Selenophilic reaction of organolithium and magnesium reagents with phosphinoselenoic chlorides

Article abstract of DOI:10.1002/hc.20091

The reaction of phosphinoselenoic chlorides 1 with various organolithium and magnesium reagents was studied. Sequential reaction of phosphinoselenoic chlorides 1 with organolithium and magnesium reagents and elemental selenium gave two types of products,

Full text of DOI:10.1002/hc.20091

Heteroatom Chemistry
Volume 16, Number 3, 2005
Selenophilic Reaction of Organolithium
and Magnesium Reagents
with Phosphinoselenoic Chlorides
Tsutomu Kimura, Toshiaki Murai, and Noriko Mizuhata
Department of Chemistry, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan
Received 25 November 2004; revised 24 December 2004
gas [3]. Nevertheless, we recently reported the
ABSTRACT: The reaction of phosphinoselenoic chlo-
isolation of phosphinoselenoic chlorides as stable
rides 1 with various organolithium and magnesium
compounds, and their substitution reactions with
reagents was studied. Sequential reaction of phosphi-
heteroatom-containing nucleophiles selectively took
noselenoic chlorides 1 with organolithium and mag-
place at the phosphorus atom [4]. On the other
nesium reagents and elemental selenium gave two
hand, the reaction of these chlorides with organo-
types of products, phosphine selenides 2 and phos-
lithium and magnesium reagents gave several types
phinodiselenoic acid esters 3. The esters 3 appeared
of products. We report here the details of the re-
to be formed via the selenophilic reaction of organo-
action of phosphinoselenoic chlorides with a vari-
lithium and magnesium reagents with the chlorides
ety of organolithium and magnesium reagents. Com-
1. Molecular orbital calculations were carried out
putational studies on a series of model compounds
for model compounds H2P(E)Cl (E = O, S and Se)
H2P(E)Cl (E = O, S and Se) are also described.
ꢀ
C
to determine their electronic structures.
2005 Wiley
Periodicals, Inc. Heteroatom Chem 16:185–191, 2005;
Published online in Wiley InterScience (www.interscience.
wiley.com). DOI 10.1002/hc.20091
RESULTS AND DISCUSSION
Initially, diphenylphosphinoselenoic chloride 1a was
treated with BuLi in THF at 0◦C for 15 min (Eq. (1),
Table 1).
INTRODUCTION
Phosphinic and phosphinothioic acid derivatives
have provided fruitful chemistry. The synthesis and
reactions of phosphinic [1] and phosphinothioic
halides [2] have been particularly well studied. In
contrast, much less attention has been paid to
the selenium-isologue, i.e., phosphinoselenoic chlo-
rides, probably because they were predicted to be
less stable and had to be handled under an inert
(1)
Correspondence to: Toshiaki Murai; e-mail: mtoshi@cc.gifu-u.
ac.jp.
Contract grant sponsor: Ministry of Education, Culture, Sports,
Science and Technology of Japan.
Contract grant number: 16033224.
2005 Wiley Periodicals, Inc.
c
ꢀ
185

186 Kimura, Murai, and Mizuhata
TABLE 1 Reaction of Phosphinoselenoic Chlorides 1a–c
BuLi initially attacks the selenium atom of the
chlorides 1 to form 5, followed by the elimination
of chloride ion from 5 to generate trivalent phos-
phinoselenous acid butyl esters 6. Selenium transfer
from other selenium-containing compounds to the
resulting esters 6 gives phosphinodiselenoic acid es-
ters 3. Alternatively, air oxidation of the esters 6 gives
phosphinoselenoic acid Se-esters 4. In the reaction of
the chloride 1b with BuLi (entry 2), 31P NMR spec-
tra of the crude reaction mixture showed the signals
due to the deselenated product t-BuPhPBu and the
ester 6b at 3.9 ppm and 57.2 ppm (1 JPSe = 234.1 Hz),
respectively.
Next, the reaction of phosphinoselenoic chlo-
rides 1a–c with various organolithium and magne-
sium reagents was carried out (Eq. (2), Table 2). Ele-
mental selenium was added to the reaction mixture
to avoid selenium transfer from selenium-containing
compounds to esters 6. As a result, in all cases, phos-
phine selenides 2 and phosphinodiselenoic acid es-
ters 3 were obtained.
with BuLia
Yield (%)b
Entry
1
2
3
4
1
1a
2
3
1b
1c
aPhosphinoselenoic chloride 1 was reacted with BuLi (1.1 equiv) at
0◦C for 15 min.
bYields of isolated products.
After the usual work-up, phosphine selenide
2a and phosphinoselenoic acid Se-butyl ester 4a
were obtained in respective yields of 19% and 19%
(entry 1). A similar reaction of tert-butyl phenyl 1b
and di-tert-butylphosphinoselenoic chlorides 1c with
BuLi gave mixtures of phosphine selenides 2, phos-
phinodiselenoic acid butyl esters 3, and phosphi-
noselenoic acid Se-butyl esters 4 (entries 2 and 3).
The products 2 may be formed by substitution reac-
tion at the phosphorus atom of 1 with BuLi. On the
other hand, 3 and 4 may be formed via selenophilic
reaction of BuLi with 1 [5]. A plausible reaction path-
way for the present reaction leading to 3 and 4 is
shown in Scheme 1.
(2)
The reaction of diphenylphosphinoselenoic chlo-
ride 1a with BuLi gave a mixture of the phosphine se-
lenide 2a and the ester 3a in a ratio of 57:43 (entry 1),
whereas the introduction of one tert-butyl group to
the phosphorus atom gave the ester 3b in an in-
creased ratio (entry 2). When the chloride 1c bearing
two tert-butyl groups was used as a substrate, the es-
ter 3c was obtained in a higher ratio (entry 3). The
use of BuMgCl increased the ratio of the phosphine
selenide 2b (entry 4) [6]. The reaction of 1b with PhLi
preferentially gave phosphinodiselenoic acid ester
3d (entry 5). Notably, this result is in marked con-
trast to the reaction of phosphinothioic chloride 7
with PhLi where phosphine sulfide 8 was selectively
obtained (Eq. (3)) [7].
(3)
The reaction of 1b with t-BuLi afforded the ester
3e in moderate yield together with a trace amount
of phosphine selenide 2e (entry 6). In this case, 31P
SCHEME 1

Selenophilic Reaction of Organolithium and Magnesium Reagents with Phosphinoselenoic Chlorides 187
TABLE 2 Reaction of Phosphinoselenoic Chlorides 1a–c
with a Variety of Carbon Nucleophilesa
(4)
Yield (%)b
1
Entry
R ꢁꢁM
Conv.(%)
2
3
salt 11 may give phosphinodiselenoic acid methyl
ester 3g [4b].
1a
BuLi
1
100
1b
BuLi
2
3
100
100
1c
BuLi
SCHEME 2
Finally, lithium phenylethynylide was reacted with
the chloride 1b (entry 7). In contrast to the reaction
with alkyl and phenyllithiums, selective introduction
of a phenylethynyl group to the phosphorus atom
took place to give 2f in 55% yield.
1b
BuMgCl
4
5
98
95
1b
PhLi
To determine the electronic structure of phos-
phinoselenoic chlorides, geometry optimization and
molecular orbital calculations for the model com-
pounds H2P(O)Cl 12ꢁ, H2P(S)Cl 7ꢁ, and H2P(Se)Cl
1ꢁ were performed at the RHF/6-31G(d) level with
the GAUSSIAN 98 programs [10]. Selected bond
lengths, atomic charges, and energies of LUMO and
LUMO+1 are listed in Table 3. The MO plots drawn
by the MOLDEN program [11] are shown in Figure 1.
No significant change in the P Cl bond lengths
was observed for these compounds, whereas the pos-
itive charge on the phosphorus atom of phosphi-
noselenoic chloride 1ꢁ was much smaller than that
of phosphinic chloride 12ꢁ. The LUMOs of 1ꢁ, 7ꢁ, and
12ꢁ were mainly P Cl antibonding orbitals. Notably,
1b
t-BuLi
6
7
94
71
1b
≡
PhC CLi
aPhosphinoselenoic chloride 1 was reacted with organometallic
reagent (1 equiv) at 0◦C (organolithium reagents) or room tempera-
ture (BuMgCl) in THF (10 ml) for 15 min. After elemental selenium
(2 equiv) was added to the reaction mixture, the mixture was stirred
at room temperature for 1 h.
bYields of isolated products.
TABLE 3 RHF/6-31G(d) Optimized Bond Lengths, Atomic
Charges and Orbital Energies of Model Compounds H2P(E)CI
NMR spectra of the crude reaction mixture showed
an unidentified signal (58.1 ppm) with relatively
high intensity. Methyl iodide was then added to the
reaction mixture to give phosphinodiselenoic acid
methyl ester 3g in 28% yield along with 2e and 3e
(Eq. (4)) [8]. A plausible reaction pathway leading
to the methyl ester 3g may involve a halogen–metal
exchange reaction to generate phosphinoselenous
acid lithium salt 10, followed by the insertion of el-
emental selenium to form phosphinodiselenoic acid
lithium salt 11 (Scheme 2) [9]. Methylation of the
H2P(E)CI
12ꢁ (E = O) 7ꢁ (E = S) 1ꢁ (E = Se)
˚
Bond length (A)
P = E
1.454
2.023
1.926
2.036
2.706
2.038
P−CI
Atomic charge
E
P
CI
−0.729
0.980
−0.202
−0.371
0.524
−0.153
−0.467
0.620
−0.154
Orbital energy (eV)
LUMO
LUMO + 1
3.833
4.412
2.383
3.860
2.206
3.569

188 Kimura, Murai, and Mizuhata
NMR spectra were measured with CDCl3 on a JEOL
ꢀ-400 spectrometer. Mass spectra were taken on SHI-
MADZU GCMS QP1000 (EI mode). High-resolution
mass spectra were measured on a JEOL JMS-GC
mate II. Elemental analyses were performed at the
Elemental Analysis Center of Kyoto University.
Synthesis of P,P-bis(1,1-dimethylethyl)
phosphinoselenoic Chloride (1c)
In a 50-mL two-necked flask, elemental selenium
(1.579 g, 20.0 mmol) was added to a toluene so-
lution (20 mL) of t-Bu2PCl (3.80 mL, 20.0 mmol)
at room temperature, and the mixture was stirred
under reflux for 15 min. The reaction mixture was
concentrated in vacuo. The residue was purified by
column chromatography on silica gel using hexane-
CH2Cl2 as eluent to give P,P-bis(1,1-dimethylethyl)-
phosphinoselenoic chloride (1c) (5.115 g, 99%) as
a colorless solid. mp (dec.) 131–132◦C; 1H NMR
3
(CDCl3) δ 1.46 (d, JHP = 18.5 Hz, 18H); 13C NMR
2
1
(CDCl3) δ 27.8 (d, JCP = 2.5 Hz), 45.5 (d, JCP
=
29.8 Hz); 31P NMR (CDCl3) δ 145.8 (1 JPSe = 816.3 Hz);
77Se NMR (CDCl3) δ −205.0 (d, JSeP = 816.3 Hz);
1
FIGURE 1 MOLDEN plots of orbitals calculated for model
compounds: (a) LUMO and (b) LUMO + 1 of H2P(O)Cl 12ꢁ;
(c) LUMO and (d) LUMO + 1 of H2P(S)Cl 7ꢁ; (e) LUMO and
(f) LUMO + 1 of H2P(Se)Cl 1ꢁ.
EIMS (m/z) 260 (M+); Anal. Calcd for C8H18ClPSe:
C, 37.01; H, 6.99. Found: C, 36.81; H, 6.86.
Reaction of P-(1,1-Dimethylethyl)-P-phenylphos-
phinoselenoic Chloride (1b) with BuLi
LUMO of 1ꢁ spread not only along the P Cl bond but
also on the selenium atom. In addition, LUMO+1s of
1ꢁ and 7ꢁ were in essence P E antibonding orbitals,
and LUMO+1 of 1ꢁ had a large back lobe of a P E
antibonding orbital at the selenium atom. Further-
more, the LUMO+1 energy of 1ꢁ was the lowest and
the energy gap between the LUMO and LUMO+1
of 1ꢁ was the smallest among the model compounds.
These results are consistent with the experimental re-
sults that a selenophilic reaction occurred between
organolithium and magnesium reagents and phos-
phinoselenoic chlorides.
In a 20-mL two-necked flask, BuLi (1.6 mol/L hexane
solution, 1.4 mL, 2.2 mmol) was added to a THF
solution (5 mL) of P-(1,1-dimethylethyl)-P-phenyl-
phosphinoselenoic chloride (1b) (0.559 g, 2.0 mmol)
at 0◦C, and the mixture was stirred at that temper-
ature for 15 min. The reaction mixture was poured
into water and extracted with CH2Cl2 (50 mL). The
organic layer was dried over MgSO4 and concen-
trated in vacuo. The residue was purified by column
chromatography on silica gel using hexane-CH2Cl2
and CHCl3-MeOH as eluent to give P-butyl-P-(1,1-
dimethylethyl)-P-phenylphosphine selenide (2b)
(0.121 g, 20%) as a pale-yellow solid, P-(1,1-dime-
thylethyl)-P-phenylphosphinodiselenoic acid butyl
ester (3b) (0.059 g, 8%) as a pale-yellow oil and
P-(1,1-dimethylethyl)-P-phenylphosphinoselenoic
acid Se-butyl ester (4b) (0.226 g, 36%) as a pale-
yellow oil. 2b: mp (dec.) 87–89◦C; 1H NMR (CDCl3) δ
CONCLUSION
Phosphinoselenoic chlorides reacted with a vari-
ety of organolithium and magnesium reagents. This
reaction may involve the selenophilic reaction of
organolithium and magnesium reagents with the
chlorides.
3
0.88 (t, J = 7.3 Hz, 3H), 1.14 (d, JHP = 16.6 Hz,
9H), 1.22–1.32 (m, 1H), 1.41 (sex, J = 7.3 Hz, 2H),
1.77–1.91 (m, 1H), 1.96–2.07 (m, 1H), 2.52–2.62
(m, 1H), 7.40–7.49 (m, 3H), 7.83–7.88 (m, 2H); 13C
EXPERIMENTAL
General
1
NMR (CDCl3) δ 13.7, 23.9, 24.1 (d, JCP = 25.6 Hz),
2
25.2 (d, JCP = 1.7 Hz), 25.3 (d, JCP = 2.5 Hz),
1
1
Melting points were measured by a Yanagimoto mi-
cromelting point apparatus and are uncorrected.
33.8 (d, JCP = 42.2 Hz), 127.0 (d, JCP = 61.2 Hz),
4
128.1 (d, JCP = 10.8 Hz), 131.3(d, JCP = 2.5 Hz),

Selenophilic Reaction of Organolithium and Magnesium Reagents with Phosphinoselenoic Chlorides 189
133.1 (d, JCP = 8.3 Hz); 31P NMR (CDCl3) δ 59.1
(1 JPSe = 708.1 Hz); 77Se NMR (CDCl3) δ –436.7 (d,
1 JSeP = 708.1 Hz); EIMS (m/z) 302 (M+); Anal. Calcd
for C14H23PSe: C, 55.81; H, 7.70. Found: C, 55.59; H,
7.58. 3b: 1H NMR (CDCl3) δ 0.81 (t, J = 6.8 Hz, 3H),
(CDCl3) δ 0.89 (t, J = 7.3 Hz, 3H), 1.20–1.56 (m,
3
2H), 1.38 (d, JHP = 17.6 Hz, 18H), 1.67 (quint,
J = 7.3 Hz, 2H), 2.85–2.91 (m, 2H); 13C NMR
(CDCl3) δ 13.7, 23.1, 28.1, 32.6 (d, JCP = 2.5 Hz), 32.8
1
(d, JCP = 2.5 Hz), 42.1 (d, JCP = 25.6 Hz); 31P NMR
(CDCl3) δ 112.7 (1 JPSe = 370.9 Hz, 742.4 Hz); 77Se
3
1.21 (d, JHP = 18.5 Hz, 9H), 1.34 (sex, J = 7.3 Hz,
1
NMR (CDCl3) δ –317.2 (d, JSeP = 742.4 Hz), 120.9
2H), 1.52–1.60 (m, 2H), 2.91–2.97 (m, 2H), 7.38–7.46
1
(d, JSeP = 370.9 Hz.); EIMS (m/z) 362 (M+); Anal.
(m, 3H), 8.06–8.11 (m, 2H); 13C NMR (CDCl3) δ 13.5,
2
Calcd for C12H27PSe2: C, 40.01; H, 7.55. Found: C,
40.28; H, 7.29.
22.9, 25.5 (d, JCP = 2.5 Hz), 31.1 (d, JCP = 2.5 Hz),
32.4 (d, JCP = 3.3 Hz), 38.7 (d, 1 JCP = 37.2 Hz), 127.8
1
(d, JCP = 11.6 Hz), 130.8 (d, JCP = 52.1 Hz), 131.4
4
(d, JCP = 2.5 Hz), 133.7 (d, JCP = 9.9 Hz); 31P NMR
P,P-Bis(1,1-dimethylethyl)phosphinoselenoic
Acid Se-Butyl Ester (4c). Pale-yellow oil; 1H
NMR (CDCl3) δ 0.87 (t, J = 7.3 Hz, 3H), 1.28 (d,
3 JHP = 15.6 Hz, 18H), 1.33–1.42 (m, 2H), 1.61–1.72
(m, 2H), 2.78–2.85 (m, 2H); 13C NMR (CDCl3) δ
13.6, 23.0, 24.3 (d, JCP = 2.5 Hz), 26.6, 33.6 (d,
(CDCl3) δ 79.9 (1 JPSe = 381.9, 756.2 Hz); 77Se NMR
1
(CDCl3) δ –277.8 (d, JSeP = 756.2 Hz), 181.4 (d,
1 JSeP = 381.9 Hz); EIMS (m/z) 382 (M+); Anal. Calcd
for C14H23PSe2: C, 44.22; H, 6.10. Found: C, 44.41; H,
6.16. 4b: 1H NMR (CDCl3) δ 0.69 (t, J = 7.3 Hz, 3H),
3
1.06 (d, JHP = 17.6 Hz, 9H), 1.20 (sex, J = 7.3 Hz,
1
JCP = 2.5 Hz), 40.7 (d, JCP = 49.6 Hz); 31P NMR
2H), 1.48 (quint, J = 7.3 Hz, 2H), 2.58–2.74 (m,
2H), 7.33–7.42 (m, 3H), 7.76–7.80 (m, 2H); 13C NMR
(CDCl3) δ 13.2, 22.6, 23.6 (d, JCP = 2.5 Hz), 24.5,
32.8 (d, JCP = 3.3 Hz), 37.4 (d, 1 JCP = 62.9 Hz), 127.9
(CDCl3) δ 87.6 (1 JPSe = 377.4 Hz); 77Se NMR (CDCl3)
1
δ 63.2 (d, JSeP = 377.4 Hz); EIMS (m/z) 298 (M+);
Anal. Calcd for C12H27OPSe: C, 48.48; H, 9.15.
Found: C, 48.68; H, 9.42.
4
(d, JCP = 11.6 Hz), 131.6 (d, JCP = 2.5 Hz), 131.7,
132.5 (d, JCP = 9.9 Hz); 31P NMR (CDCl3) δ 67.3
(1 JPSe = 398.4 Hz); 77Se NMR (CDCl3) δ 129.5 (d,
1 JSeP = 398.4 Hz); EIMS (m/z) 318 (M+); Anal. Calcd
for C14H23OPSe: C, 53.00; H, 7.31. Found: C, 53.19;
H, 7.44.
Reaction of P-(1,1-Dimethylethyl)-P-phenylphos-
phinoselenoic Chloride (1b) with BuLi and
Elemental Selenium
In a 20-mL two-necked flask, BuLi (1.6 mol/L hexane
solution, 0.63 mL, 1.0 mmol) was added to a THF so-
lution (10 mL) of 1b (0.280 g, 1.0 mmol) at 0◦C, and
the mixture was stirred at that temperature for 15
min. To the reaction mixture was added elemental
selenium (0.158 g, 2.0 mmol), and the mixture was
stirred at room temperature for 1 h. The reaction
mixture was poured into water and extracted with
CH2Cl2 (50 mL). The organic layer was dried over
MgSO4 and concentrated in vacuo. The residue was
purified by column chromatography on silica gel us-
ing hexane-CH2Cl2 as eluent to give 2b (0.071 g, 24%)
and 3b (0.141 g, 37%).
P,P-Diphenylphosphinoselenoic Acid Se-Butyl
Ester (4a). Pale-yellow oil; H NMR (CDCl3) δ 0.75
1
(t, J = 7.3 Hz, 3H), 1.25 (sex, J = 7.3 Hz, 2H), 1.54–
1.61 (m, 2H), 2.73–2.79 (m, 2H), 7.37–7.47 (m, 6H),
7.79–7.84 (m, 4H); 13C NMR (CDCl3) δ 13.2, 22.6,
25.1 (d, JCP = 2.5 Hz), 32.6, 128.5 (d, JCP = 13.2 Hz),
4
131.1 (d, JCP = 10.8 Hz), 132.0 (d, JCP = 2.5 Hz),
1
134.2 (d, JCP = 97.6 Hz); 31P NMR (CDCl3) δ 39.9
(1 JPSe = 395.4 Hz); 77Se NMR (CDCl3) δ 211.9 (d,
1 JSeP = 395.4 Hz); EIMS (m/z) 338 (M+); HRMS
Calcd for C16H19OPSe: 338.0339. Found: 338.0312.
P-Butyl-P,P-bis(1,1-dimethylethyl)phosphine Se-
lenide (2c). Pale-yellow solid; mp (dec.) 106–109◦C;
1H NMR (CDCl3) δ 0.87 (t, J = 7.3 Hz, 3H), 1.27 (d,
3 JHP = 14.6 Hz, 18H), 1.27–1.41 (m, 2H), 1.58–1.67
(m, 2H), 1.74–1.81 (m, 2H); 13C NMR (CDCl3) δ 13.7,
22.2 (d, 1 JCP = 36.4 Hz), 24.4 (d, JCP = 14.1 Hz), 27.9,
P,P-Diphenylphosphinodiselenoic Acid Butyl Es-
ter (3a). Pale-yellow oil; H NMR (CDCl3) δ 0.81 (t,
1
J = 7.3 Hz, 3H), 1.33 (sex, J = 7.3 Hz, 2H), 1.60
3
(quint, J = 7.3 Hz, 2H), 2.99 (td, J = 7.3 Hz, JHP
=
12.7 Hz), 7.38–7.47 (m, 6H), 7.89–7.96 (m, 4H); 13C
NMR (CDCl3) δ 13.5, 22.8, 31.5 (d, JCP = 1.7 Hz),
32.1 (d, JCP = 4.1 Hz), 128.4 (d, JCP = 12.4 Hz),
1
28.3 (d, JCP = 3.3 Hz), 36.9 (d, JCP = 33.9 Hz); 31P
NMR (CDCl3) δ 76.9 (1 JPSe = 688.5 Hz); 77Se NMR
1
4
(CDCl3) δ –464.2 (d, JSeP = 688.5 Hz); EIMS (m/z)
131.7 (d, JCP = 3.3 Hz), 131.8 (d, JCP = 11.6 Hz),
1
282 (M+); Anal. Calcd for C12H27PSe: C, 51.24; H,
9.68. Found: C, 51.07; H, 9.87.
133.9 (d, JCP = 68.6 Hz); 31P NMR (CDCl3) δ 40.3
(1 JPSe = 371.3, 765.2 Hz); 77Se NMR (CDCl3) δ –176.5
1
1
(d, JSeP = 765.2 Hz), 289.0 (d, JSeP = 371.3 Hz);
EIMS (m/z) 402 (M+); HRMS Calcd for C16H19PSe2:
401.9555. Found: 401.9579.
P,P-Bis(1,1-dimethylethyl)phosphinodiselenoic
Acid Butyl Ester (3c). Pale-yellow oil; 1H NMR

190 Kimura, Murai, and Mizuhata
P-(1,1-Dimethylethyl)-P-phenylphosphinodisele-
noic Acid Phenyl Ester (3d). Pale-yellow solid;
mp (dec.) 95–98◦C; 1H NMR (CDCl3) δ 1.33 (d,
3 JHP = 19.0 Hz, 9H), 7.22–7.28 (m, 2H), 7.32–7.41
(m, 1H), 7.44–7.51 (m, 5H), 8.16–8.21 (m, 2H);
Reaction of P,P-Diphenylphosphinothioic
Chloride (7) with PhLi and Elemental Selenium
In a 20-mL two-necked flask, PhLi (0.94 mol/L
cyclohexane-Et2O solution, 1.05 mL, 1.0 mmol)
was added to a THF solution (10 mL) of P,P-
diphenylphosphinothioic chloride (7) (0.253 g, 1.0
mmol) at 0◦C, and the mixture was stirred at that
temperature for 15 min. To the reaction mixture was
added elemental selenium (0.087 g, 1.1 mmol), and
the mixture was stirred at room temperature for
1 h. The reaction mixture was poured into water
and extracted with Et2O (50 mL). The organic layer
was dried over MgSO4 and concentrated in vacuo.
The residue was purified by column chromatogra-
phy on silica gel using hexane-Et2O as eluent to give
triphenylphosphine sulfide (8) (0.230 g, 78%) as a
colorless solid.
2
13C NMR (CDCl3) δ 25.9 (d, JCP = 1.7 Hz), 39.6 (d,
1 JCP = 34.7 Hz), 125.0 (d, JCP = 5.8 Hz), 127.9 (d,
JCP = 11.6 Hz), 128.9 (d, JCP = 1.7 Hz), 129.4
1
(d, JCP = 1.7 Hz), 129.8 (d, JCP = 52.1 Hz),
131.5 (d, JCP = 2.5 Hz), 134.1 (d, JCP = 9.1 Hz),
137.4 (d, JCP = 3.3 Hz); 31P NMR (CDCl3) δ 85.7
(1 JPSe = 371.4, 774.2 Hz); 77Se NMR (CDCl3) δ –239.6
1
1
(d, JSeP = 774.2 Hz), 365.4 (d, JSeP = 371.4Hz);
EIMS (m/z) 402 (M+); Anal. Calcd for C16H19PSe2:
C, 48.02; H, 4.79. Found: C, 47.76; H, 4.69.
P,P-Bis(1,1-dimethylethyl)-P-phenylphosphine Se-
lenide (2e). Pale-yellow solid; mp (dec.) 140–145◦C;
3
1H NMR (CDCl3) δ 1.39 (d, JHP = 15.6 Hz, 18H),
7.40–7.48 (m, 3H), 8.20–8.30 (m, 2H); 13C NMR
P-(1,1-Dimethylethyl)-P-phenylphosphinodisele-
1
noic Acid Methyl Ester (3g). Pale-yellow oil; 1H
(CDCl3) δ 28.8, 38.1 (d, JCP = 33.9 Hz), 127.6 (d,
3
1 JCP = 54.2 Hz), 127.7 (d, JCP = 10.8 Hz), 131.1 (d,
NMR (CDCl3) δ 1.23 (d, JHP =19.5 Hz, 9H), 2.18 (d,
3 JHP =12.2 Hz, 3H), 7.40–7.48 (m, 3H), 8.05–8.11
(m, 2H); 13C NMR (CDCl3) δ 9.2 (d, JCP = 2.5 Hz),
25.6 (d, JCP = 2.5 Hz), 39.0 (d, JCP = 36.4 Hz), 128.0
(d, JCP = 11.6 Hz), 129.8 (d, JCP = 52.9 Hz), 131.6
(d, JCP = 3.3 Hz), 133.7 (d, JCP = 9.1 Hz); 31P NMR
(CDCl3) δ 82.6 (1 JPSe = 366.2, 762.9 Hz); 77Se NMR
4 JCP = 2.5 Hz), 134.8; 31P NMR (CDCl3) δ 79.5 (1 JPSe
=
=
1
708.1 Hz); 77Se NMR (CDCl3) δ –423.9 (d, JSeP
708.1 Hz); EIMS (m/z) 302 (M+); Anal. Calcd for
C14H23PSe: C, 55.81; H, 7.70. Found: C, 55.81; H, 7.88.
P-(1,1-Dimethylethyl)-P-phenylphosphinodisele-
1
(CDCl3) δ –279.7 (d, JSeP = 762.9 Hz), 112.6 (d,
noic Acid 1,1-Dimethylethyl Ester (3e). Pale-yellow
1 JSeP = 366.2 Hz); EIMS (m/z) 340 (M+); Anal. Calcd
for C11H17PSe2: C, 39.07; H, 5.07. Found: C, 39.28;
H, 4.91.
1
solid; mp (dec.) 102–105◦C; H NMR (CDCl3) δ 1.17
3
4
(d, JHP = 19.0 Hz, 9H), 1.51 (d, JHP = 1.0 Hz,
9H), 7.41–7.44 (m, 3H), 8.19–8.25 (m, 2H); 13C
1
NMR (CDCl3) δ 25.5, 33.1, 39.4 (d, JCP = 37.2 Hz),
2
53.1 (d, JCP = 4.1 Hz), 127.6 (d, JCP = 11.6 Hz),
REFERENCES
1
4
130.8 (d, JCP = 50.5 Hz), 131.2 (d, JCP = 2.5 Hz),
134.2 (d, JCP = 9.9 Hz); 31P NMR (CDCl3) δ 65.8
(1 JPSe = 420.9, 745.6 Hz); 77Se NMR (CDCl3) δ –237.8
[1] (a) Au-Yeung, T.-L.; Chan, K.-Y.; Chan, W.-K.; Haynes,
R. K.; Williams, I. D.; Yeung, L. L. Tetrahedron
Lett 2001, 42, 453; (b) Horner, L.; Schlotthauer, B.
Phosphorus Sulfur 1978, 4, 155.
[2] (a) Omelanczuk, J.; Mikolajczyk, M. J Chem Soc,
Chem Comm 1994, 2223; (b) Omelanczuk, J. Heteroat
Chem 1992, 3, 403; (c) Ha¨gele, G.; Ku¨ckelhaus, W.;
Tossing, G.; Seega, J.; Harris, R. K.; Creswell, C. J.;
Jageland, P. T. J Chem Soc, Dalton Trans 1987, 795.
1
1
(d, JSeP = 745.6 Hz), 385.2 (d, JSeP = 420.9 Hz);
EIMS (m/z) 382 (M+); Anal. Calcd for C14H23PSe2:
C, 44.22; H, 6.10. Found: C, 44.22; H, 5.97.
P-(1,1-Dimethylethyl)-P-phenyl-P-phenylethynyl-
1
phosphine Selenide (2f). Pale-yellow oil; H NMR
[3] Bayandina,
E.
V.;
Nuretdinov,
I.
A.;
3
(CDCl3) δ 1.26 (d, JHP =19.5 Hz, 9H), 7.35–7.51 (m,
Nurmukhamedova, L. V. Zh Obshch Khim 1978, 48,
2673.
[4] (a) Kimura, T.; Murai, T. Chem Lett 2004, 878; (b)
Kimura, T.; Murai, T. J Org Chem, 2005, 70, 952.
[5] Kawashima, T.; Iwanaga, H.; Okazaki, R. Heteroat
Chem 1995, 6, 235.
[6] Buina, N. A.; Sibgatullina, F. G.; Nuretdinov, I. A. Zh
Obshch Khim 1979, 49, 2386.
[7] Phosphinic chlorides were also reported to react
with organometallic reagents to give the correspond-
ing phosphine oxides: Tsvetkov, E. N.; Syundyukova,
V. Kh.; Baulin, V. E. Izv Akad Nauk SSSR Ser Khim
1989, 147.
6H), 7.58 (d, J = 7.8 Hz, 2H), 8.04–8.09 (m, 2H);
2
13C NMR (CDCl3) δ 24.5 (d, JCP = 3.3 Hz), 36.1 (d,
1
1 JCP = 50.5 Hz), 78.4 (d, JCP = 128.2 Hz), 106.4
2
(d, JCP = 19.0 Hz), 120.3 (d, JCP = 4.1 Hz), 128.1
1
(d, JCP = 13.2 Hz), 128.3 (d, JCP = 77.7 Hz), 128.6,
130.5, 131.8 (d, JCP = 3.3 Hz), 132.4 (d, JCP = 1.7 Hz),
132.7 (d, JCP = 10.8 Hz); 31P NMR (CDCl3) δ 34.3
(1 JPSe = 742.7 Hz); 77Se NMR (CDCl3) δ –316.3 (d,
1 JSeP = 742.7 Hz); EIMS (m/z) 346 (M+); HRMS
Calcd for C18H19PSe: 346.0390. Found: 346.0395.

Selenophilic Reaction of Organolithium and Magnesium Reagents with Phosphinoselenoic Chlorides 191
[8] In the absence of MeI, a liberation of red selenium
Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.;
Raghavachari, K.; Foresman, J. B.; Cioslowski, J.;
Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko,
A.; Piskorz, P.; Komaromi, I.; Gomperts, R.;
Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham,
M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.;
Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen,
W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-
Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98,
revision A.7; Gaussian, Inc., Pittsburgh PA, 1998.
[11] Schaftenaar, G.; Noordik, J. H. Molden: a pre- and
post-processing program for molecular and elec-
tronic structures. J Comput-Aided Mol Design 2000,
14, 123.
was observed when the organic layer was washed
with water. It may be due to the decomposition of
the salt 11.
[9] Davies, R. P.; Martinelli, M. G. Inorg Chem 2002, 41,
348.
[10] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria,
G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski,
V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.;
Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels,
A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.;
Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Men-
nucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.;
Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui,