.s, 2 H, CH2); 7.55—7.68 (m, 15 H,
H arom.). 13C NMR (CDCl3), δ: 14.40 (s, Me); 28.47 (d,
1JC,P = 125.9 Hz); 59.68 (s, OCH2); 116.92 (d, CN, JC,P = 3.0 Hz);
References
1. E. D. Matveeva, M. V. Proskurnina, N. S. Zefirov, Heteroatom
Chem., 2006, 17, 595.
2. N. Sh. Pirkuliev, V. K. Brel´, N. S. Zefirov, Usp. Khim.,
2000, 69, 118 [Russ. Chem. Rev., 2000, 69 (Engl. Transl.)].
3. P. J. Stang, J. Org. Chem., 2003, 68, 2997.
1
124.81 (d, ipsoꢀC arom., JC,P = 92.9 Hz); 128.84 (d, mꢀC
4. V. V. Zhdankin, P. J. Stang, Chem. Rev., 2002, 102, 2523.
5. E. D. Matveeva, T. A. Podrugina, Yu. K. Grishin, V. V.
Tkachev, V. V. Zhdankin, S. M. Aldoshin, N. S. Zefirov, Zh.
Org. Khim., 2003, 39, 572 [Russ. J. Org. Chem., 2003, 39
(Engl. Transl.)].
6. E. D. Matveeva, T. A. Podrugina, Yu. K. Grishin, A. S.
Pavlova, N. S. Zefirov, Zh. Org. Khim., 2007, 43, 209 [Russ.
J. Org. Chem., 2007, 43 (Engl. Transl.)].
arom., JC,P = 12.5 Hz); 132.61 (d, pꢀC arom., JC,P = 3.0 Hz);
133.72 (d, oꢀC arom., JC,P = 9.5 Hz); 164.84 (s, C=O).
IR, ν/cm–1: 2150 (C≡N); 1670 (C=C). Found (%): C, 68.13;
H, 4.97. C23H20NO2PS. Calculated (%): C, 68.15; H, 4.94.
Amino{[2ꢀoxoꢀ1ꢀ(triphenylphospharanylidene)ꢀ2ꢀethoxyꢀ
ethyl]sulfanyl}methaniminium tetrafluoroborate (5). Thiourea
(0.048 g, 0.628 mmol) was added to a solution of ylide 1 (0.2 g,
0.314 mmol) in anhydrous acetone (5 mL). The reaction mixꢀ
ture was stirred under argon for 6 h. The completion of the
reaction was determined by TLC based on the disappearance of
ylide 1. The reaction mixture was concentrated in vacuo, the
7. V. V. Zhdankin, O. Maydanovych, J. Herschbach, J. Bruno,
E. D. Matveeva, N. S. Zefirov, J. Org. Chem., 2003, 68,
1018.

Oneꢀpot process for phosphoniumꢀiodonium ylides Russ.Chem.Bull., Int.Ed., Vol. 57, No. 2, February, 2008
405
8. Zh. Huang, X. Yu, X. Huang, J. Org. Chem., 2002, 67, 8261.
9. J.ꢀC. Le Menn, J. Sarrazin, A. Tallec, Can. J. Chem., 1989,
67, 1332.
15. M. C. Burla, M. Camalli, B. Carrozzini, G. Cascarano, C.
Giacovazzo, G. Polidori, R. Spagna, J. Appl. Crystallogr.,
2003, 36, 1103.
10. R. Rossi, F. Bellina, Ch. Bechini, L. Mannina, P. Vergamini,
Tetrahedron, 1998, 54, 135.
11. J. C. J. Bart, J. Chem. Soc. B, 1969, 350.
12. F. S. Stephens, J. Chem. Soc., 1965, 5640.
13. A. J. Sreziale, K. W. Ratts, J. Am. Chem. Soc., 1965, 87,
5603.
16. V. Petricek, M. Dusek, L. Palatinus, Jana2000. Structure
Determination Software Program, Institute of Physics, Praha
(Czech Republic), 2000.
Received July 6, 2007;
in revised form December 18, 2007
14. J. P. Marino, R. J. Linderman, J. Org. Chem., 1983, 48,
4621.