Chemoselective reactions of secondary phosphine chalcogenides with vinyloxyalkylamines: Synthesis of a novel family of functional phosphinohalcogenic amides

Article abstract of DOI:10.1055/s-0032-1316750

The reactions of secondary phosphine halcogenides with vinyloxyalkylamines proceed chemoselectively in triethylamine-carbon tetrachloride under mild conditions to give the corresponding phosphinohalcogenic amides bearing vinyloxy moieties in 78-95% yields. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0032-1316750

2786▌
PAPER
paper
Chemoselective Reactions of Secondary Phosphine Chalcogenides with
Vinyloxyalkylamines: Synthesis of a Novel Family of Functional
Phosphinoсhalcogenоic Amides
Synthesis of Functional Phosphinoсhalcogenоic Amides
Nina K. Gusarova, Pavel A. Volkov, Nina I. Ivanova, Ludmila A. Oparina, Nikita A. Kolyvanov, Oksana V. Vysotskaya,
Ludmila I. Larina, Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk,
Russian Federation
Fax +7(3952)419346; E-mail: boris_trofimov@irioch.irk.ru
Received: 17.05.2012; Accepted after revision: 23.06.2012
substituents based on the chemoselective reaction of
Abstract: The reactions of secondary phosphine сhalcogenides
vinyloxyalkylamines
with
secondary
phosphine
with vinyloxyalkylamines proceed chemoselectively in triethyl-
amine–carbon tetrachloride under mild conditions to give the corre-
sponding phosphinoсhalcogenоic amides bearing vinyloxy
moieties in 78–95% yields.
сhalcogenides, which recently became available via one-
pot syntheses from red phosphorus and styrenes.6 The
choice of vinyloxyalkylamines as substrates is appropri-
ate as these compounds are produced by industrially fea-
sible direct vinylation of amino alcohols with ethyne.7
Key words: amines, amides, chalcogenides, chemoselective, cross-
coupling
The outcomes of the reactions of vinyloxyalkylamines
with secondary phosphine сhalcogenides are not always
predictable. Theoretically, this reaction can proceed by
way of oxidative cross-coupling of secondary phosphine
сhalcogenides with the NH groups of the vinyloxyalkyl-
amines in the triethylamine–carbon tetrachloride (Et3N–
CCl4) system,8 or via addition of the secondary phosphine
сhalcogenide to the double bond of the vinyloxy moiety.9
Furthermore, it is known that vinyl ethers are able to react
with carbon tetrachloride under certain conditions.10
Phosphinic, phosphinothioic and phosphinoselenoic am-
ides find wide application in the design of multi-purpose
metal complexes.1,2 For example, complexes of phosphi-
nochalcogenoic amides with zirconium and lanthanides
were shown to be effective precatalysts for intramolecular
alkene hydroaminations.1 Amides with phosphinochal-
cogenoic moieties were used to generate active palladium
catalysts for the Suzuki–Miyaura reaction.2h Phosphino-
chalcogenoic amides were also employed as catalysts for
the asymmetric N,O-acetalization of aldehydes.2i Com-
plexes of di(tert-butyl)selenophosphinic amides with
transition metals (Ti,2a Zn, Cd,2b Cr, Mn, Fe, Co, Ni2f) are
popular single-source precursors for the preparation of
nano-sized metal selenides possessing unique semicon-
ductor and magneto-optical properties. Moreover, phos-
phinochalcogenoic amides have attracted interest as
intermediates for drug design,3 and as building blocks for
organic and element-organic synthesis.3a,4 Diphe-
nylphosphinothioic and diphenylphosphinoselenoic am-
ides can function as acetylcholinesterase inhibitors,3c
while several derivatives of diphenylphosphinic amide
display high fungicidal activity.3a Functional phosphino-
chalcogenoic amides bearing, for example, vinyloxy moi-
eties as attractive building blocks and monomers/co-
monomers deserve particular attention in view of the rich
and diverse chemistry of vinyl ethers.5 To the best of our
knowledge, the literature lacks any data on such function-
al phosphinochalcogenoic amides.
As our experiments showed, secondary phosphine oxide
1, phosphine sulfides 2 and 3 and phosphine selenides 4–
6 reacted with vinyloxyalkylamines 7–9 in the triethyl-
amine–carbon tetrachloride system, under mild condi-
tions (r.t., 0.5–1.5 h, argon), to afford chemoselectively,
phosphinochalcogenoic amides 10a–m in 78–95% yield
(Table 1).
The reaction was found to be general in character. Sec-
ondary phosphine chalcogenides 1–6, possessing aryl and
arylalkyl substituents, as well as various primary (7 and 8)
and secondary (9) amines participated readily in this pro-
cess. The obtained results showed that the reactivity of the
secondary phosphine chalcogenides in reactions with
amines 7–9 decreased in the following order: secondary
phosphine selenides ≥ secondary phosphine sulfides >
secondary phosphine oxides (Table 1, compare entries 1,
4 and 9), which is in agreement with previously published
data.11
The mechanism of the reaction is likely triggered by
deprotonation of the secondary phosphine сhalcogenide
by triethylamine to give P,X-ambident сhalcogeno-
phosphinite anion А. The latter takes part in one-electron
transfer with carbon tetrachloride (oxidizer) to afford the
free radical of the secondary phosphine chalcogenide, B
and anion radical C, the interaction of which leads to
Herein, we report a convenient approach to a novel family
of phosphinochalcogenoic amides possessing vinyloxy
SYNTHESIS 2012, 44, 2786–2792
Advanced online publication: 08.08.2012
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
DOI: 10.1055/s-0032-1316750; Art ID: SS-2012-T0451-OP
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Functional Phosphinoсhalcogenоic Amides
2787
Table 1 Oxidative Cross-Coupling of Secondary Phosphine Chalcogenides with Amines for the Synthesis of Phosphinochalcogenoic Amidesa
R1
R1
R1
R1
X
H
X
H
Et3N–CCl4, r.t.
+
P
N(CH2)nOCH=CH2
P
R2
N(CH2)nOCH=CH2
7–9
R2
1–6
10a–m
Entry
(R1)2P(X)H
X
R1
Amine
R2
n
Time (h)
Product
Yield (%)
1
1
2
2
3
3
3
4
4
5
5
5
6
6
O
Ph(CH2)2
Ph
7
7
8
7
8
9
7
8
7
8
9
7
8
H
2
2
3
2
3
2
2
3
2
3
2
2
3
1.5
0.5
0.5
0.5
0.5
1
10a
10b
10c
10d
10e
10f
78
84
87
90
88
79
80
87
92
90
80
89
95
2
S
H
3
S
Ph
H
4
S
Ph(CH2)2
Ph(CH2)2
Ph(CH2)2
Ph
H
5
S
H
6
S
Me
H
7
Se
Se
Se
Se
Se
Se
Se
0.5
0.5
0.5
0.5
1.5
0.5
0.5
10g
10h
10i
8
Ph
H
9
Ph(CH2)2
Ph(CH2)2
Ph(CH2)2
PhCH(Me)CH2
PhCH(Me)CH2
H
10
11
12
13
H
10j
Me
H
10k
10l
H
10m
a Reaction conditions: phosphine chalcogenide 1–6 (1 mmol), amine 7–9 (1 mmol), Et3N (1 mmol), CCl4 (4 mL), r.t., 0.5–1.5 h.
phosphinochalcogenoic chloride D and a carbanion (–CCl3). The synthesized amides bearing reactive vinyloxy groups
This step is followed by protonation of the carbanion with represent promising building blocks for organic synthesis.
a triethylammonium cation to regenerate triethylamine Thus, we have shown that amides 10d,i readily, and al-
and to form chloroform. The reaction between chloride D most quantitatively, cyclize on heating in an intramolecu-
and a vinyloxyalkylamine in the presence of triethylamine lar fashion to afford oxazolidines 11 and 12 (Scheme 2).
furnishes the target phosphinochalcogenoic amide prod-
uct and triethylammonium chloride (Scheme 1). In sup-
port of this mechanism, triethylammonium chloride was
X
X
N
toluene
consistently isolated from the reaction mixture (by filtra-
tion) and the presence of chloroform was confirmed by
GC–MS.
P
P
75 °C, 3.5–10 h
N
O
H
O
10d,i
X = S (10d, 11) 80%; X = Se (10i, 12) 90%
11, 12
R1
R1
R1
–
X
H
Et3N
R1
R1
CCl4
– e–
•
P
X
X
·–CCl4
+
P
P
R1
– Et3HN+
Scheme 2 Synthesis of 3-(diphenethylphosphorochalcogenoyl)-2-
methyl-1,3-oxazolidines 11 and 12
A
B
C
R1
R1
X
P
Cl
B
–CCl3
+
C
+
In the case of compound 10k, it was discovered that ben-
zenethiol adds to the vinyloxy group at 60–80 °C (4–6 h,
1,4-dioxane) to give Markovnikov adduct 13 in up to 70%
yield (Scheme 3). This reaction is the subject of further
study and the experimental details will be published else-
where.
D
–CCl3
Et3HN+
+
Et3N
+
CHCl3
R2
R1
R1
X
P
N
Et3N
R2
D
H
N
[Et3NH]Cl
+
+
(CH2)nOCH=CH2
(CH2)nOCH=CH2
X = O, S, Se
Scheme 1 A tentative mechanism for the formation of phosphino-
chalcogenoic amides 10
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2786–2792

2788
N. K. Gusarova et al.
PAPER
N-[2-(Vinyloxy)alkyl]phosphinochalcogenoic Amides 10a–m;
General Procedure
Se
A mixture of secondary phosphine chalcogenide 1–6 (1.0 mmol)
and Et3N (101 mg, 139 μL, 1.0 mmol) in CCl4 (4 mL) was stirred at
20–22 °C for 10 min. The vinyloxyalkylamine 7–9 (1.0 mmol) was
added, and the resulting mixture stirred at 20–22 °C for 0.5–1.5 h
(see Table 1). The solvent was removed under reduced pressure,
and 1,4-dioxane (3 mL) was added. The precipitated white solid,
[Et3NH]Cl, was removed by filtration and the 1,4-dioxane was
evaporated. The residue obtained was rinsed with hot hexane (2 × 3
mL), and the hexane soln was allowed to stand for 12 h at –8 °C.
The soln was decanted from the precipitate and the solvent was
evaporated under vacuum. The residue was dried under vacuum to
give phosphinochalcogenoic amides 10a,d–f,i–m. With amides
10b,c,g,h, the residues (after evaporation of 1,4-dioxane under vac-
uum) were re-precipitated from Et2O into hexane to afford the pure
products.
P
HS
+
O
N
Me
10k
Se
1,4-dioxane
60–80 °C, 4–6 h
P
S
O
N
Me
13
Scheme 3 Regioselective addition of benzenethiol to P,P-di-
phenethyl-N-methyl-N-[2-(vinyloxy)ethyl]phosphinoselenoic amide
(10k)
P,P-Diphenethyl-N-[2-(vinyloxy)ethyl]phosphinic Amide (10a)
Yield: 268 mg (78%); white powder; mp 80–81 °C (Et2O–hexane,
1:1).
In summary, an efficient route to a series of phosphino-
chalcogenoic amides functionalized with vinyloxy groups
has been developed using the chemoselective reaction of
secondary phosphine chalcogenides with vinyloxyalkyl-
amines. The cross-coupling proceeds easily at ambient
temperature in the triethylamine–carbon tetrachloride sys-
tem to afford the target compounds in high yields. The
products are prospective monomers and potentially highly
reactive building blocks for target organic synthesis, li-
gands for the preparation of metal complexes, promising
intermediates for the production of conducting nanomate-
rials and precursors for the design of biologically and
pharmaceutically important compounds.
IR (KBr): 3187 (NH), 1637 (OC=C), 1619, 1161 (P=O), 1031
(P–N–C), 699 cm–1.
1H NMR (400.13 MHz, CDCl3): δ = 2.00–2.07 (m, 4 H, CH2P), 2.74
(br s, 1 H, NH), 2.88–2.94 (m, 4 H, PhCH2), 3.22 (m, 2 H, NCH2),
3.73 (t, 3JНН = 5.1 Hz, 2 H, OCH2), 4.05 (dd, 3JНН = 6.7 Hz, 2JНН
=
2.2 Hz, 1 H, =CH2), 4.21 (dd, 3JНН = 14.3 Hz, 2JНН = 2.2 Hz, 1 H,
=CH2), 6.45 (dd, 3JНН = 14.3 Hz, 3JНН = 6.7 Hz, 1 H, OCH=), 7.19–
7.24 (m, 6 Н, Hо, Hр, Ph), 7.30 (dd, 3JНН = 7.8 Hz, 3JНН = 7.2 Hz, 4
Н, Hm, Ph).
13C NMR (100.61 MHz, CDCl3): δ = 28.2 (d, 2JРС = 3.0 Hz, PhСH2),
30.6 (d, 1JРС = 82.6 Hz, СH2Р), 39.3 (NCH2), 68.7 (d, 3JРС = 4.8 Hz,
CH2O), 87.3 (=CН2), 126.0 (Сp), 128.1 (Сo), 128.7 (Сm), 141.1 (d,
3JРС = 13.6 Hz, Ci), 151.4 (OCH=).
31P NMR (161.98 MHz, CDCl3): δ = 44.4.
15N NMR (40.56 MHz, CDCl3): δ = –338.0.
All reactions were carried out under an argon atmosphere. All sol-
vents were dried and/or purified according to standard procedures.12
Secondary phosphine chalcogenides 1, 3, 5 and 6 were prepared
from styrene or α-methylstyrene and elemental phosphorus as pre-
viously reported.6 Diphenylphosphine sulfide (2) and diphe-
nylphosphine selenide (4) were prepared by oxidation of
commercially available diphenylphosphine (Aldrich) with elemen-
tal sulfur or gray selenium.13 Vinyloxyalkylamines 7–9 were syn-
thesized via direct vinylation of the corresponding
hydroxyalkylamines with ethyne.14 The reactions were monitored
by 31P NMR spectroscopy by following the disappearance of the
signals due to the starting secondary phosphine chalcogenides 1–6
and the appearance of new resonances corresponding to N-[(vi-
nyloxy)alkyl]phosphinochalcogenoic amides 10a–m. Melting
points were recorded on a Stuart melting point apparatus and are un-
corrected. IR spectra were obtained using a Bruker Vertex 70 spec-
trometer. 1H, 13C, 15N, 31P and 77Se NMR spectra were recorded on
Bruker DPX 400 and Bruker AV-400 spectrometers (400.13,
100.61, 40.56, 161.98 and 76.31 MHz, respectively) in CDCl3 and
referenced to TMS (1H NMR, 13C NMR), MeNO2 (15N NMR),
H3PO4 (31P NMR) and Me2Se (77Se NMR). The 15N chemical shifts
of the products were determined to within 0.1 ppm using 2D 1Н–15N
NMR HMBC. Mass spectra (EI, 70 eV) were obtained on a Shimadzu
GCMS–QP5050 A (quadruple mass analyzer, the range of detected
mass was from 34 to 650 Da); capillary column SPB–5ms (60 m ×
0.25 mm × 0.25 μm), gas carrier helium, flow rate 0.7 mL/min, tem-
perature of injector and ion source 250 °С, pressure 100 kPa; tem-
perature programming from 50 to 250°С, 10 °C/min. The C, H and
N elemental analyses were performed with a Flash E112 Thermo
Finnigan Elemental Analyzer. The P elemental analyses were ob-
tained with a Specoll 11 spectrophotometer.
Anal. Calcd for С20Н26NO2P: С, 69.95; Н, 7.63; N, 4.08; Р, 9.02.
Found: С, 69.67; Н, 7.59; N, 4.03; Р, 8.78.
P,P-Diphenyl-N-[2-(vinyloxy)ethyl]phosphinothioic Amide
(10b)
Yield: 254 mg (84%); white powder; mp 83–85 °C (hexane).
IR (KBr): 3192 (NH), 1637 (OC=C), 1621, 1094 (P–N–C), 694, 613
(P=S) cm–1.
1H NMR (400.13 MHz, CDCl3): δ = 2.92 (br s, 1 H, NH), 3.28 (dt,
3JРН = 16.2 Hz, 3JНН = 5.0 Hz, 2 H, NCH2), 3.82 (t, 3JНН = 5.0 Hz, 2
H, CH2O), 4.03 (dd, 3JНН = 7.0 Hz, 2JНН = 2.0 Hz, 1 H, =CH2), 4.20
(dd, 3JНН = 14.6 Hz, 2JНН = 2.0 Hz, 1 H, =CH2), 6.46 (dd, 3JНН = 14.6
3
Hz, JНН = 7.0 Hz, 1 H, OCH=), 7.45–7.51 (m, 6 Н, Hm, Hр, Ph),
8.01 (dd, 3JPН = 13.6 Hz, 3JHН = 7.3 Hz, 4 Н, Ho, Ph).
13C NMR (100.61 MHz, CDCl3): δ = 40.5 (NCH2), 67.9 (d, 3JРС
=
8.4 Hz, CH2O), 87.5 (=CН2), 128.6 (d, 3JРС = 12.8 Hz, Сm), 131.6
(d, 2JРС = 11.0 Hz, Со), 131.8 (d, 4JРС = 3.3 Hz, Ср), 132.9 (d, 1JРС
=
102.0 Hz, Ci), 151.4 (OCH=).
31P NMR (161.98 MHz, CDCl3): δ = 60.7.
15N NMR (40.56 MHz, CDCl3): δ = –336.3.
Anal. Calcd for С16Н18NOPS: С, 63.35; Н, 5.98; N, 4.62; Р, 10.21;
S, 10.57. Found: С, 62.99; Н, 5.96; N, 4.61; Р, 9.89; S, 10.49.
P,P-Diphenyl-N-[3-(vinyloxy)propyl]phosphinothioic Amide
(10c)
Yield: 276 mg (87%); white powder; mp 66–67 °C (hexane).
IR (KВr): 3240 (NH), 1632 (OC=C), 1614, 1100 (P–N–C), 693, 611
(P=S) cm–1.
Synthesis 2012, 44, 2786–2792
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Functional Phosphinoсhalcogenоic Amides
2789
1H NMR (400.13 MHz, CDCl3): δ = 1.88 (m, 2 H, NСН2СН2), 2.79
(br s, 1 H, NH), 3.05–3.10 (m, 2 H, NCH2), 3.77 (t, 3JНН = 5.7 Hz,
2 H, CH2O), 3.99 (dd, 3JНН = 6.8 Hz, 2JНН = 2.0 Hz, 1 H, =CH2), 4.15
(dd, 3JНН = 14.4 Hz, 2JНН = 2.0 Hz, 1 H, =CH2), 6.40 (dd, 3JНН = 14.4
3.11 (m, 4 H, PhCH2), 3.41 (dt, 3JРН = 10.8 Hz, 3JНН = 5.3 Hz, 2 H,
CH2N), 3.82 (t, 3JНН = 5.3 Hz, 2 H, OCH2), 4.06 (dd, 3JНН = 6.7 Hz,
2JНН = 2.3 Hz, 1 H, =CH2), 4.23 (dd, 3JНН = 14.2 Hz, 2JНН = 2.3 Hz,
1 H, =CH2), 6.49 (dd, 3JНН = 14.2 Hz, 3JНН = 6.7 Hz, 1 H, OCH=),
7.17–7.29 (m, 10 Н, Ph).
3
Hz, JНН = 6.8 Hz, 1 H, OCH=), 7.41–7.49 (m, 6 Н, Hm, Hp, Ph),
7.96 (dd, 3JPН = 13.4 Hz, 3JHН = 6.9 Hz, 4 Н, Ho, Ph).
13C NMR (100.61 MHz, CDCl3): δ = 28.4 (d, 2JРС = 2.8 Hz, PhСH2),
3
1
13C NMR (100.61 MHz, CDCl3): δ = 30.5 (d, JРС = 8.8 Hz,
34.1 (d, JРС = 63.1 Hz, СH2Р), 35.0 (NMe), 48.2 (NCH2), 67.6
NСН2СН2), 39.1 (NCH2), 66.1 (CH2O), 86.9 (=CН2), 128.5 (d,
3JРС = 12.5 Hz, Сm), 131.6 (Сp), 131.7 (Со), 134.1 (d, 1JРС = 102.1
Hz, Ci), 151.6 (OCH=).
31P NMR (161.98 MHz, CDCl3): δ = 60.2.
15N NMR (40.56 MHz, CDCl3): δ = –331.9.
(CH2O), 87.1 (=CН2), 126.4 (Сp), 128.3 (Сo), 128.8 (Сm), 141.2 (d,
3JРС = 15.2 Hz, Ci), 151.5 (OCH=).
31P NMR (161.98 MHz, CDCl3): δ = 78.8.
15N NMR (40.56 MHz, CDCl3): δ = –355.9.
Anal. Calcd for С21Н28NOPS: С, 67.53; Н, 7.56; N, 3.75; Р, 8.29; S,
8.59. Found: С, 67.49; Н, 7.53; N, 3.71; Р, 8.14; S, 8.56.
Anal. Calcd for С17Н20NOPS: С, 64.33; Н, 6.35; N, 4.41; Р, 9.76; S,
10.11. Found: С, 63.93; Н, 6.35; N, 4.38; Р, 9.27; S, 10.02.
P,P-Diphenyl-N-[2-(vinyloxy)ethyl]phosphinoselenoic Amide
(10g)
Yield: 280 mg (80%); beige powder; mp 115–117 °C (Et2O–hex-
ane, 1:1).
P,P-Diphenethyl-N-[2-(vinyloxy)ethyl]phosphinothioic Amide
(10d)
Yield: 323 mg (90%); waxy solid.
IR (neat): 3369, 3278 (NH), 1636 (OC=C), 1619, 1117 (P–N–C),
1083 (sh), 698, 617 (P=S) cm–1.
IR (KBr): 3165 (NH), 1637 (OC=C), 1621, 1094 (P–N–C), 694, 546
(P=Sе) cm–1.
1H NMR (400.13 MHz, CDCl3): δ = 2.14–2.24 (m, 4 H, CH2P),
2.87–3.05 (m, 4 H, PhCH2), 3.16–3.19 (m, 2 H, CH2N), 3.68 (t,
3JНН = 5.1 Hz, 2 H, CH2O), 4.04 (dd, 3JНН = 6.8 Hz, 2JНН = 2.2 Hz,
1 H, =CH2), 4.18 (dd, 3JНН = 14.2 Hz, 2JНН = 2.2 Hz, 1 H, =CH2),
6.43 (dd, 3JНН = 14.2 Hz, 3JНН = 6.8 Hz, 1 H, OCH=), 7.19–7.30 (m,
10 Н, Ph).
1H NMR (400.13 MHz, CDCl3): δ = 2.81 (br s, 1 H, NH), 3.24 (dt,
3JРН = 16.2 Hz, 3JНН = 5.2 Hz, 2 H, NCH2), 3.82 (t, 3JНН = 5.2 Hz, 2
H, CH2O), 4.03 (dd, 3JНН = 6.8 Hz, 2JНН = 1.8 Hz, 1 H, =CH2), 4.18
(dd, 3JНН = 14.4 Hz, 2JНН = 1.8 Hz, 1 H, =CH2), 6.43 (dd, 3JНН = 14.4
3
Hz, JНН = 6.8 Hz, 1 H, OCH=), 7.44–7.49 (m, 6 Н, Hm, Hр, Ph),
7.97 (dt, 3JPН = 13.8 Hz, 3JHН = 6.9 Hz, 4 Н, Ho, Ph).
13C NMR (100.61 MHz, CDCl3): δ = 28.7 (d, 2JРС = 1.9 Hz, PhСH2),
35.6 (d, 1JРС = 63.4 Hz, СH2Р), 40.5 (NCH2), 68.3 (d, 3JРС = 6.4 Hz,
CH2O), 87.4 (=CН2), 126.5 (Сp), 128.4 (Сo), 128.8 (Сm), 140.9 (d,
3JРС = 14.5 Hz, Ci), 151.4 (OCH=).
13C NMR (100.61 MHz, CDCl3): δ = 41.5 (NCH2), 67.6 (d, 3JРС
=
8.5 Hz, CH2O), 87.4 (=CН2), 128.6 (d, 3JРС = 12.9 Hz, Сm), 131.8
(d, 2JРС = 11.4 Hz, Со), 131.9 (d, 4JРС = 2.9 Hz, Ср), 133.7 (d, 1JРС
=
91.4 Hz, Ci), 151.4 (OCH=).
31P NMR (161.98 MHz, CDCl3): δ = 71.9.
15N NMR (40.56 MHz, CDCl3): δ = –341.5.
31P NMR (161.98 MHz, CDCl3): δ = 58.3 (s) (+ d satellite, 1JPSe
783 Hz).
15N NMR (40.56 MHz, CDCl3): δ = –338.8.
77Se NMR (76.31 MHz, CDCl3): δ = –268.5 (d, 1JPSe = 783 Hz).
=
Anal. Calcd for С20Н26NOPS: С, 66.83; Н, 7.29; N, 3.90; Р, 8.62; S,
8.91. Found: С, 66.77; Н, 7.28; N, 3.88; Р, 8.46; S, 8.87.
Anal. Calcd for С16Н18NOPSe: С, 54.87; Н, 5.18; N, 4.00; Р, 8.84;
Se, 22.54. Found: С, 54.78; Н, 5.11; N, 4.04; Р, 8.39; Se, 22.79.
P,P-Diphenethyl-N-[3-(vinyloxy)propyl]phosphinothioic
Amide (10e)
Yield: 329 mg (88%); waxy solid.
P,P-Diphenyl-N-[3-(vinyloxy)propyl]phosphinoselenoic Amide
(10h)
Yield: 317 mg (87%); white powder; mp 75–76 °C (hexane).
IR (neat): 3367, 3268 (NH), 1636 (OC=C), 1617, 1096 (P–N–C),
698, 615 (P=S) cm–1.
1H NMR (400.13 MHz, CDCl3): δ = 1.82 (m, 2 H, NСН2СН2), 2.16
IR (KBr): 3213 (NH), 1637 (OC=C), 1617, 1621, 1068 (P–N–C),
(m, 1 H, NH), 2.17–2.25 (m, 4 H, CH2P), 2.95–3.05 (m, 6 H,
694, 555 (P=Sе) cm–1.
PhCH2, NCH2), 3.75 (t, 3JНН = 5.9 Hz, 2 H, OCH2), 4.04 (dd, 3JНН
6.8 Hz, 2JНН = 2.1 Hz, 1 H, =CH2), 4.20 (dd, 3JНН = 14.4 Hz, 2JНН
=
1H NMR (400.13 MHz, CDCl3): δ = 1.93 (quin, 3JНН = 6.2 Hz, 2 H,
NСН2СН2), 2.64 (br s, 1 H, NH), 3.06 (m, 2 H, NCH2), 3.77 (t,
3JНН = 5.9 Hz, 2 H, CH2O), 4.00 (dd, 3JНН = 6.8 Hz, 2JНН = 2.2 Hz,
1 H, =CH2), 4.15 (dd, 3JНН = 14.3 Hz, 2JНН = 2.2 Hz, 1 H, =CH2),
6.40 (dd, 3JНН = 14.3 Hz, 3JНН = 6.8 Hz, 1 H, OCH=), 7.28–7.44 (m,
6 Н, Hm, Hр, Ph), 7.97 (dd, 3JPН = 13.0 Hz, 3JHН = 6.7 Hz, 4 Н, Ho,
Ph).
=
2.1 Hz, 1 H, =CH2), 6.45 (dd, 3JНН = 14.4 Hz, 3JНН = 6.8 Hz, 1 H,
OCH=), 7.23–7.34 (m, 10 Н, Ph).
13C NMR (100.61 MHz, CDCl3): δ = 29.2 (d, 2JРС = 2.4 Hz, PhСH2),
30.9 (d, 3JРС = 7.6 Hz, NСН2СН2), 34.8 (d, 1JРС = 63.1 Hz, СH2Р),
2
38.8 (d, JРС = 2.4 Hz, NCH2), 65.5 (CH2O), 87.0 (=CН2), 126.5
3
(Сp), 128.4 (Сo), 128.7 (Сm), 140.5 (d, JРС = 14.8 Hz, Ci), 151.5
3
13C NMR (100.61 MHz, CDCl3): δ = 30.0 (d, JРС = 9.2 Hz,
(OCH=).
NСН2СН2), 39.9 (NCH2), 65.9 (CH2O), 86.7 (=CН2), 128.3 (d,
3JРС = 12.8 Hz, Сm), 131.5 (Сp), 131.6 (Сo), 133.5 (d, 1JРС = 94.7 Hz,
Ci), 151.3 (OCH=).
31P NMR (161.98 MHz, CDCl3): δ = 71.2.
15N NMR (40.56 MHz, CDCl3): δ = –336.1 (d, 1JNH = 87.8 Hz).
31P NMR (161.98 MHz, CDCl3): δ = 56.4 (s) (+ d satellite, 1JPSe
=
Anal. Calcd for С21Н28NOPS: С, 67.53; Н, 7.56; N, 3.75; Р, 8.29; S,
8.59. Found: С, 66.90; Н, 7.67; N, 3.65; Р, 8.18; S, 8.43.
750 Hz).
15N NMR (40.56 MHz, CDCl3): δ = –333.9 (d, 1JNH = 78.8 Hz).
77Se NMR (76.31 MHz, CDCl3): δ = –265.5 (d, 1JPSe = 750 Hz).
P,P-Diphenethyl-N-methyl-N-[2-(vinyloxy)ethyl]phosphinothi-
oic Amide (10f)
Yield: 295 mg (79%); waxy solid.
Anal. Calcd for С17Н20NOPSe: С, 56.05; Н, 5.53; N, 3.85; Р, 8.50;
Se, 21.68. Found: С, 55.82; Н, 5.51; N, 3.83; Р, 8.39; Se, 21.51.
IR (neat): 1635 (OC=C), 1618, 1073 (P–N–C), 698, 605 (P=S)
cm–1.
P,P-Diphenethyl-N-[2-(vinyloxy)ethyl]phosphinoselenoic
Amide (10i)
Yield: 374 mg (92%); waxy solid.
1H NMR (400.13 MHz, CDCl3): δ = 2.13–2.20 and 2.31–2.37 (m, 4
H, CH2P), 2.74 (d, 3JPН = 10.2 Hz, 3 H, NMe), 2.85–2.93 and 3.01–
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2786–2792

2790
N. K. Gusarova et al.
PAPER
IR (neat): 3362, 3257 (NH), 1637 (OC=C), 1619, 1115 (P–N–C),
Anal. Calcd for С21Н28NOPSe: С, 60.00; Н, 6.71; N, 3.33; Р, 7.37;
Se, 18.78. Found: С, 60.07; Н, 6.54; N, 3.13; Р, 7.31; Se, 18.69.
1082 (sh), 698, 579 (P=Sе) cm–1.
1H NMR (400.13 MHz, CDCl3): δ = 2.25–2.34 (m, 4 H, CH2P), 2.42
P,P-Вis(2-phenylpropyl)-N-[2-(vinyloxy)ethyl]phosphinosele-
noic Amide (10l)
(br s, 1 H, NH), 2.94–2.99 (m, 4 H, PhCH2), 3.15 (m, 2 H, CH2N),
3.67 (t, 3JНН = 5.0 Hz, 2 H, CH2O), 4.04 (dd, 3JНН = 6.7 Hz, 2JНН
=
Yield: 387 mg (89%); waxy solid.
2.2 Hz, 1 H, =CH2), 4.18 (dd, 3JНН = 14.3 Hz, 2JНН = 2.2 Hz, 1 H,
=CH2), 6.42 (dd, 3JНН = 14.3 Hz, 3JНН = 6.7 Hz, 1 H, OCH=), 7.18–
7.30 (m, 10 Н, Ph).
IR (neat): 3366, 3266 (NH), 1636 (OC=C), 1619, 1112 (sh, P–N–
C), 1086, 701, 561 (P=Sе) cm–1.
1H NMR (400.13 MHz, CDCl3): δ = 1.14, 1.23 and 1.31 (3 d, 3JHH
=
13C NMR (100.61 MHz, CDCl3): δ = 29.1 (PhСH2), 35.8 (d, 1JРС
=
3
3
7.1 Hz, JHH = 7.1 Hz, JHH = 7.6 Hz, 6 H, MeCH, respectively),
1.56–1.60 (m, 1 H, NH), 1.82–1.90, 1.95–2.03, 2.06–2.12 and 2.15–
2.28 (m, 4 H, CH2Р), 2.49–2.54, 2.59–2.64, 2.70–2.78 and 2.88–
54.3 Hz, СH2Р), 41.2 (NCH2), 67.7 (d, 3JРС = 6.8 Hz, CH2O), 87.2
(=CН2), 126.4 (Сp), 128.2 (Сo), 128.6 (Сm), 140.4 (d, 3JРС = 14.8 Hz,
Ci), 151.1 (OCH=).
2
3
2.94 (m, 2 H, NCH2), 3.15 (t, JHH = JНН = 5.1 Hz, 1 H, ОCH2),
3.20–3.29 and 3.30–3.36 (m, 2 H, CHMe), 3.43 (t, 2JHH = 3JНН = 5.1
Hz, 1 H, ОCH2), 3.90, 3.91 and 3.93 (3 dd, 3JНН = 6.9 Hz, 2JНН = 2.0
31P NMR (161.98 MHz, CDCl3): δ = 65.1 (s) (+ d satellite, 1JPSe
=
731 Hz).
Hz, 1 H, =CH2), 4.00, 4.01 and 4.05 (3 dd, 3JНН = 14.2 Hz, 2JНН
2.0 Hz, 1 H, =CH2), 6.20, 6.23 and 6.28 (3 dd, 3JНН = 14.2 Hz, 3JНН
6.9 Hz, 1 H, ОСН=), 7.09–7.26 (m, 10 Н, Ph).
=
=
15N NMR (40.56 MHz, CDCl3): δ = –343.5.
77Se NMR (76.31 MHz, CDCl3): δ = –325.5 (d, 1JPSe = 731 Hz).
Anal. Calcd for С20Н26NOPSe: С, 59.11; Н, 6.45; N, 3.45; Р, 7.62;
Se, 19.43. Found: С, 59.08; Н, 6.42; N, 3.41; Р, 7.48; Se, 19.39.
13C NMR (100.61 MHz, CDCl3): δ = 24.0, 24.1 and 24.6 (3 d, 3JPC
=
12.5 Hz, 3JPC = 12.9 Hz, 3JPC = 14.0 Hz, MeCH, respectively), 34.6,
35.0, 35.5 and 35.7 (4 d, 2JPC = 2.2 Hz, 2JРС = 2.6 Hz, 2JРС = 1.5 Hz,
2JРС = 1.8 Hz, MeCH, respectively), 40.3, 40.4 and 40.7 (3 s,
NCH2), 41.0, 42.4, 43.1 and 43.8 (4 d, 1JРС = 53.8 Hz, 1JРС = 52.7
Hz, 1JРС = 56.0 Hz, 1JРС = 56.4 Hz, СH2Р, respectively), 66.9, 67.1
P,P-Diphenethyl-N-[3-(vinyloxy)propyl]phosphinoselenoic
Amide (10j)
Yield: 378 mg (90%); waxy solid.
IR (neat): 3361, 3250 (NH), 1636 (OC=C), 1617, 1090 (P–N–C),
3
3
3
and 67.4 (3 d, JPC = 8.1 Hz, JPC = 7.7 Hz, JPC = 7.7 Hz, OСH2,
respectively), 86.5, 86.6 and 86.7 (3 s, =CН2), 126.37, 126.41 and
126.5 (3 s, Cp), 126.8, 126.9 and 127.0 (3 s, Cm), 128.3, 128.4 and
128.5 (3 s, Co), 145.5–145.8 (m, Ci), 150.9 and 151.0 (2 s, ОСН=).
698, 579 (P=Sе) cm–1.
1H NMR (400.13 MHz, CDCl3): δ = 1.82 (m, 2 H, NСН2), 2.09 (m,
1 H, NH), 2.25–2.36 (m, 4 H, CH2P), 2.95–3.04 (m, 6 H, PhCH2,
NCH2CH2), 3.75 (t, 3JНН = 5.9 Hz, 2 H, OCH2), 4.04 (dd, 3JНН = 6.8
Hz, 2JНН = 2.0 Hz, 1 H, =CH2), 4.20 (dd, 3JНН = 14.2 Hz, 2JНН = 2.0
31P NMR (161.98 MHz, CDCl3): δ = 66.4 (s) (+ d satellites, 1JPSe
=
1
727.4 Hz), 66.5 (s) (+ d satellites, JPSe = 724.5 Hz), 66.7 (s) (+ d
3
3
Hz, 1 H, =CH2), 6.45 (dd, JНН = 14.2 Hz, JНН = 6.8 Hz, 1 H,
OCH=), 7.20–7.35 (m, 10 Н, Ph).
satellites, 1JPSe = 723 Hz).
15N NMR (40.56 MHz, CDCl3): δ = –343.3, –340.7.
13C NMR (100.61 MHz, CDCl3): δ = 29.2 (PhСH2), 30.7 (d, 2JРС
=
77Se NMR (76.31 MHz, CDCl3): δ = –313.1 (d, 1JPSe = 726.7 Hz),
7.6 Hz, NСН2), 35.6 (d, 1JРС = 54.3 Hz, СH2Р), 39.6 (d, 3JРС = 3.6
Hz, NCH2CH2), 65.4 (CH2O), 87.1 (=CН2), 126.5 (Сp), 128.4 (Сo),
128.7 (Сm), 140.6 (d, 3JРС = 14.4 Hz, Ci), 151.5 (OCH=).
–295.3 (d, 1JPSe = 726.7 Hz), –292.3 (d, 1JPSe = 726.7 Hz).
Anal. Calcd for С22Н30NOPSe: С, 60.83; Н, 6.96; N, 3.22; Р, 7.13;
Se, 18.18. Found: С, 60.88; Н, 6.94; N, 3.26; Р, 7.09; Se, 18.12.
31P NMR (161.98 MHz, CDCl3): δ = 65.2 (s) (+ d satellite, 1JPSe
=
744 Hz).
P,P-Вis(2-phenylpropyl)-N-[3-(vinyloxy)propyl]phosphinosele-
noic Amide (10m)
Yield: 426 mg (95%); waxy solid.
15N NMR (40.56 MHz, CDCl3): δ = –337.9 (d, 1JNН = 82 Hz).
77Se NMR (76.31 MHz, CDCl3): δ = –320.3 (d, 1JPSe = 744 Hz).
IR (neat): 3364, 3256 (NH), 1636 (OC=C), 1617, 1119 (sh, P–N–
Anal. Calcd for С21Н28NOPSe: С, 60.00; Н, 6.71; N, 3.33; Р, 7.37;
Se, 18.78. Found: С, 60.23; Н, 6.64; N, 3.34; Р, 7.29; Se, 18.73.
C), 1085, 701, 561 (P=Sе) cm–1.
1H NMR (400.13 MHz, CDCl3): δ = 1.21, 1.32 and 1.38 (3 d, 3JHH
=
3
3
P,P-Diphenethyl-N-methyl-N-[2-(vinyloxy)ethyl]phosphi-
noselenoic Amide (10k)
Yield: 336 mg (80%); waxy solid.
6.9 Hz, JHH = 7.1 Hz, JHH = 7.1 Hz, 6 H, MeCH, respectively),
3
1.42–1.46 (m, 1 H, NCH2CH2), 1.56 (quin, JHH = 6.2 Hz, 1 H,
NCH2CH2), 1.88, 1.90, 1.91 and 1.94 (4 d, 2JPH = 4.8 Hz, 1 H, NH),
1.99–2.32 (m, 4 H, CH2Р), 2.36–2.46, 2.59–2.67 and 2.77–2.84 (m,
2 H, NCH2), 3.14–3.20 and 3.38–3.46 (m, 2 H, CHMe), 3.46–3.48
and 3.54–3.57 (m, 2 H, ОCH2), 3.99, 4.00, 4.02 and 4.06 (4 dd,
3JHH = 6.8 Hz, 2JHH = 2.0 Hz, 1 H, =CH2), 4.10, 4.12, 4.15 and 4.23
(4 dd, 3JHH = 14.2 Hz, 2JHH = 2.0 Hz, 1 H, =CH2), 6.37, 6.39, 6.42
and 6.51 (4 dd, 3JНН = 14.2 Hz, 3JНН = 6.8 Hz, 1 H, ОСН=), 7.18–
7.32 (m, 10 Н, Ph).
IR (neat): 1636 (OC=C), 1618, 1121 (P–N–C), 1077 (sh), 698, 579
(P=Sе) cm–1.
1H NMR (400.13 MHz, CDCl3): δ = 2.25–2.28 and 2.48–2.53 (m, 4
H, CH2P), 2.74 (d, 3JPН = 10.5 Hz, 3 H, NMe), 2.89–2.93 and 3.02–
3.09 (m, 4 H, PhCH2), 3.40 (dt, 3JРН = 11.2 Hz, 3JНН = 5.3 Hz, 2 H,
NCH2), 3.82 (t, 3JНН = 5.3 Hz, 2 H, OCH2), 4.07 (dd, 3JНН = 7.0 Hz,
2JНН = 2.2 Hz, 1 H, =CH2), 4.24 (dd, 3JНН = 14.2 Hz, 2JНН = 2.2 Hz,
1 H, =CH2), 6.49 (dd, 3JНН = 14.2 Hz, 3JНН = 7.0 Hz, 1 H, OCH=),
7.22–7.35 (m, 10 Н, Ph).
13C NMR (100.61 MHz, CDCl3): δ = 24.3, 24.4, 24.7 and 24.8 (4 d,
3
3
3
3JPC = 12.8 Hz, JPC = 12.8 Hz, JPC = 14.8 Hz, JPC = 13.6 Hz,
MeCH, respectively), 30.0, 30.2 and 30.4 (3 d, 3JРС = 9.2 Hz, 3JРС
=
13C NMR (100.61 MHz, CDCl3): δ = 29.1 (PhСH2), 34.7 (d, 1JРС
=
8.8 Hz, 3JРС = 8.4 Hz, NCH2CH2, respectively), 34.9, 35.3, 35.8 and
36.1 (4 d, 2JРС = 2.8 Hz, 2JРС = 3.6 Hz, 2JРС = 0.4 Hz, 2JРС = 2.4 Hz,
CHMe, respectively), 38.1–38.8 (4 s, NCH2), 40.3, 42.1, 42.9 and
43.3 (4 d, 1JРС = 53.1 Hz, 1JРС = 53.1 Hz, 1JРС = 55.5 Hz, 1JРС = 57.5
Hz, СH2Р, respectively), 65.1, 65.2 and 65.4 (3 s, CH2O), 86.6, 86.7
and 86.8 (3 s, =CН2), 126.7–126.8, 127.3–127.4 and 128.7–128.8
(m, Co, Cm, Cp), 145.9–146.2 (m, Ci), 151.3, 151.5 and 151.6 (3 s,
ОСН=).
54.7 Hz, СH2Р), 35.3 (NMe), 49.5 (NCH2), 67.4 (d, 3JРС = 3.2 Hz,
CH2O), 87.2 (=CН2), 126.4 (Сp), 128.5 (Сo), 128.8 (Сm), 140.8 (d,
3JРС = 15.6 Hz, Ci), 151.5 (OCH=).
31P NMR (161.98 MHz, CDCl3): δ = 75.2 (s) (+ d satellite, 1JPSe
=
763 Hz).
15N NMR (40.56 MHz, CDCl3): δ = –358.5.
77Se NMR (76.31 Hz, CDCl3): δ = –353.0 (d, 1JPSe = 763 Hz).
Synthesis 2012, 44, 2786–2792
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Functional Phosphinoсhalcogenоic Amides
2791
31P NMR (161.98 MHz, CDCl3): δ = 65.2 (s) (+ d satellites, 1JPSe
723.2 Hz), 66.8 (s) (+ d satellites; 1JPSe = 723.2 Hz).
=
Anal. Calcd for С20Н26NOPSe: С, 59.11; Н, 6.45; N, 3.45; Р, 7.62;
Se, 19.43. Found: С, 59.02; Н, 6.47; N, 3.43; Р, 7.56; Se, 19.38.
15N NMR (40.56 MHz, CDCl3): δ = –335.8.
N-Methyl-P,P-diphenethyl-N-{2-[1-(phenylsulfanyl)eth-
77Se NMR (76.31 MHz, CDCl3): δ = –309.2 (d, 1JPSe = 722.2 Hz),
oxy]ethyl}phosphinoselenoic Amide (13)
–292.9 (d, 1JPSe = 721.1 Hz), –289.1 (d, 1JPSe = 715.9 Hz).
A
mixture of P,P-diphenethyl-N-methyl-N-[2-(vinyloxy)eth-
yl]phosphinoselenoic amide (10k; 210 mg, 0.50 mmol) and ben-
zenethiol (68 mg, 0.62 mmol) in dioxane (2 mL) was stirred at 75
°C for 5.5 h. The solvent was removed under reduced pressure. The
residue obtained was washed with hexane (5 × 0.2 mL), the solvent
was removed by decantation, and the residue was dried under vac-
uum to give product 13.
Anal. Calcd for С23Н32NOPSe: С, 61.60; Н, 7.19; N, 3.12; Р, 6.91;
Se, 17.61. Found: С, 61.53; Н, 7.17; N, 3.08; Р, 6.89; Se, 17.55.
3-(Diphenethylphosphorochalcogenoyl)-2-methyl-1,3-oxazoli-
dines 11 and 12; General Procedure
A soln of N-[2-(vinyloxy)alkyl]phosphinochalcogenoic amide 10d
or 10i (0.6 mmol) in toluene (2.3 mL), in a sealed ampoule, was
stirred at 75 °C (10 h for phosphinothioic amide 10d, 3.5 h for phos-
phinoselenoic amide 10i). The progress of the reaction was moni-
tored using 31P NMR spectroscopy by following the disappearance
of the signal due to the starting phosphinochalcogenoic amide (at
ca. 65–72 ppm) and the appearance of a new resonance in the region
of 68–72 ppm for the product. The mixture was filtered through a
layer of Al2O3 (activity level II, 1.5 cm, eluent: toluene). The sol-
vent was removed by distillation under reduced pressure to give 2-
methyl-1,3-oxazolidine 11 or 12.
Yield: 186 mg (70%); waxy solid.
IR (neat): 3060 (CH3), 1107, 698, 578 (P=Sе) сm–1.
3
1H NMR (400.13 MHz, CDCl3): δ = 1.51 (d, JHH = 6.2 Hz, 3 H,
Me), 2.23–2.30 and 2.41–2.49 (m, 4 H, CH2P), 2.72 (d, 3JPH = 11.2
Hz, 3 H, NMe), 2.49–2.87 and 2.93–3.04 (m, 4 H, PhCH2), 3.22–
3.29 and 3.31–3.40 (m, 2 H, NCH2), 3.55–3.60 and 3.97–4.02 (m, 2
H, CH2O), 4.36 (q, 3JHH = 6.2 Hz, 1 H, CHMe), 7.20–7.24 and 7.27–
7.32 (m, 10 H, Ph), 7.47 (d, 3JHH = 7.7 Hz, 2 H, Co, SPh), 7.48 (m,
2 H, Cm, SPh), 7.52 (d, 3JHH = 7.7 Hz, 1 H, Cp, SPh).
13C NMR (100.61 MHz, CDCl3): δ = 22.6 (Me), 29.3 (PhCH2), 34.7
(d, 1JPC = 54.7 Hz, CH2P), 35.0 (NMe), 49.8 (NCH2), 66.4 (CH2O),
85.1 (CHS), 126.4 (Cр), 127.6 (Cр, PhS), 128.3 (Co), 128.6 (Cm),
3-(Diphenethylphosphorothioyl)-2-methyl-1,3-oxazolidine (11)
Yield: 174 mg (80%); waxy product.
128.8 (Cm, PhS), 129.5 (Ci, PhS), 133.6 (Co, PhS), 140.9 (d, 3JPC
=
IR (neat): 2978 (COCH2), 1602 (C=C, Ph), 1161 (P–N–C), 698, 619
(P=S) cm–1.
15.6 Hz, Ci).
3
1H NMR (400.13 MHz, CDCl3): δ = 1.32 (d, JHH = 5.2 Hz, 3 H,
31P NMR (161.98 MHz, CDCl3): δ = 74.7 (s) (+ d satellite, 1JPSe
=
Me), 2.06–2.25 (m, 4 H, PhCH2), 2.80–3.02 (m, 4 H, CH2P), 3.08–
736 Hz).
3.16 and 3.40–3.48 (m, 2 H, NCH2), 3.76–3.82 and 3.96–4.00 (m, 2
15N NMR (40.56 MHz, CDCl3): δ = –358.0.
77Se NMR (76.31 MHz, CDCl3): δ = –349.3 (d, 1JPSe = 736 Hz).
3
3
H, CH2O), 5.42 (dq, JPH = 10.0 Hz, JHH = 5.2 Hz, 1 H, CHMe),
7.12–7.22 (m, 6 Н, Ho, Hр, Ph), 7.24 (dd, 3JHН = 8.4 Hz, 3JHН = 7.2
Hz, 4 Н, Hm, Ph).
Anal. Calcd for С27Н34NOPSSe: С, 61.12; Н, 6.46; N, 2.64; Р, 5.84;
S, 6.04; Se, 14.88. Found: С, 61.07; Н, 6.44; N, 2.62; Р, 5.79; S,
6.01; Se, 14.85.
3
13C NMR (100.61 MHz, CDCl3): δ = 22.8 (d, JPC = 3.6 Hz, Me),
28.3 and 28.5 (2 d, 2JPC = 2.4 Hz, 2JPC = 2.8 Hz, PhCH2, respective-
1
ly), 34.2 and 34.6, (2 d, JPC = 61.1 Hz, 1JPC = 64.3 Hz, PCH2, re-
3
spectively), 44.8 (NCH2), 65.8 (d, JPC = 4.0 Hz, OCH2), 87.4 (d,
2JPC = 3.2 Hz, CMe), 126.3 (Cр), 128.1 (d, 4JPC = 6.0 Hz, Co), 128.5
Acknowledgment
(d, 5JPC = 0.8 Hz, Cm), 140.4 (d, 3JPC = 15.2 Hz, Ci).
This work was supported by the President of the Russian Federation
(program for the support of leading scientific schools, grant no.
NSh-3230.2010.3).
31P NMR (161.98 MHz, CDCl3): δ = 72.1.
15N NMR (40.56 MHz, CDCl3): δ = –317.9.
Anal. Calcd for С20Н26NOPS: С, 66.83; Н, 7.29; N, 3.90; Р, 8.62; S,
8.92. Found: С, 66.79; Н, 7.23; N, 3.87; Р, 8.59; S, 8.88.
References
3-(Diphenethylphosphoroselenoyl)-2-methyl-1,3-oxazolidine
(1) (a) Kim, Y. K.; Livinghouse, T.; Horino, Y. J. Am. Chem.
Soc. 2003, 125, 9560. (b) Kim, H.; Lee, P. H.; Livinghouse,
T. Chem. Commun. 2005, 5205. (c) Kim, H.; Kim, Y. K.;
Shim, J. H.; Kim, M.; Han, M.; Livinghouse, T.; Lee, P. H.
Adv. Synth. Catal. 2006, 348, 2609.
(12)
Yield: 219 mg (90%); waxy solid.
IR (neat): 2978 (COCH2), 1603 (C=C, Ph), 1157 (P–N–C), 698, 580
(P=Se) cm–1.
3
1H NMR (400.13 MHz, CDCl3): δ = 1.22 (d, JHH = 5.1 Hz, 3 H,
(2) (a) Bochmann, M.; Bwembya, G. C.; Whilton, N.; Song, X.;
Hursthouse, M. B.; Coles, S. J.; Karaulov, A. J. Chem. Soc.,
Dalton Trans. 1995, 1887. (b) Bochmann, M.; Bwembya, G.
C.; Hursthouse, M. B.; Coles, S. J. J. Chem. Soc., Dalton
Trans. 1995, 2813. (c) Slawin, A. M. Z.; Smith, M. B.;
Woollins, J. D. J. Chem. Soc., Dalton Trans. 1996, 4567.
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J.; Woollins, J. D. Inorg. Chem. 1996, 35, 2695. (e) Rŏsler,
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Soc., Dalton Trans. 1996, 391. (f) Song, X.; Bochmann, M.
J. Chem. Soc., Dalton Trans. 1997, 2689. (g) Necas, M.;
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New J. Chem. 2001, 25, 1256. (h) Williams, D. B. G.; Evans,
S. J.; de Bod, H.; Mokhadinyana, M. S.; Hughes, T.
Synthesis 2009, 3106. (i) Vellalath, S.; Čoricŕ, I.; List, B.
Angew. Chem. Int. Ed. 2010, 49, 9749. (j) Popovici, C.;
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Me), 2.30–2.43 (m, 4 H, PhCH2), 2.91–3.05 (m, 4 H, CH2P), 3.16–
3.19 and 3.51–3.53 (m, 2 H, NCH2), 3.30–3.89 and 4.04–4.05 (m, 2
3
3
H, CH2O), 5.38 (dq, JPH = 10.1 Hz, JHH = 5.1 Hz, 1 H, CHMe),
7.19–7.26 (m, 6 Н, Ho, Hр, Ph), 7.31 (dd, 3JHН = 8.6 Hz, 3JHН = 7.1
Hz, 4 Н, Hm, Ph).
13C NMR (100.61 MHz, CDCl3): δ = 22.8 (d, 3JPC = 4.8 Hz, Me),
29.2 and 29.3 (2 s, PhCH2), 35.0 and 35.5 (2 d, 1JPC = 55.8 Hz, 1JPC
=
53.1 Hz, PCH2, respectively), 45.6 (NCH2), 65.9 (d, 3JPC = 4.0 Hz,
2
4
OCH2), 88.1 (d, JPC = 2.8 Hz, CMe), 126.4 (Cр), 128.2 (d, JPC
=
6.0 Hz, Co), 128.7 (Cm), 140.4 (d, 3JPC = 15.2 Hz, Ci).
31P NMR (161.98 MHz, CDCl3): δ = 68.2 (s) (+ d satellite, 1JPSe
742 Hz).
15N NMR (40.56 MHz, CDCl3): δ = –320.8.
77Se NMR (76.31 MHz, CDCl3): δ = –334.7 (d, 1JPSe = 742 Hz).
=
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2786–2792

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