A simple one-pot synthesis of phosphinoselenoic amides and diamides from secondary phosphine selenides and amines using Et3N-CCl4

Article abstract of DOI:10.1016/j.tetlet.2011.02.095

The multi-component reaction between secondary phosphine selenides and amines (primary, secondary, and primary diamines) proceeds using the Et ₃N-CCl₄ system under mild conditions to give phosphinoselenoic amides or diamides in 81-89

Full text of DOI:10.1016/j.tetlet.2011.02.095

Tetrahedron Letters 52 (2011) 2367–2369
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Tetrahedron Letters
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A simple one-pot synthesis of phosphinoselenoic amides and diamides
from secondary phosphine selenides and amines using Et3N-CCl4
⇑
Nina K. Gusarova, Pavel A. Volkov, Nina I. Ivanova, Ludmila I. Larina, Boris A. Trofimov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1, Favorsky Str., RUS-664033 Irkutsk, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
The multi-component reaction between secondary phosphine selenides and amines (primary, secondary,
and primary diamines) proceeds using the Et3N-CCl4 system under mild conditions to give phosphinose-
lenoic amides or diamides in 81–89% isolated yields.
Received 30 December 2010
Revised 27 January 2011
Accepted 21 February 2011
Available online 26 February 2011
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
Secondary phosphine selenides
Amines
Phosphinoselenoic amides
Phosphinic and phosphinothioic amides and diamides are em-
ployed extensively as ligands for the design of metal-complexes,1
precursors of biologically active drugs2 and building blocks in or-
ganic and elementoorganic synthesis.3 Phosphinoselenoic amides
and diamides also attract continued research interest. For example,
complexes of these phosphinoselenoic amides with transition met-
als (Ti, Cr, Mn, Fe, Co, Ni, Zn, Cd)4 are successfully used as single-
source precursors for the preparation of metal selenide thin
films.4c,d Diphenylphosphinoselenoic amides are known to be ace-
tylcholinesterase inhibitors.5 However, the conventional syntheses
of phosphinoselenoic amides are tedious and involve utilizing
moisture- and air-sensitive phosphorus halides4a,5,6 and, in some
cases, difficult to obtain organylamides of alkali metals.4a,6c–f The
Todd–Atherton reaction, which was discovered and investigated
using dialkyl phosphites,7 and briefly described for secondary
phosphine oxides and phosphine sulfides,8 represents a simple
and convenient approach to phosphinoselenoic amides. Reports
on the possible application of secondary phosphine selenides in
Todd–Atherton type reactions are absent in the literature.
In this paper, we report for the first time the multi-component
one-pot reaction of secondary phosphine selenides with primary
and secondary amines and primary diamines using the Et3N-CCl4
system.
The mechanism of this reaction can be rationalized as follows
(Scheme 1). P,Se-ambident selenophosphinite anion A, formed via
deprotonation of the secondary phosphine selenide 1 or 2 under
the action of triethylamine, reacts with carbon tetrachloride to fur-
nish phosphinoselenoic chloride B and the –CCl3 carbanion. Proto-
nation of the latter by a triethylammonium cation leads to
regeneration of triethylamine and formation of chloroform. Phos-
phinoselenoic chloride B reacts with the primary or secondary
amine 3–7 in the presence of triethylamine to give phosphinosele-
noic amides 8a–f and triethylammonium chloride. Bis(2-phen-
ethyl)phosphinoselenoic chloride10 and chloroform were
identified in the reaction mixture by 1H, 13C and 31P NMR
spectroscopy.
The reaction was found to be general in character. Secondary
phosphine selenides possessing aryl and arylalkyl substituents, as
well as different primary and secondary amines, including unsatu-
rated examples, participated readily in this multi-component reac-
tion. The general character of the reaction is additionally supported
by the fact that diamines can also be employed in this reaction.
For example, primary diamines 9–12 react readily (20–25 °C,
1 h) with two equivalents of the secondary phosphine selenides 1
or 2 in Et3N-CCl4 to furnish the corresponding diamides 13a–e in
81–89% yield11 (Table 2).
Experiments have shown9 that secondary phosphine selenides
1 and 2 react with primary 3 and 4, or secondary amines 5–7 using
the Et3N-CCl4 system under mild conditions (20–25 °C, 1 h) to af-
ford diphenyl- and bis(2-phenylethyl)phosphinoselenoic amides
8a–f in 82–87% isolated yields (Table 1).
In summary, the multi-component reaction between secondary
phosphine selenides and various amines or diamines using the
Et3N-CCl4 system affords phosphinoselenoic amides and diamides
in high yields. The polyfunctional compounds synthesized are pro-
spective ligands for the preparation of metal-complexes, promising
intermediates for the production of conducting nanomaterials, pre-
cursors for the design of biologically active compounds, and build-
ing blocks for elementoorganic synthesis.
⇑
Corresponding author. Fax: +7 3952 396046.
E-mail address: boris_trofimov@irioch.irk.ru (B.A. Trofimov).
0040-4039/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2011.02.095

2368
N. K. Gusarova et al. / Tetrahedron Letters 52 (2011) 2367–2369
Table 1
Synthesis of phosphinoselenoic amides 8a–fa
R1
R1
R1
R1
Se
H
1, 2
Et3N/CCl4, r.t., 1 h
Se
HNR2R3
P
P
+
NR2R3
8a-f
- [Et3NH]Cl
- CHCl3
3-7
Entry
R12P(Se)H 1, 2 (1 mmol)
R1
R2R3NH 3–7 (1 mmol)
R2
R3
Product
Yield (%)
b
c
1
2
3
4
5
6
1
2
2
2
2
2
6
3
4
5
6
7
n-Pr
H
n-Pr
Allyl
Ph
8a
8b
8c
8d
8e
8f
90
89
94
91
93
90
82
83
86
83
87
82
H
Et
Et
n-Pr
n-Bu
n-Pr
n-Bu
a
b
c
All experiments were carried out under argon at r.t. for 1 h; Et3N (1 mmol) and CCl4 (4 ml) were used.
Yields calculated from the 31P NMR spectra of the crude products.
Isolated yield.
R1
R1
R1
R1
R1
R1
Se
Cl
Se
H
Et3N
CCl4
Acknowledgments
P
Se
P
+
CCl3
P
_ Et3HN
B
A
1, 2
This work was supported by the President of the Russian Feder-
ation (program for the support of leading scientific schools, grant
no. NSh-3230.2010.3 and young Russian scientists MK-
629.2010.3).
CCl3
+
Et3N
Se
+
+
CHCl3
Et3HN
R1
HNR2R3
Et3N
3-7
B
P
[Et3NH]Cl
NR2R3
R1
A. Supplementary data
8
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.tetlet.2011.02.095.
Scheme 1. A tentative mechanism for the formation phosphinoselenoic amides.
Table 2
Reaction of phosphine selenides 1 and 2 with diamines 9–12a
R1
Se
H
R1
R1
R1
R1
Se
N
Se
N
Et3N/CCl4, r.t., 1 h
P
+
H2N
NH2
P
H
P
H
X
R1
1, 2
- [Et3NH]Cl
- CHCl3
X
9-12
13a-e
Entry
R12P(Se)H 1, 2 (1 mmol)
R1
H2NXNH2 9–12 (0.5 mmol)
X
Product
Yield (%)
b
c
1
2
3
4
5
1
2
2
2
2
11
9
(CH2)6
13a
13b
13c
13d
13e
90
87
89
93
91
85
81
83
89
86
CH2(Me)CH
(CH2)5
10
11
12
(CH2)6
(CH2)7
a
b
c
All experiments were carried out under argon at r.t. for 1 h; Et3N (1 mmol) and CCl4 (4 ml) were used.
Yields calculated from the 31P NMR spectra of the crude products.
Isolated yield.

N. K. Gusarova et al. / Tetrahedron Letters 52 (2011) 2367–2369
2369
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9. General procedure for the synthesis of phosphinoselenoic amides 8a–f. A mixture
of secondary phosphine selenide
1 or 2 (1.0 mmol) and Et3N (101 mg,
1.0 mmol) in CCl4 (4 ml) was stirred at 20–25 °C for 10 min. A solution of
amine 3–7 (1.0 mmol) in CCl4 (1 ml) was added, and the mixture was stirred at
20–25 °C for 50 min. The solvent was removed under reduced pressure, and
1,4-dioxane (3 ml) was added. The precipitated white solid (triethylammonium
chloride) was removed by filtration and the 1,4-dioxane evaporated under
vacuum. The residue obtained was washed with hot hexane (2 Â 3 ml), and the
hexane solution was allowed to stand for 12 h at 0–1 °C. The hexane layer was
filtered and evaporated under vacuum. The residue was dried in vacuo to give
amides 8a–f.
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Trofimov, B. A. Russ. J. Gen. Chem. Engl. Transl. 2010, 80, 1043.
11. General procedure for the synthesis of phosphinoselenoic diamides 13a–e.
A
mixture of secondary phosphine selenide 1 or 2 (1.0 mmol) and Et3N (101 mg,
1.0 mmol) in CCl4 (4 ml) was stirred at 20–25 °C for 10 min. A solution of
diamine 9–12 (0.5 mmol) in CCl4 (1 ml) was added, and the reaction mixture
stirred at 20–25 °C for 50 min. The solvent was removed under reduced
pressure, and 1,4-dioxane (3 ml) was added. The precipitated white solid
(triethylammonium chloride) was removed by filtration and the 1,4-dioxane
evaporated under vacuum. The crude product was washed with hot hexane
(3 Â 2 ml), and the hexane was removed by decanting. The residue was dried
under vacuo to give diamides 13a–e.