Three-component reaction between vinyl ethers, secondary phosphines, and elemental selenium: One-pot synthesis of 1-(Alkoxy)ethyl and 1-(Aryloxy)ethyl phosphinodiselenoates

Article abstract of DOI:10.1055/s-0031-1289655

A family of previously unknown phosphinodiselenoic esters containing a selenoacetal moiety, R²(=Se)SeCH(Me)OR¹ (R¹, R²=alkyl, aryl, etc.), were synthesized by means of a three-component reaction between the elem

Full text of DOI:10.1055/s-0031-1289655

PAPER
431
Three-Component Reaction between Vinyl Ethers, Secondary Phosphines,
and Elemental Selenium: One-Pot Synthesis of 1-(Alkoxy)ethyl and
1-(Aryloxy)ethyl Phosphinodiselenoates
O
ne-Pot Synthesis
i
of 1-(A
n
lkoxy)ethyl
a
and 1-(Aryloxy)e
K
thyl Phosphinodis
.
elenoate
s
Gusarova, Alexander V. Artem’ev, Ludmila A. Oparina, Nikita A. Kolyvanov, Svetlana F. Malysheva,
Oksana V. Vysotskaya, 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 8 November 2011; revised 23 November 2011
In this context, we studied the reaction of vinyl esters with
secondary phosphines and elemental selenium. The
choice of vinyl ethers as functional alkenes was partially
motivated by their ready availability.10
Abstract: A family of previously unknown phosphinodiselenoic
esters containing a selenoacetal moiety, R2 P(=Se)SeCH(Me)OR1
2
(R1, R2 = alkyl, aryl, etc.), were synthesized by means of a three-
component reaction between the elemental selenium and the corre-
sponding vinyl ether and secondary phosphine. The reaction pro-
ceeds readily in 1,4-dioxane at 90 °C for 1–1.5 hours and gives the
phosphinodiselenoic esters quantitatively and in an entirely atom-
economic manner. The reaction proceeds through electrophilic ad-
dition to the electron-rich double bond of the phosphinodiselenoic
acids generated in situ.
The three-component reaction between vinyl ethers 1a–i,
secondary phosphines 2a–d, and elemental selenium pro-
ceeded practically quantitatively when the reactants were
mixed in a 1/2/Se ratio of 1.05:1:2 in 1,4-dioxane and
heated at 90 °C for 1–1.5 h, giving the 1-(alkoxy)ethyl and
1-(aryloxy)ethyl phosphinodiselenoates 3a–o (Table 1).
Numerous combinations of various vinyl ethers and sec-
ondary phosphines reacted effectively to give the corre-
sponding phosphinodiselenoic esters, demonstrating the
general character of the synthesis. Note that vinyl ethers
bearing electron-donating substituents and those bearing
electron-withdrawing substituents both participated suc-
cessfully in the three-component reaction.
Key words: phosphines, multicomponent reactions, phosphorus,
selenium, phosphinodiselenoate esters
A recently discovered three-component reaction between
aryl- or hetarylalkenes, secondary phosphines, and ele-
mental selenium provides an expedient route to novel
family of phosphinodiselenoic esters.1 Compounds of this
type are currently attracting an increasing degree of atten-
tion as potential candidates for the design of
pharmaceuticals2 or pesticides,3 as prospective capping
agents and selenium sources for the fabrication of seleni-
um-containing nanocrystals,4,5 as building blocks for or-
ganic synthesis,6 and as selenium-donating ligands for the
design of metal complexes (including catalysts).7 Further-
more, phosphinodiselenoic esters are efficient reagents
for living reversible addition–fragmentation chain-trans-
fer (RAFT) polymerization of vinyl monomers.8 There-
fore, the further elaboration of fundamental and practical
aspects of this promising multicomponent reaction is a
logical step in organoselenophosphorus chemistry.
The preparation of bis-ester 3p in 96% yield from 1,4-
bis(vinyloxy)benzene, phosphine 2a, and elemental sele-
nium under the same conditions provided an additional
demonstration of the general nature of this reaction by
showing that divinyl ethers participate readily in the syn-
thesis (Scheme 1).
1,4-dioxane
90 °C, 1.5 h
O
+
2 R2PH + 4 Se
O
2a
R
P
R
Se
O
Se
P
Se
The aim of this work was to extend the scope of the reac-
tion to vinyl ethers, another large family of functional alk-
enes of theoretical and synthetic importance, thereby
opening a shortcut to hitherto unknown functional phos-
phinodiselenoic esters containing selenoacetal moieties.
The selenoacetals are known to be useful intermediates
and building blocks in total syntheses of several biologi-
cally significant compounds.9
O
3p R = Ph(CH2)2 (96%)
Se
R
R
Scheme 1 Synthesis of bisphosphinodiselenoic ester 3p
The experimental protocol that we developed was also
shown to be also applicable to the synthesis of optically
active phosphinodiselenoic esters (for example, 3q) by us-
ing vinyl ethers of carbohydrates and their derivatives,
such as the vinyl ether of di-O-isopropylidene-a-D-gluco-
furanose 1j11 (Scheme 2). It is worth emphasizing that the
reaction proceeded chemoselectively at the vinyloxy
group of ether 1j; in other words, both the acetal and sugar
moieties tolerate the reaction conditions.
SYNTHESIS 2012, 44, 431–438
x
x
.x
x
.2
0
1
1
Advanced online publication: 23.12.2011
DOI: 10.1055/s-0031-1289655; Art ID: Z105011SS
© Georg Thieme Verlag Stuttgart · New York

432
N. K. Gusarova et al.
PAPER
Table 1 Phosphinodiselenoic Esters 3a–o from Vinyl Esters 1a–i, Secondary Phosphines 2a–d, and Elemental Selenium
R1
R2
R2
R2 Se
P
O
90 °C, 1–1.5 h
dioxane
R1
H
P
+
+ 2 Se
O
R2
Se
Me
3a–o
1a–i
2a–d
Ether
1a
1b
1c
Entrya
1
R1
Phosphine
2a
R2
Product
3a
Yield (%)b
Bu
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2-4-MeOC6H4
(CH2)2-4-MeOC6H4
2-(2-furyl)ethyl
2-(2-furyl)ethyl
Ph
96
94
92
97
99
90
98
99
97
95
91
96
94
98
90
2
(CH2)4Me
CH2CHEt2
CH2(CF2)2H
CH2(CF2)4H
2-furylmethyl
Ph
2a
3b
3c
3
2a
4
1d
1e
2a
3d
3e
5
2a
6
1f
2a
3f
7
1g
1h
1i
2a
3g
8
3-Tol
2a
3h
3i
9
2,6-Me2C6H3
CH2(CF2)4H
3-Tol
2a
10
11
12
13
14
15
1e
2b
3j
1h
1g
1h
1e
2b
3k
3l
Ph
2c
3-Tol
2c
3m
3n
3o
CH2(CF2)4H
Ph
2d
1g
2d
Ph
a Reaction conditions: vinyl ether (1a–i) (2.1 mmol), secondary phosphine (2a–d) (2.0 mmol), elemental Se (4.0 mmol), 1,4-dioxane (8 mL),
90 °C, 1–1.5 h. According to the 31P NMR spectra, yields of the compounds 3a–o were near quantitative.
b Isolated yields based on phosphines 2a–d.
The synthesized phosphinodiselenoic esters are air- and In the 1H NMR spectra of products 3a–q, doublets of the
moisture-stable viscous oils with a shelf life of several methyl protons of the selenoacetal moieties,
months in a closed vessel and they have a particular odor. SeCH(Me)OR1, were observed at d = 1.79–2.17 ppm with
They are readily soluble in hydrocarbons, diethyl ether, a 3JHH coupling constant of 5.6–6.2 Hz. The multiplets in
chlorinated solvents, or 1,4-dioxane, but barely soluble in the region d = 5.41–6.07 ppm were assigned to the meth-
ethanol. Esters 3a–q were characterized by means of their yne protons of the selenoacetal moieties. In the 13C NMR
1H, 13C, 31P, and 77Se NMR and IR spectra.
spectra, the methyl group gave a signal in the region d =
3
25.3–26.9 ppm with a JCP coupling constant of 2.2–2.9
Hz, whereas the methyne carbon atom resonated at d =
87.4–95.2 ppm.
O
Each of the 31P NMR spectra of the synthesized esters
1,4-dioxane
90 °C, 1.5 h
O
O
O
+
R2PH
+
2 Se
showed a sharp singlet at d = 37.51–49.82 ppm which was
O
1
accompanied by two sets of 77Se satellites: JPSe = 344–
O
2a
1j
370 and 1JPSe = 738–768 Hz. The couplings with the lower
magnitude were assigned to the P–Se single bond, and
those of a higher magnitude were assigned to the P=Se
double bond.
Se
R
P
O
O
Se
R
O
O
The 77Se NMR spectra of the phosphinodiselenoates
showed two distinct signals: a doublet at d = –237 to –156
ppm with a 1JPSe coupling constant of 738–768 Hz, and a
doublet at 310–427 ppm with a 1JPSe coupling constant of
344–370 Hz. These were assigned to the P=Se and P–Se
bonds, respectively.
O
O
3q R = Ph(CH2)2 (87%)
Scheme 2 Synthesis of an optically active phosphinodiselenoic
ester 3q
Synthesis 2012, 44, 431–438
© Thieme Stuttgart · New York

PAPER
One-Pot Synthesis of 1-(Alkoxy)ethyl and 1-(Aryloxy)ethyl Phosphinodiselenoates
433
+
A plausible pathway for the three-component reaction is
shown in Scheme 3. The first step involves oxidation of
the secondary phosphine 2 with elemental selenium to
form the secondary phosphine selenide A, which reacts
with a second equivalent of elemental selenium to gener-
ate the phosphinodiselenoic acid B. Subsequent electro-
philic addition of the latter to the electron-rich double
bond of vinyl ether 1 affords the expected Markovnikov-
type adduct, the phosphinodiselenoic ester 3.
R
R
Se–
Se
H2N
H3N
P
O
O
1,4-dioxane
90 °C, 15 min
1k
4 R = Ph(CH2)2 (94%)
+
R2PH
2a
+
H2N
R
R
Se
Se
P
2 Se
O
3r
Scheme 4 Synthesis of organoammonium salt 4 bearing a vinyloxy
moiety
R1
R2
R2
Se
H
R2
Se
O
1
Se
Se
P
H
P
P
R2
R2
SeH
R2
2
B
A
17 diverse organophosphorus compounds were detectable
(31P NMR) in the reaction mixture.
R1
R2
Se
O
P
In conclusion, a three-component reaction of vinyl ethers,
secondary phosphines, and elemental selenium was dis-
covered and developed. The reaction can be applied to vi-
nyl ethers containing alkyl, polyfluoroalkyl, aryl, or
hetaryl substituents, as well as vinyl ethers of optically ac-
tive sugar derivatives. The secondary phosphines can be
substituted with aryl, arylalkyl, or hetarylalkyl groups.
R2
Se
3
Scheme 3 A plausible mechanism for the three-component reaction
between vinyl ethers 1, secondary phosphines 2, and elemental sele-
nium
The formation of secondary phosphine selenides A from
phosphines 2a–d and elemental selenium has been report-
ed previously.12 The presence of a secondary phosphine
selenide A [R2 = (CH2)2Ph] in the reaction mixture has
been detected by 31P NMR as a singlet at d = 2 ppm with
The reaction provides a general, straightforward, and
atom-economic route to a novel family of phosphinodise-
lenoic esters bearing rare selenoacetal moieties. The syn-
thesized phosphinodiselenoic esters may be useful as
capping agents for the preparation of metal selenide nano-
particles, as ligands for metallocomplexes with a range of
applications, or as building blocks for drug and pesticide
design. The results contribute to the fundamental chemis-
try of vinyl ethers, organic phosphines, and elemental
selenium, as well as to the synthesis of organoselenophos-
phorus compounds by means of multicomponent reac-
tions.
1
a JPSe coupling constant of 710 Hz,12a thus confirms the
initial step of the mechanism shown above. The absence
of anti-Markovnikov-type adducts in the reaction mixture
(1H and 31P NMR data) implies that homolytic addition of
the intermediary phosphinodiselenoic acid B to vinyl
ethers (which might be initiated by the first two redox
steps in Scheme 3) does not take place under our condi-
tions. To the best of our knowledge, there are no published
reports of electrophilic addition of Se–H acids (either C–
SeH or P–SeH acids) to vinyl ethers.
All reactions were performed under an atmosphere of dry argon.
1,4-Dioxane and Et2O were dried and freshly distilled from metallic
Phosphinodiselenoic acids cannot add directly to vinyl Na before use. Vinyl ethers 1a–c,15 1d,e,16 1f,17 and 1k18 were pre-
ethers because of the instability of these acids.13,14 An at-
pared according to the published methods. Vinyl ethers 1g–i and the
1,4-bis(vinyloxy)benzene were synthesized by direct vinylation of
tempt to synthesize free phosphinodiselenoic acids by ox-
the corresponding phenol or hydroquinone with acetylene in KOH–
idation of secondary phosphines with two equivalents of
DMSO suspension (unpublished data). The optically active vinyl
ether 1j was obtained by direct vinylation of commercial 1,2:5,6-di-
elemental selenium did not give the expected result.14 Fur-
O-isopropylidene-a-D-glucofuranose with acetylene.11 Diphenyl-
phosphine (2d) was a commercial product (Aldrich). Secondary
phosphines 2a–c were prepared by a known procedure from red
phosphorus and styrene, 4-methoxystyrene, or 2-vinylfuran, respec-
tively.19 The 1H, 13C, 31P, and 77Se NMR spectra were recorded on a
Bruker DPX 400 spectrometer or a Bruker AV-400 spectrometer
(400.13, 100.62, 161.98, and 76.31 MHz, respectively) and are ref-
thermore, acidolysis of alkali metal salts of these acids
leads to a mixture of a bis(selenophosphoryl)monose-
lenide [Se(Se=PR2)2] and -triselenide [Se3(Se=PR2)2].13
Besides, the suggested generation of the intermediary
phosphinodiselenoic acids (step two) is in keeping with
the result obtained for 2-(vinyloxy)ethylamine (1k),
which formed salt 4 in 94% yield instead of the expected erenced to H3PO4 (31P NMR) or Me2Se (77Se NMR). Chemical
shifts (d) are expressed in ppm downfield from HMDS as an internal
standard. Fourier-transform IR spectra were recorded on a Bruker
Vertex 70 spectrometer. Optical rotations were measured on a Pola-
mat A polarimeter at 23 °C. Microanalyses were performed on a
vinyl-group adduct 3r (Scheme 4).
Esters 3a–q are stable up to 120 °C. The expected10c elim-
ination of alcohols from these esters to afford the corre-
sponding vinyl esters of the phosphinodiselenoic acids did Flash EA 1112 Series elemental analyzer.
not take place even at 150 °C in vacuo (10 mmHg) in the
Phosphinodiselenoate Esters 3a–o; General Procedure
presence or the absence of small amount (5 mol%) of 4-
toluenesulfonic acid. In the presence of the acid, at least
Vinyl ester 1a–i (2.1 mmol) and powdered gray Se (316 mg, 4.0
mmol) were added consecutively to a soln of secondary phosphine
2a–d (2.0 mmol) in 1,4-dioxane (8 mL) at r.t. The suspension was
© Thieme Stuttgart · New York
Synthesis 2012, 44, 431–438

434
N. K. Gusarova et al.
PAPER
stirred at 90 °C until the Se residue dissolved (~1–1.5 h) to give a
clear yellow soln. The solvent was removed under reduced pressure
(50–60 °C, 1 Torr), and the residue was purified by flash chroma-
tography [alumina (3 cm), hexane]; yield: 90–99%.
1054, 963, 915, 901, 863, 839, 747, 698, 633, 576 (P=Se), 554 (P–
Se), 466 cm–1.
3
1H NMR (400.13 MHz, CDCl3): d = 0.88 (t, JHH = 7.4 Hz, 6 H,
MeCH2), 1.34–1.50 [m, 5 H, CH(CH2Me)2], 1.94 (d, 3JHH = 6.1 Hz,
3 H, MeCH), 2.55–2.64 (m, 4 H, CH2P), 2.92–3.06 (m, 4 H,
CH2Ph), 3.50 and 3.66 (dt, 3JHH = 5.0 and 5.9 Hz, 2JHH = 9.4 Hz, 2
H, CH2O), 5.41 (m, 1 H, CHSe), 7.20–7.28 (m, 10 H, Ph).
The bisphosphinodiselenoic diester 3p was synthesized by the same
protocol from 1,4-bis(vinyloxy)benzene (162.2 mg, 1.0 mmol).
1-(Butoxy)ethyl Bis(2-phenylethyl)phosphinodiselenoate (3a)
Yield: 961 mg (96%); colorless oil.
13C NMR (100.62 MHz, CDCl3): d = 11.5 (Me), 23.7 (CH2Me),
3
26.3 (d, JPC = 2.7 Hz, MeCH), 29.3 and 29.5 (CH2Ph), 39.8 and
IR (film): 3105, 3085, 3062, 3027, 2927, 2870, 1602, 1584, 1496,
1453, 1396, 1374, 1331, 1288, 1254, 1222, 1198, 1178, 1154, 1119,
1094, 1072, 1047, 1030, 1006, 965, 945, 907, 882, 874, 836, 747,
698, 613, 577 (P=Se), 556 (P–Se), 467 cm–1.
40.5 (d, 1JPC = 38.7 and 37.0 Hz, CH2P), 41.1 (CHEt), 72.5 (CH2O),
93.7 (CHSe), 126.6, 126.7, 127.67, 127.7, 128.8, and 128.9 (o-,
m-, p-C, Ph), 140.8 (d, 3JPC = 12.8 Hz, i-C, Ph).
1
31P NMR (100.62 MHz, CDCl3): d = 47.01 (s, JP–Se = 364 Hz,
3
1H NMR (400.13 MHz, CDCl3): d = 0.91 (t, JHH = 7.3 Hz, 3 H,
1JP=Se = 749 Hz).
MeCH2), 1.41 (m, 2 H, CH2Me), 1.59 (m, 2 H, CH2Et), 1.98 (d,
77Se NMR (76.31 MHz, CDCl3): d = –232 (d, 1JP=Se = 749 Hz), 386
3JHH = 6.0 Hz, 3 H, MeCH), 2.46–2.53 (m, 4 H, CH2P), 2.99–3.26
(d, 1JP–Se = 364 Hz).
3
(m, 4 H, CH2Ph), 3.64 and 3.91 (dt, JHH = 6.4 and 6.6 Hz,
2JHH = 16.0 Hz, 2 H, CH2O), 5.84 (m, 1 H, CHSe), 7.14–7.30 (m, 10
Anal. Calcd for C24H35OPSe2: C, 54.55; H, 6.68; P, 5.86; Se, 29.88.
Found: C, 54.52; H, 6.51; P, 5.63; Se, 30.06.
H, Ph).
13C NMR (100.62 MHz, CDCl3): d = 13.5 (MeCH2), 19.1 (CH2Me),
1-(2,2,3,3-Tetrafluoropropoxy)ethyl Bis(2-phenylethyl)phos-
phinodiselenoate (3d)
Yield: 1180 mg (97%); yellowish oil.
3
26.4 (d, JPC = 2.9 Hz, MeCH), 29.9 and 30.2 (CH2Ph), 31.1
1
(CH2Et), 39.8 and 40.2 (d, JPC = 38.7 and 37.0 Hz, CH2P), 69.5
(CH2O), 95.2 (CHSe), 126.1, 126.2, 127.3, 127.5, 128.3, 128.4 (o-,
m-, p-C, Ph), 140.7 (d, 3JPC = 13.2 Hz, i-C, Ph).
IR (film): 3085, 3062, 3027, 2926, 2856, 1646, 1603, 1587, 1496,
1453, 1400, 1379, 1276, 1231, 1203, 1104, 1003, 943, 895, 874,
835, 746, 699, 613, 575 (P=Se), 554 (P–Se), 467 cm–1.
1
31P NMR (161.98 MHz, CDCl3): d = 45.38 (s, JP–Se = 361 Hz,
1JP=Se = 755 Hz).
3
1H NMR (400.13 MHz, CDCl3): d = 1.93 (d, JHH = 6.1 Hz, 3 H,
77Se NMR (76.31 MHz, CDCl3): d = –230 (d, 1JP=Se = 755 Hz), 390
MeCH), 2.53–2.65 (m, 4 H, CH2P), 2.85–3.03 (m, 4 H, CH2Ph),
4.18 (m, 2 H, CH2O), 5.47 (m, 1 H, CHSe), 5.86 (tt, 2JHF = 53.3 Hz,
3JHH = 5.4 Hz, 1 H, CF2H), 7.16–7.28 (m, 10 H, Ph).
(d, 1JP–Se = 361 Hz).
Anal. Calcd for C22H31OPSe2: C, 52.81; H, 6.24; P, 6.19; Se, 31.56.
Found: C, 52.74; H, 6.19; P, 6.11; Se, 31.63.
13C NMR (100.62 MHz, CDCl3): d = 25.8 (MeCH), 30.0 and 30.1
(CH2Ph), 39.5 and 40.4 (d, 1JPC = 36.6 and 37.2 Hz, CH2P), 65.9 (t,
1-(Pentyloxy)ethyl Bis(2-phenylethyl)phosphinodiselenoate
(3b)
Yield: 967 mg (94%); yellowish oil.
1
2JCF = 28.8 Hz, CH2O), 92.8 (CHSe), 109.0 (tt, JCF = 248.0 Hz,
2JCF = 34.3 Hz, CF2H), 114.4 (tt, 1JCF = 256.50 Hz, 2JCF = 29.85 Hz,
CF2), 126.6, 126.6, 128.3, and 128.7 (o-, m-, p-C, Ph), 139.8 (d,
3JPC = 17.0 Hz, i-C, Ph).
IR (film): 3106, 3085, 3062, 3028, 2950, 2926, 2873, 1603, 1585,
1490, 1453, 1394, 1335, 1276, 1254, 1223, 1203, 1174, 1156, 1121,
1095, 1057, 1003, 962, 872, 835, 746, 699, 614, 575 (P=Se), 554
(P–Se), 467 cm–1.
1
31P NMR (161.98 MHz, CDCl3): d = 48.61 (s, JP–Se = 349 Hz,
1JP=Se = 748 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –225 (d, 1JP=Se = 748 Hz), 323
3
1H NMR (400.13 MHz, CDCl3): d = 0.87 (t, JHH = 7.6 Hz, 3 H,
(d, 1JP–Se = 349 Hz).
MeCH2), 1.27–1.37 (m, 4 H, (CH2)2Me), 1.48–1.55 (m, 2 H,
3
Anal. Calcd for C22H25F6OPSe2: C, 43.44; H, 4.14; F, 18.74; P,
5.09; Se, 25.96. Found: C, 43.52; H, 4.51; F, 18.80; P, 5.23; Se,
25.86.
CH2Pr), 1.93 (d, JHH = 6.1 Hz, 3 H, MeCH), 2.50–2.69 (m, 4 H,
3
CH2P), 2.87–3.15 (m, 4 H, CH2Ph), 3.53 and 3.91 (dt, JHH = 6.8
and 6.6 Hz, 2JHH = 15.9 Hz, 2 H, CH2O), 5.43 (m, 1 H, CHSe), 7.14–
7.30 (m, 10 H, Ph).
1-[(2,2,3,3,4,4,5,5-Octafluoropentyl)oxy]ethyl Bis(2-phenyleth-
yl)phosphinodiselenoate (3e)
Yield: 1303 mg (99%); yellowish oil.
13C NMR (100.62 MHz, CDCl3): d = 13.3 (MeCH2), 21.7 (CH2Me),
3
23.4 (CH2Et), 26.4 (d, JPC = 2.8 Hz, MeCH), 29.7 and 30.2
(CH2Ph), 31.3 (CH2Pr), 40.0 and 40.5 (d, 1JPC = 38.0 and 37.6 Hz,
CH2P), 69.7 (CH2O), 94.9 (CHSe), 125.5, 125.6, 127.9, 128.1,
128.4 (o-, m-, p-C, Ph), 140.6 (d, 3JPC = 14.7 Hz, i-C, Ph).
IR (film): 3087, 3064, 3028, 2928, 2860, 1603, 1585, 1497, 1454,
1400, 1379, 1360, 1325, 1287, 1228, 1204, 1173, 1131, 1096, 1044,
1031, 991, 956, 946, 904, 876, 838, 809, 748, 698, 631, 614, 576,
567 (P=Se), 548 (P–Se), 466 cm–1.
31P NMR (161.98 MHz, CDCl3): d = 46.85 (s, JP–Se = 362 Hz,
1
1JP=Se = 751 Hz).
3
1H NMR (400.13 MHz, CDCl3): d = 1.97 (d, JHH = 6.2 Hz, 3 H,
77Se NMR (76.31 MHz, CDCl3): d = –237 (d, 1JP=Se = 751 Hz), 387
MeCH), 2.51–2.71 (m, 4 H, CH2P), 2.82–3.13 (m, 4 H, CH2Ph),
4.12–4.20 (m, 2 H, CH2O), 5.50 (m, 1 H, CHSe), 6.02 (tt,
2JHF = 51.9 Hz, 3JHH = 5.4 Hz, 1 H, CF2H), 7.16–7.31 (m, 10 H, Ph).
(d, 1JP–Se = 362 Hz).
Anal. Calcd for C23H33OPSe2: C, 53.70; H, 6.47; P, 6.02; Se, 30.70.
Found: C, 54.12; H, 6.51; P, 5.83; Se, 30.86.
1
13C NMR (100.62 MHz, CDCl3): d = 25.7 (d, JPC = 2.6 Hz,
1
MeCH), 29.9 and 30.0 (CH2Ph), 39.3 and 40.3 (d, JPC = 37.2 and
1-(2-Ethylbutoxy)ethyl Bis(2-phenylethyl)phosphinodisele-
noate (3c)
Yield: 972 mg (92%); yellowish oil.
36.8 Hz, CH2P), 65.7 (t, 3JCF = 26.0 Hz, CH2O), 93.0 (CHSe), 107.5
1
2
(tt, JCF = 255.40 Hz, JCF = 29.85 Hz, CF2H), 109.7–113.5 (m,
CF2CF2), 114.8 (tt, 1JCF = 256.50 Hz, 2JCF = 29.85 Hz, CF2), 126.5,
126.6, 128.2, 128.2, 128.6, and 128.6 (o-, m-, p-C, Ph), 139.6 (d,
3JPC = 16.6 Hz, i-C, Ph).
IR (film): 3107, 3086, 3064, 3028, 2961, 2926, 2875, 1603, 1585,
1486, 1395, 1379, 1338, 1262, 1237, 1225, 1211, 1169, 1122, 1098,
Synthesis 2012, 44, 431–438
© Thieme Stuttgart · New York

PAPER
One-Pot Synthesis of 1-(Alkoxy)ethyl and 1-(Aryloxy)ethyl Phosphinodiselenoates
435
1
3
31P NMR (161.98 MHz, CDCl3): d = 49.30 (s, JP–Se = 344 Hz,
1H NMR (400.13 MHz, CDCl3): d = 2.16 (d, JHH = 6.1 Hz, 3 H,
MeCH), 2.36 (s, 3 H, MeC6H4), 2.38–2.41 and 2.56–2.59 (m, 4 H,
CH2Ph), 2.78–3.09 (m, 4 H, CH2P), 6.07 (m, 1 H, CHSe), 6.86 (d,
3J = 7.4 Hz, 1 H, H4 in C6H4), 7.02 (d, 3J = 8.1 Hz, 1 H, H5 in C6H4),
7.06–7.10 (m, 2 H, H2,6 in C6H4), 7.29–7.35 (m, 10 H, Ph).
1JP=Se = 754 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –237 (d, 1JP=Se = 754 Hz), 327
(d, 1JP–Se = 344 Hz).
Anal. Calcd for C23H25F8OPSe2: C, 41.96; H, 3.83; F, 23.09; P,
4.70; Se, 23.99. Found: C, 41.54; H, 3.68; F, 22.89; P, 4.78; Se,
23.65.
13C NMR (100.62 MHz, CDCl3): d = 20.9 (MeC6H4), 26.0 (d,
3JPC = 2.6 Hz, MeCH), 29.5 and 29.7 (d, JPC = 2.6 and 2.2 Hz,
3
1
CH2Ph), 38.4 and 39.3 (d, JPC = 37.7 and 35.4 Hz, CH2P), 88.9
(CHSe), 114.7, 118.4, and 123.5 (C2,4,6 in C6H4), 125.9, 126.1,
127.8, 127.9, 128.1, and 128.2 (o-, m-, p-C, Ph), 128.7, 139.0 (C3,5
in C6H4), 139.7 (d, 3JPC = 11.4 Hz, i-C, Ph), 155.4 (C1 in C6H4).
1-(2-Furylmethyloxy)ethyl Bis(2-phenylethyl)phosphinodi-
selenoate (3f)
Yield: 944 mg (90%); yellowish oil.
31P NMR (161.98 MHz, CDCl3): d = 47.10 (s, JP–Se = 358 Hz,
1
IR (film): 3109, 3084, 3061, 3026, 2923, 2860, 1603, 1497, 1453,
1396, 1377, 1328, 1267, 1223, 1150, 1100, 1016, 945, 921, 902,
852, 816, 745, 699, 599 (P=Se), 575 (P–Se), 467 cm–1.
1JP=Se = 744 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –233 (d, 1JP=Se = 744 Hz), 325
(d, 1JP–Se = 358 Hz).
1H NMR (400.13 MHz, CDCl3): d = 1.99 (d, JHH = 6.2 Hz, 3 H,
3
MeCH), 2.61–2.73 (m, 4 H, CH2P), 2.97–3.11 (m, 4 H, CH2Ph),
Anal. Calcd for C25H29OPSe2: C, 56.19; H, 5.47; P, 5.80; Se, 29.55.
Found: C, 56.02; H, 5.58; P, 5.90; Se, 29.42.
4.63 and 4.76 (d, 2JHH = 12.4 Hz, 2 H, CH2O), 5.62 (m, 1 H, CHSe),
6.35 (dd, JHH = 1.9 Hz, JHH = 3.1 Hz, 1 H, H4 in Fur), 6.44 (d,
3JHH = 3.1 Hz, 1 H, H3 in Fur), 7.14–7.30 (m, 10 H, Ph), 7.37 (s, 1
H, H5 in Fur).
3
3
1-(2,6-Dimethylphenoxy)ethyl Bis(2-phenylethyl)phosphinodi-
selenoate (3i)
Yield: 1064 mg (97%); yellowish oil.
3
13C NMR (100.62 MHz, CDCl3): d = 26.4 (d, JPC = 2.9 Hz,
1
MeCH), 29.8 and 30.1 (CH2Ph), 39.6 and 39.7 (d, JPC = 36.5 and
IR (film): 3084, 3061, 3026, 2951, 2921, 2857, 1602, 1495, 1473,
1453, 1397, 1375, 1327, 1261, 1240, 1190, 1129, 1082, 1030, 1000,
945, 918, 837, 815, 769, 747, 699, 579 (P=Se), 546 (P–Se), 524, 467
cm–1.
37.2 Hz, CH2P), 63.3 (CH2O), 92.7 (CHSe), 110.0, 110.2 (C3,4 in
Fur), 126.4, 128.2, 128.5 (o-, m-, p-C, Ph), 139.8 (d, 3JPC = 17.3 Hz,
i-C, Ph), 142.9 and 150.0 (C2,5 in Fur).
1
3
31P NMR (161.98 MHz, CDCl3): d = 47.30 (s, JP–Se = 358 Hz,
1H NMR (400.13 MHz, CDCl3): d = 2.17 (d, JHH = 6.1 Hz, 3 H,
1JP=Se = 750 Hz).
MeCH), 2.28–2.58 (m, 10 H, CH2P, 2,6-Me2C6H3), 2.88–3.04 (m, 4
H, CH2Ph), 5.93 (m, 1 H, CHSe), 6.81 (d, 3J = 7.5 Hz, 1 H, H4 in
C6H3), 6.95 (d, 3J = 7.5 Hz, 2 H, H3,5 in C6H3), 7.16–7.32 (m, 10 H,
Ph).
77Se NMR (76.31 MHz, CDCl3): d = –228 (d, 1JP=Se = 750 Hz), 310
(d, 1JP–Se = 358 Hz).
Anal. Calcd for C23H27O2PSe2: C, 52.68; H, 5.19; P, 5.91; Se, 30.12.
Found: C, 52.45; H, 5.28; P, 5.78; Se, 30.20.
13C NMR (100.62 MHz, CDCl3): d = 17.5 (MeC6H3), 26.2 (MeCH),
1
29.7 (CH2Ph), 37.8 and 37.9 (d, JPC = 38.3 and 34.9 Hz, CH2P),
93.7 (CHSe), 124.6 and 126.3 (C3,4,5 in C6H3), 128.2, 128.4, 128.5
and 129.0 (o-, m-, p-C, Ph), 130.7 (C2,6 in C6H3), 139.9 (t, 3J = 17.3
Hz, i-C, Ph), 153.1 (C1 in C6H3).
1-Phenoxyethyl Bis(2-phenylethyl)phosphinodiselenoate (3g)
Yield: 1020 mg (98%); yellowish oil.
IR (film): 3085, 3061, 3027, 2922, 2853, 1592, 1495, 1454, 1395,
1377, 1334, 1291, 1234, 1213, 1174, 1154, 1092, 1072, 1028, 1005,
929, 908, 874, 836, 796, 753, 695, 613, 576, 565 (P=Se), 512 (P–
Se), 466 cm–1.
1
31P NMR (161.98 MHz, CDCl3): d = 49.82 (s, JP–Se = 360 Hz,
1JP=Se = 738 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –231 (d, 1JP=Se = 738 Hz), 328
(d, 1JP–Se = 360 Hz).
3
1H NMR (400.13 MHz, CDCl3): d = 2.13 (d, JHH = 6.1 Hz, 3 H,
MeCH), 2.34–2.40, 2.51–2.56 (m, 4 H, CH2P), 2.71–3.07 (m, 4 H,
CH2Ph), 6.04 (m, 1 H, CHSe), 7.05 (m, 3 H, PhO), 7.17–7.33 (m,
12 H, Ph).
Anal. Calcd for C26H31OPSe2: C, 56.94; H, 5.70; P, 5.65; Se, 28.80.
Found: C, 56.45; H, 5.88; P, 5.72; Se, 28.75.
1-[(2,2,3,3,4,4,5,5-Octafluoropentyl)oxy]ethyl Bis[2-(4-Meth-
oxyphenyl)ethyl]phosphinodiselenoate (3j)
Yield: 1368 mg (95%); yellowish oil.
3
13C NMR (100.62 MHz, CDCl3): d = 26.2 (d, JPC = 2.9 Hz,
1
MeCH), 29.6 and 29.8 (CH2Ph), 38.6 and 39.6 (d, JPC = 37.6 and
35.8 Hz, CH2P), 89.1 (CHSe), 117.9, 122.8 (o-, p-C, PhO), 126.1,
126.2, 127.9, 128.0, 128.2, and 128.4 (o-, m-, p-C, Ph), 129.1 (m-C,
PhO), 139.7 (d, 3JPC = 17.0 Hz, i-C, Ph), 155.65 (i-C, PhO).
31P NMR (161.98 MHz, CDCl3): d = 48.59 (s, JP–Se = 354 Hz,
IR (film): 3080, 3062, 2999, 2932, 2838, 1612, 1584, 1513, 1462,
1445, 1401, 1300, 1247, 1175, 1130, 1097, 1036, 992, 954, 901,
874, 816, 734, 635, 579 (P=Se), 549 (P–Se), 480 cm–1.
1
3
1JP=Se = 744 Hz).
1H NMR (400.13 MHz, CDCl3): d = 1.94 (d, JHH = 5.6 Hz, 3 H,
MeCH), 2.46–2.56 (m, 4 H, CH2P), 2.79–2.96 (m, 4 H, CH2Ph),
3.74 (s, 6 H, MeO), 4.12–4.17 (m, 2 H, CH2O), 5.48 (m, 1 H,
CHSe), 6.00 (tt, 2JHF = 52.2 Hz, 3JHH = 5.4 Hz, 1 H, HCF2), 6.79 (m,
4 H, H2,6 in C6H4), 6.08 (m, 4 H, H3,5 in C6H4).
77Se NMR (76.31 MHz, CDCl3): d = –233 (d, 1JP=Se = 744 Hz), 326
(d, 1JP–Se = 354 Hz).
Anal. Calcd for C24H27OPSe2: C, 55.40; H, 5.23; P, 5.95; Se, 30.35.
Found: C, 55.70; H, 5.11; P, 6.27; Se, 30.56.
13C NMR (100.62 MHz, CDCl3): d = 25.7 (MeCH), 29.2
1
(CH2C6H4), 39.5 and 40.3 (d, JPC = 36.1 Hz, CH2P), 55.2 (MeO),
1-(3-Methylphenoxy)ethyl Bis(2-phenylethyl)phosphinodisele-
noate (3h)
Yield: 1058 mg (99%); yellowish oil.
3
65.7 (t, JCF = 25.8 Hz, CH2CF2), 92.8 (CHSe), 107.6 (tt,
1JCF = 253.1 Hz, 2JCF = 30.5 Hz, CF2H), 108.1–114.1 (m, CF2CF2),
1
2
115.2 (tt, JCF = 256.5 Hz, JCF = 30.9 Hz, CF2), 114.1, 129.2
(C2,3,5,6 in C6H4), 131.6, 131.8 (d, 3JPC = 16.6 Hz, C1 in C6H4), 158.3
(C4 in C6H4).
IR (film): 3060, 3027, 2965, 2922, 2859, 2735, 2676, 2603, 1947,
1891, 1806, 1735, 1603, 1587, 1492, 1452, 1396, 1377, 1337, 1288,
1256, 1217, 1086, 1011, 948, 894, 871, 745, 696, 619, 571 (P=Se),
548 (P–Se), 467 cm–1.
1
31P NMR (161.98 MHz, CDCl3): d = 48.38 (s, JP–Se = 348 Hz,
1JP=Se = 746 Hz).
© Thieme Stuttgart · New York
Synthesis 2012, 44, 431–438

436
N. K. Gusarova et al.
PAPER
3
77Se NMR (76.31 MHz, CDCl3): d = –225 (d, 1JP=Se = 746 Hz), 323
(d, 1JP–Se = 348 Hz).
1H NMR (400.13 MHz, CDCl3): d = 2.03 (d, JHH = 6.1 Hz, 3 H,
MeCH), 2.28 (s, 3 H, MeC6H4), 2.25–2.31 and 2.41–2.51 (m, 4 H,
CH2P), 2.61–2.72 and 2.80–3.06 (m, 4 H, CH2Fur), 5.88–5.91 (m, 2
H, CHSe, H3 in Fur), 5.99 (d, 3JHH = 1.8 Hz, 1 H, H3 in Fur), 6.20–
6.24 (m, 2 H, H4 in Fur), 6.80 (d, 3JHH = 7.5 Hz, 1 H, H4 in C6H4),
6.88 (d, 3JHH = 8.0 Hz, 1 H, H6 in C6H4), 6.94 (s, 1 H, H2 in C6H4),
7.13 (t, 3J = 7.5 Hz, 1 H, H5 in C6H4), 7.23 and 7.26 (s, 2 H, H5 in
Fur).
Anal. Calcd for C25H29F8O3PSe2: C, 41.80; H, 4.07; F, 21.16; P,
4.31; Se, 21.98. Found: C, 41.53; H, 4.12; F, 21.45; P, 4.15; Se,
21.62.
1-(3-Methylphenoxy)ethyl Bis[2-(4-methoxyphenyl)ethyl]phos-
phinodiselenoate (3k)
Yield: 1082 mg (91%); yellowish oil.
13C NMR (100.62 MHz, CDCl3): d = 21.1 (MeC6H4), 22.5 and 22.7
3
(CH2Fur), 26.2 (d, JPC = 2.6 Hz, MeCH), 34.8 and 35.8 (d,
IR (film): 3029, 2995, 2951, 2927, 2854, 2835, 1610, 1586, 1512,
1490, 1458, 1445, 1377, 1300, 1247, 1176, 1159, 1129, 1085, 1035,
949, 871, 820, 781, 732, 692, 614, 550 (P=Se), 519 P–Se), 495, 477,
449 cm–1.
1JPC = 39.8 and 37.6 Hz, CH2P), 89.5 (CHSe), 105.5, 105.7, 110.0
and 110.1 (C3,4 in Fur), 115.0, 118.6, 123.7, 128.9, and 139.2
(C2,3,4,5,6 in C6H4), 141.1 and 141.2 (C5 in Fur), 152.7, 152.9 (C2 in
Fur), 155.5 (C1 in C6H4).
3
1H NMR (400.13 MHz, CDCl3): d = 2.07 (d, JHH = 5.6 Hz, 3 H,
31P NMR (161.98 MHz, CDCl3): d = 46.13 (s, JP–Se = 361 Hz,
1
MeCH), 2.27 (s, 3 H, MeC6H4), 2.27–2.29 and 2.40–2.44 (m, 4 H,
CH2P), 2.57–2.66 (m, 1 H, CH2C6H4), 2.74–2.98 (m, 3 H,
CH2C6H4), 3.74 (s, 6 H, MeO), 5.98 (m, 1 H, CHSe), 6.79–7.08 (m,
12 H, Ar).
1JP=Se = 746 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –236 (d, 1JP=Se = 746 Hz), 324
(d, 1JP–Se = 361 Hz).
13C NMR (100.62 MHz, CDCl3): d = 21.3 (MeC6H4), 26.4 (d,
3JPC = 2.2 Hz, MeCH), 29.0 and 29.2 (CH2C6H4), 39.4 and 40.2 (d,
1JPC = 36.8 and 34.6 Hz, CH2P), 55.2 (MeO), 89.0 (CHSe), 113.9,
114.0, 115.1, 118.8, 123.8, 129.1, and 129.2 (Ar), 132.04 (d,
3JPC = 16.9 Hz, i-C, C6H4), 139.4, 155.9, and 158.1 (Ar).
Anal. Calcd for C21H25O3PSe2: C, 49.04; H, 4.90; P, 6.02; Se, 30.70.
Found: C, 49.23; H, 4.85; P, 6.12; Se, 30.68.
1-[(2,2,3,3,4,4,5,5-Octafluoropentyl)oxy]ethyl Diphenylphos-
phinodiselenoate (3n)
Yield: 1179 mg (98%); yellowish oil.
1
31P NMR (161.98 MHz, CDCl3): d = 46.99 (s, JP–Se = 357 Hz,
1JP=Se = 742 Hz).
IR (film): 3145, 3056, 2972, 2928, 2883, 2859, 1479, 1437, 1403,
1378, 1331, 1308, 1287, 1228, 1173, 1131, 1092, 1044, 1029, 996,
958, 902, 809, 747, 691, 618, 575 (P=Se), 542 (P–Se), 502, 475, 420
cm–1.
77Se NMR (76.31 MHz, CDCl3): d = –230 (d, 1JP=Se = 742 Hz), 325
(d, 1JP–Se = 357 Hz).
Anal. Calcd for C27H33O3PSe2: C, 54.55; H, 5.60; P, 5.21; Se, 26.57.
Found: C, 54.62; H, 5.58; P, 5.26; Se, 26.71.
1H NMR (400.13 MHz, CDCl3): d = 1.89 (d, JHH = 5.8 Hz, 3 H,
3
MeCH), 3.93 (t, 3JHH = 13.8 Hz, 2 H, CH2O), 5.57 (m, 1 H, CHSe),
2
3
6.00 (tt, JHF = 52.2 Hz, JHH = 5.4 Hz, 1 H, HCF2), 7.48 (m, 6 H,
1-Phenoxyethyl Bis[2-(2-furyl)ethyl]phosphinodiselenoate (3l)
H3,4,5 in Ph), 7.87 (m, 2 H, H6 in Ph), 7.99 (m, 2 H, H2 in Ph).
Yield: 961 mg (96%); yellowish oil.
13C NMR (100.62 MHz, CDCl3): d = 25.3 (MeCH), 65.9 (t,
IR (film): 3149, 3114, 3061, 3040, 2967, 2921, 2854, 1720, 1655,
1593, 1505, 1490, 1437, 1398, 1378, 1333, 1290, 1232, 1213, 1174,
1147, 1091, 1073, 1007, 917, 886, 850, 798, 753, 733, 692, 638, 599
(P=Se), 564 (P–Se), 512, 479, 419 cm–1.
3JCF = 26.2 Hz, CH2O), 92.0 (CHSe), 107.5 (tt, JCF = 254.7 Hz,
1
2JCF = 30.6 Hz, CF2H), 110.3–114.1 (m, CF2CF2), 114.74 (tt,
1JCF = 256.5 Hz, 2JCF = 29.8 Hz, CF2), 128.7, 131.7, 132.0 (o-, m-,
3
3
p-C, Ph), 133.7 (d, JPC = 41.3 Hz, i-C, Ph), 134.4 (d, JPC = 43.1
Hz, i-C, Ph).
1H NMR (400.13 MHz, CDCl3): d = 2.05 (d, JHH = 6.1 Hz, 3 H,
3
MeCH), 2.29–2.35 and 2.43–2.54 (m, 4 H, CH2P), 2.64–2.75 and
2.80–3.07 (m, 4 H, CH2Fur), 5.90 (d, 3J = 3.1 Hz, 1 H, H3 in Fur),
5.93 (m, 1 H, CHSe), 6.00 (d, 3JHH = 2.9 Hz, 1 H, H3 in Fur), 6.22
and 6.25 (s, 2 H, H4 in Fur), 7.01 (t, 3J = 7.3 Hz, 1 H, H4 in Ph), 7.10
(d, 3J = 7.3 Hz, 2 H, H4 in Ph), 7.12–7.29 (m, 4 H, Ph, H5 in Fur).
1
31P NMR (161.98 MHz, CDCl3): d = 39.05 (s, JP–Se = 361 Hz,
1JP=Se = 768 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –164 (d, 1JP=Se = 768 Hz), 419
(d, 1JP–Se = 361 Hz).
3
13C NMR (100.62 MHz, CDCl3): d = 22.8 (d, JPC = 19.4 Hz,
Anal. Calcd for C19H17F8OPSe2: C, 37.89; H, 2.85; F, 25.24; P,
5.14; Se, 26.22. Found: C, 37.94; H, 2.72; F, 25.44; P, 5.35; Se,
26.08.
CH2Fur), 26.3 (MeCH) 35.1 and 36.1 (d, 1JPC = 40.1 and 37.6 Hz,
CH2P), 89.6 (CHSe), 105.9, 105.9, 110.3 and 110.3 (C3,4 in Fur),
118.3, 123.2, and 129.4 (o-, m-, p-C, Ph), 141.3 and 141.4 (C5 in
Fur), 153.0 and 153.2 (C2,5 in Fur), 155.9 (i-C, Ph).
1-(Phenoxy)ethyl Diphenylphosphinodiselenoate (3o)
Yield: 836 mg (90%); yellowish oil.
1
31P NMR (161.98 MHz, CDCl3): d = 47.38 (s, JP–Se = 356 Hz,
1JP=Se = 754 Hz).
IR (film): 3086, 3050, 2975, 2923, 2852, 2799, 2720, 1591, 1490,
1481, 1435, 1378, 1331, 1306, 1233, 1212, 1174, 1157, 1090, 1026,
998, 929, 889, 874, 845, 795, 749, 691, 617, 573 P=Se), 541 (P–Se),
515, 502, 475, 421 cm–1.
77Se NMR (76.31 MHz, CDCl3): d = –237 (d, 1JP=Se = 754 Hz), 323
(d, 1JP–Se = 356 Hz).
Anal. Calcd for C20H23O3PSe2: C, 48.02; H, 4.63; P, 6.19; Se, 31.57.
Found: C, 48.33; H, 4.35; P, 6.15; Se, 31.62.
1H NMR (400.13 MHz, CDCl3): d = 2.00 (d, JHH = 6.0 Hz, 3 H,
3
MeCH), 6.07 (m, 1 H, CHSe), 6.95 (t, 3JHH = 8.4 Hz, 1 H, H4 in Ph),
7.12 (d, 3JHH = 8.6 Hz, 2 H, H2,6 in Ph), 7.31 (m, 2 H, H3,5 in Ph),
7.48 (m, 6 H, H3,4,5 in Ph), 7.87 (m, 2 H, H6 in Ph), 7.99 (m, 2 H, H2
in Ph).
1-(3-Methylphenoxy)ethyl Bis[2-(2-furyl)ethyl]phosphinodi-
selenoate (3m)
Yield: 968 mg (94%); yellowish oil.
13C NMR (100.62 MHz, CDCl3): d = 26.2 (MeCH), 87.4 (CHSe),
117.2, 122.6, 127.5, 127.6, 128.5, 128.6, 129.3, and 131.2 (o-, m-,
IR (film): 3145, 3115, 3035, 2969, 2921, 2857, 1589, 1506, 1489,
1438, 1399, 1378, 1333, 1288, 1257, 1230, 1217, 1171, 1151, 1086,
1009, 950, 915, 885, 856, 796, 782, 732, 691, 638, 599 (P=Se), 567
(P–Se), 499, 479 cm–1.
3
3
p-C, Ph), 133.8 (d, JPC = 33.2 Hz, i-C, Ph), 134.6 (d, JPC = 34.7
Hz, i-C, Ph), 155.9 (i-C, PhO).
Synthesis 2012, 44, 431–438
© Thieme Stuttgart · New York

PAPER
One-Pot Synthesis of 1-(Alkoxy)ethyl and 1-(Aryloxy)ethyl Phosphinodiselenoates
437
1
31P NMR (161.98 MHz, CDCl3): d = 37.91 (s, JP–Se = 370 Hz,
1JP=Se = 764 Hz).
105.1, 105.2, and 105.3 (C1), 108.7, 109.2, 111.9, and 112.0 (m,
OCO), 126.4, 126.5, 126.7, 128.3, 128.5, and 128.6 (o-, m-, p-C,
Ph), 139.9, 140.0, and 140.1 (i-C, Ph).
77Se NMR (76.31 MHz, CDCl3): d = –168 (d, 1JP=Se = 764 Hz), 425
(d, 1JP–Se = 370 Hz).
31P NMR (161.98 MHz, CDCl3): d = 37.51 and 38.65 (s, JP–Se
=
1
370 and 367 Hz, 1JP=Se = 768 and 764 Hz) in a 1:2 ratio.
Anal. Calcd for C20H19OPSe2: C, 51.74; H, 4.13; P, 6.67; Se, 34.02.
Found: C, 51.82; H, 4.24; P, 6.62; Se, 34.11.
77Se NMR (76.31 MHz, CDCl3): d = –161 and –156 (d, 1JP=Se = 764
and 768 Hz), 406 and 427 (d, 1JP–Se = 367 and 370 Hz).
1,4-Phenylenebis(oxyethane-1,1-diyl) Bis[bis(2-phenyleth-
yl)(phosphinodiselenoate)] (3p)
Yield: 924 mg (96%); yellowish oil.
Anal. Calcd for C30H41O6PSe2: C, 52.48; H, 6.02; P, 4.51; Se, 23.00.
Found: C, 52.61; H, 6.09; P, 4.65; Se, 23.18.
IR (film): 3060, 3028, 2959, 2917, 2853, 1953, 1877, 1810, 1731,
1641, 1600, 1500, 1447, 1381, 1240, 1205, 1120, 1083, 1003, 930,
877, 939, 747, 702, 568 (P=Se), 548 (P–Se), 471 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 2.06, 2.08, 2.11, and 2.13 (d,
3JHH = 5.9 Hz, 6 H, MeCH), 2.24–2.60 (m, 8 H, CH2P), 2.65–3.12
(m, 8 H, CH2Ph), 5.88–6.03 (m, 2 H, CHSe), 7.07–7.32 (m, 24 H,
Ar).
[2-(Vinyloxy)ethyl]ammonium bis(2-phenylethyl)phosphino-
diselenoate (4)
[2-(Vinyloxy)ethyl]amine (1k; 183 mg, 2.1 mmol) and powdered
gray Se (316 mg, 4.0 mmol) were added consecutively to a soln of
bis(2-phenylethyl)phosphine (2a; 485 mg, 2.0 mmol) in 1,4-diox-
ane (8 mL) at r.t. The suspension was stirred at 90 °C until the Se
residue dissolved (~15 min) to give a clear colorless soln. The sol-
vent was removed under reduced pressure (30–40 °C, 1 Torr) and
the residue was washed with Et2O (2 × 10 mL) and dried in vacuo
(40 °C, 1 Torr); yield: 916 mg (94%); mp 78–87 (dec).
3
13C NMR (100.62 MHz, CDCl3): d = 26.1 (d, JPC = 2.5 Hz,
MeCH), 29.3, 29.6, 29.8, and 30.0 (CH2Ph), 38.6, 38.7, 39.3, and
1
39.5 (d, JPC = 38.1, 37.5, 38.4, and 38.8 Hz, CH2P), 89.7, 89.9,
IR (film): 3163, 3050, 2933, 2849, 2702, 1641, 1620, 1600, 1578,
1495, 1478, 1453, 1396, 1365, 1320, 1270, 1198, 1123, 1064, 1021,
994, 967, 945, 829, 761, 743, 698, 571 (P–Se), 489, 421 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 2.44–2.50 (m, 4 H, CH2P),
2.93–3.00 (m, 4 H, CH2Ph), 3.51 (t, 3JHH = 4.5 Hz, 2 H, CH2N), 4.00
(m, 3 H, CH2O, H2C= ), 4.13 (dd, 3JHH = 14.4 Hz, 2JHH = 1.8 Hz, 1
H, H2C= ), 6.32 (dd, 3JHH = 6.8 and 14.4 Hz, 1 H, HC= ), 7.13–7.21
(m, 10 H, Ph), 7.86 (s, 3 H, HN).
90.0, and 90.3 (CHSe), 117.6 (C2,3,5,6 in C6H4), 126.1, 126.2, 126.4,
127.9, 128.0, 128.3, 128.4, and 128.5 (o-, m-, p-C, Ph), 139.5,
139.6, and 137.7 (d, 3JPC = 16.5, 16.9, and 16.5 Hz, i-C, Ph), 151.3
(C1,4 in C6H4).
31P NMR (161.98 MHz, CDCl3): d = 48.65, 48.84, and 49.15 (s,
1JP–Se = 354 Hz, 1JP=Se = 747, 746, and 747 Hz) in the ratio 1:2.2:1.8.
77Se NMR (76.31 MHz, CDCl3): d = –232, –230, and –231 (d,
1
1JP=Se = 747, 746, and 747 Hz), 320, 321, and 322 (d, JP–Se = 354
13C NMR (100.62 MHz, CDCl3): d = 30.6 (CH2Ph), 38.7 (CH2N),
Hz).
1
43.0 (d, JPC = 35.3 Hz, CH2P), 62.5 (CH2O), 88.3 ( =CH2), 125.5
1
The presence of several signals in the H, 13C, 31P, and 77Se NMR
(p-C, Ph), 128.2 and 128.3 (o-, m-C, Ph), 140.7 (d, 3JPC = 17.2 Hz,
i-C, Ph), 149.9 (=CH).
spectra of bisphosphinodiselenoate 3p might be due to the existence
of two asymmetric carbon atoms in the molecule.
31P NMR (161.98 MHz, CDCl3): d = 25.70 (s, 1JP–Se = 558 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –67 (d, 1JPSe = 558 Hz).
Anal. Calcd for C42H48O2P2Se4: C, 52.40; H, 5.03; P, 6.44; Se,
32.81. Found: C, 52.47; H, 4.93; P, 6.36; Se, 32.70.
Anal. Calcd for C20H28NOPSe2: C, 49.29; H, 5.79; P, 6.36; Se,
32.40. Found: C, 49.44; H, 5.81; P, 6.12; Se, 32.34.
1-(1,2:5,6-Di-O-isopropylidene-d-glucofuranosyloxy)ethyl
Bis(2-phenylethyl)phosphinodiselenoate (3q)
1,2:5,6-Di-O-isopropylidene-3-O-vinyl-a-D-glucofuranose (1j; 573
mg, 2.0 mmol) and powdered gray Se (316 mg, 4.0 mmol) were
added consecutively to a soln of secondary phosphine 2a (485 mg,
2.0 mmol) in 1,4-dioxane (8 mL) at r.t. The suspension was stirred
at 90 °C until the Se residue dissolved (~1.5 h) to give a clear yel-
lowish soln. The solvent was then removed under reduced pressure
(50–60 °C, 1 Torr) and the residue was washed sequentially with
EtOH (2 × 5 mL) and hexane (2 × 5 mL) then dried in vacuo (40–
45 °C, 1 Torr) to give a yellowish oil; yield: 1195 mg (87%). The
NMR spectra suggest that this phosphinodiselenoate was obtained
as a mixture of two diastereomers; [a]D23 –21.3 (c 2, CHCl3).
Acknowledgment
This work was supported by the Russian Foundation for Basic Re-
search (Grant No. 11-03-00334) and the President of the Russian
Federation (Program for the Support of Leading Scientific Schools:
Grant No. NSh-3230.2010.3).
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IR (film): 3053, 2985, 2933, 2890, 2854, 1478, 1453, 1436, 1373,
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Synthesis 2012, 44, 431–438
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