Cross-coupling between secondary phosphine selenides and primary or secondary amines: Halogen-free synthesis of phosphinoselenoic amides

Article abstract of DOI:10.1016/j.mencom.2013.09.004

Secondary phosphine selenides react with primary or secondary amines at 60-65 C in dioxane to give phosphinoselenoic amides.

Full text of DOI:10.1016/j.mencom.2013.09.004

Mendeleev
Communications
Mendeleev Commun., 2013, 23, 253–254
Cross-coupling between secondary phosphine
selenides and primary or secondary amines:
halogen-free synthesis of phosphinoselenoic amides
Nina K. Gusarova, Svetlana I. Verkhoturova, Tatyana I. Kazantseva,
Svetlana N. Arbuzova, Alexander I. Albanov and Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
664033 Irkutsk, Russian Federation. Fax: +7 3952 41 9346; e-mail: boris_trofimov@irioch.irk.ru
DOI: 10.1016/j.mencom.2013.09.004
Secondary phosphine selenides react with primary or secondary amines at 60–65°C in dioxane to give phosphinoselenoic amides.
Se
H
R2
R3
R1
R1
The chemistry of phosphinoselenoic amides has been developed
very intensely in the recent decade.1 Of special interest are organo-
metallic complexes with phosphinoselenoic amide ligands.2 For
example, their complexes with yttrium catalyzes intramolecular
alkene hydroamination,2(a) whereas the ruthenium complexes act
as precatalysts for the transfer hydrogenation of acetophenone.2(b)
Complexes of phosphinoselenoic amides with transition metals
(Ti, Cr, Mn, Fe, Co, Ni, Zn, Cd)3 are successfully used as single-
source precursors of remarkable nanomaterials.3(c),(d) Phosphino-
selenoic amides are also prospective intermediates for pharma-
ceuticals.1(a),(e) In general, phosphinoselenoic amides are prepared
from chemically aggressive phosphorus halides, amines or alkali
metal organylamides.1(a)–(i),3(a),4 Recently a new approach to phos-
phinoselenoicamidesbasedontheoxidative cross-coupling between
secondary phosphine selenides and NH-amines in the Et3N/CCl4
system has been published (Scheme 1),1(j) triethylammonium
chloride and chloroform being formed as the by-products. Apart
from these, diorganylphosphinoselenoic chlorides have been
identified in the reaction mixture.1(j)
+
P
HN
1 R1 = Ph
3 R2 = H, R3 = Allyl
4 R2 = H, R3 = Bn
5 R2 = R3 = Et
2 R1 = PhCH2CH2
6 R2 = R3 = Bu
R1
R1
Se
P
60–65 °C, 2–7 h
dioxane, Ar
N
R2
R3
7a R1 = Ph, R2 = H, R3 = Allyl
7b R1 = Ph, R2 = H, R3 = Bn
7c R1 = Ph, R2 = R3 = Et
7d R1 = Ph, R2 = R3 = Bu
7e R1 = PhCH2CH2, R2 = H, R3 = Allyl
7f R1 = PhCH2CH2, R2 = H, R3 = Bn
Scheme 2
R2
Table 1 Reaction of secondary phosphine selenides with primary or secondary
amines (dioxane, 60–65°C).
HN
R1
R1
R1
R1
Se
H
Se
Cl
R3
Et3N/CCl4
P
P
Phosphine
selenide
Isolated
yield (%)
Entry
Amine
t/h
Amide
R1
Se
P
+
[Et3NH]Cl + CHCl3
1
1
1
1
1
2
2
2
2
3
4
5
6
3
4
4
3
2
4
2
2
2
7
7
9
7a
7b
7c
7d
7e
7f
33
25
28
27
44
36
36
10
R1
N
R2
2
R3
3
4
Scheme 1
5
6
Herein, we report for the first time on unexpected halogen-
free version of cross-coupling reaction between secondary
phosphine selenides and NH-amines.
We have found that secondary phosphine selenides 1, 2 react
with primary (3, 4) or secondary (5, 6) amines in an equimolar
ratio at 60–65°C for 2–7 h in dioxane under argon to afford
7a
8b
7f
7e
a Experiment was carried out at 90–95°C. b Benzene was used instead of
dioxane.
mixtures contained corresponding secondary phosphines 8, ammonium
phosphinodiselenoates 9 and phosphinoselenoates 10. After isolation (see
below) pure phosphinoselenoic amides 7 were obtained as solids or oils.
The 1H, 13C, 15N, 31P and 77Se NMR spectra were recorded on Bruker
DPX-400 and AV-400 spectrometers (400.13, 100.62, 40.55, 161.98 and
76.31 MHz, respectively). Chemical shifts 15N of the compounds were
determined to within 0.1 ppm using 2D 1H-15N NMR HMBC technique.
N-Allyl(diphenyl)phosphinoselenoic amide 7a. Dioxane was removed
under reduced pressure, the residue was dissolved in 2 ml of benzene
and the solution was passed through a layer of Al2O3 (0.8 cm, benzene as
d
iphenyl- and diphenethylphosphinoselenoic amides 7a–f in 25–44%
isolated yields† (Scheme 2, Table 1, entries 1–6).
†
Synthesis of compounds 7 (general procedure). All operations were
performed in the laboratory fume hood. A solution of secondary phosphine
selenide 1, 2 (0.4 mmol) and amine 3–6 (0.4 mmol) in 2 ml of dioxane
was blown with argon and stirred at 60–65°C for 2–7 h. The reaction
was monitored by 31P NMR up to disappearance of peaks of the initial
compounds 1, 2 (3–8 ppm). Along with the target amides 7, the reaction
© 2013 Mendeleev Communications. All rights reserved.
– 253 –

Mendeleev Commun., 2013, 23, 253–254
An attempt to raise the yields of amides 7 by increasing the
at heating (60–65°C) to deliver amides 7 and H2Se. This assump-
tion has been experimentally proved on the example of phosphino-
diselenoate 9e (synthesized according to published protocol6),
which, when heated (60–65°C, 2 h, dioxane), gives amide 7e
almost quantitatively.
reaction temperature up to 90–95°C gave no desirable results
(Table 1, cf. entries 6 and 7). The application of benzene as a
solvent (instead of dioxane) decreases dramatically the efficacy
of the process (Table 1, cf. entries 5 and 8).
Note that corresponding secondary phosphines 8 (–70 to
Thus, formation of phosphinoselenoic amides 7 proceeds
probably via reaction of secondary phosphine selenides 1, 2 and
amines 3–6 at room temperature resulting in secondary phos-
phines 8 and ammonium phosphinodiselenoates 9. The latter
then decompose at heating to amides 7 and hydrogen selenide.
Such direction is possible as exemplified by the decomposition
of ammonium phenylphosphonamidodiselenoates (toluene, reflux,
12 h) to phenylphosphonoselenoic diamides with releasing of
hydrogen selenide.1(k)
In conclusion, cross-coupling reaction between secondary
phosphine selenides and NH-amines represents a novel convenient
halogen-free approach to phosphinoselenoic amides, prospective
ligands for metal complex catalysts, single-source precursors of
nanomaterials and intermediates for pharmaceuticals.
1
–40 ppm, JPH ~ 200 Hz), ammonium phosphinodiselenoates 9
1
(22–25 ppm, JPSe ~ 560–610 Hz) as well as ammonium phos-
1
phinoselenoates‡ 10 (50–65 ppm, JPSe ~ 635–675 Hz) are also
identified in the reaction mixture (31P NMR data). The latter
result probably from partial oxidation of the phosphine selenides
1, 2 to phosphinoselenoic acids followed by their reaction with
amines 3–6. This fact was proved by the increasing the content
of phosphinoselenoates 10 in the reaction mixture when reaction
proceeded on contact with air.
Compounds 8 and 9 are formed obviously by the direct
interaction of the initial reactants 1, 2 and 3–6 (Scheme 3).
Se
R1
R1
R1
R1
Se
H
R2
R3
R1
R1
R2
R3
+
+
PH
P
H2N
2
P
HN
This work was supported by the President of the Russian
Federation (grant for support of leading scientific schools no.
NSh-1550.2012.3) and the Russian Foundation for Basic Research
(grant no. 11-03-00286).
Se
1, 2
3–6
8
9
Scheme 3
Such reaction was reported for bis(2-phenylethyl)phosphine
selenide and diisopropylamine, which react in the molar ratio of
2:1 at room temperature for 10 min to afford the corresponding
ammonium phosphinodiselenoate and bis(2-phenylethyl)phosphine.5
We assume that under the conditions elaborated (Table 1), the
initially formed ammonium phosphinodiselenoates 9 decompose
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.mencom.2013.09.004.
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tion as mentioned for the product 7a. Yield 0.038 g (28%), white solid,
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mp 75–76°C (lit.,1(e) 77–78°C). H NMR (CDCl3) d: 1.11 (t, 6H, Me,
3JHH 7.1 Hz), 3.02 (dq, 4H, CH2, 3JHP 12.4 Hz, 3JHH 7.2 Hz), 7.47 (m, 6H,
m-HPh, p-HPh), 8.01 (m, 4H, o-HPh). 13C NMR (CDCl3) d: 13.54 (d, Me,
3JCP 5.8 Hz), 41.33 (d, CH2, 2JCP 3.4 Hz), 128.33 (d, m-CPh, 3JCP 12.7 Hz),
131.63 (d, p-CPh, 4JCP 2.9 Hz), 132.39 (d, o-CPh, 2JCP 11.0 Hz), 133.26 (d,
i
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77Se NMR (CDCl3) d: –276.5 (d, 1JSeP 747.3 Hz). 15N NMR, d: –334.5.
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C16H20NPSe (%): C, 57.15; H, 5.99; N, 4.17; P, 9.21; Se, 23.48.
‡
Diethylammonium diphenylphosphinoselenoate 10c. Yield 0.013 g (9%),
white solid, mp 147–150°C (decomp.). 1H NMR (CDCl3) d: 1.21 (t, 6H,
Me, 3JHH 7.5 Hz), 2.74 (q, 4H, CH2, 3JHH 7.5 Hz), 7.32 (m, 6H, m-HPh
,
p-HPh), 7.85 (m, 4H, o-HPh), 9.47 (br.s, 2H, NH2). 13C NMR (CDCl3)
d: 11.44 (Me), 42.18 (CH2), 127.81 (d, m-CPh
3JCP 12.3 Hz), 129.99
(d, p-CPh, 4JCP 2.9 Hz), 130.41 (d, o-CPh, 2JCP 11.1 Hz), 142.61 (d, i-CPh
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,
1JCP 91.9 Hz). 31P NMR (CDCl3) d: 53.68 (s + d satellite, 1JPSe 650.5 Hz).
77Se NMR (CDCl3) d: –140.3 (d, 1JSeP 650.5 Hz). 15N NMR, d: –328.8.
Found (%): C, 53.88; H, 6.21; N, 3.91; P, 9.08; Se, 21.98. Calc. for
C16H22NOPSe (%): C, 54.24; H, 6.26; N, 3.95; P, 8.74; Se, 22.29.
For characteristics of compounds 7b,d–f and 10d, see Online Supple-
mentary Materials.
Received: 20th June 2013; Com. 13/4139
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