Three-component reaction between secondary phosphine sulfides, elemental selenium and vinyl ethers: The first examples of Markovnikov addition of thioselenophosphinic acids to double bond

Article abstract of DOI:10.1016/j.tet.2013.05.038

Thioselenophosphinic acids, R₂P(Se)SH, generated in situ from secondary phosphine sulfides and elemental selenium, easily add to various vinyl ethers (equimolar ratio, 100 C, 1,4-dioxane, up to 40 min) to give earlier unknown S- and Se-[1-(orga

Full text of DOI:10.1016/j.tet.2013.05.038

Accepted Manuscript
Three-component reaction between secondary phosphine sulfides, elemental
selenium and vinyl ethers: the first examples of Markovnikov addition of
thioselenophosphinic acids to double bond
Ludmila A. Oparina, Alexander V. Artem’ev, Oksana V. Vysotskaya, Nikita A.
Kolyvanov, Irina Yu. Bagryanskaya, Evgeniya P. Doronina, Nina K. Gusarova
PII:
S0040-4020(13)00773-4
10.1016/j.tet.2013.05.038
TET 24376
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 21 February 2013
Revised Date: 30 April 2013
Accepted Date: 13 May 2013
Please cite this article as: Oparina LA, Artem’ev AV, Vysotskaya OV, Kolyvanov NA, Bagryanskaya
IY, Doronina EP, Gusarova NK, Three-component reaction between secondary phosphine sulfides,
elemental selenium and vinyl ethers: the first examples of Markovnikov addition of thioselenophosphinic
acids to double bond, Tetrahedron (2013), doi: 10.1016/j.tet.2013.05.038.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Three-component reaction between secondary
phosphine sulfides, elemental selenium and vinyl
Leave this area blank for abstract info.
ethers: the first examples of Markovnikov addition of thioselenophosphinic acids to double bond
1

ACCEPTED MANUSCRIPT
Three-component reaction between secondary phosphine sulfides, elemental
selenium and vinyl ethers: the first examples of Markovnikov addition of
thioselenophosphinic acids to double bond
a
a
a
a
Ludmila A. Oparina, Alexander V. Artem’ev, Oksana V. Vysotskaya, Nikita A. Kolyvanov, Irina Yu.
b
a
a*
Bagryanskaya, Evgeniya P. Doronina and Nina K. Gusarova
a
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1
Favorsky Str., 664033 Irkutsk, Russian Federation
b
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian
Academy of Sciences, 9 Lavrentiev Ave., 630090 Novosibirsk, Russian Federation
Abstract. Thioselenophosphinic acids, R
sulfides and elemental selenium, easily add to various vinyl ethers (equimolar ratio, 100 C, 1,4-
2
P(Se)SH, generated in situ from secondary phosphine
o
dioxane,
up
to
40
min)
to
give
earlier
unknown
S-
and
Se-[1-
(
organyloxy)ethyl]thioselenophosphinates, i.e. R P(Se)SCH(Me)OR′ and R P(S)SeCH(Me)OR′ (R, R′
2
2
=
alkyl, aralkyl, hetaralkyl and aryl), the S-esters being predominant (73-95% total yield).
Keywords: vinyl ethers, secondary phosphine sulfides, selenium, thioselenophosphinic acids
1
. Introduction
Currently, vinyl ethers attract increasing attention of researchers as monomers for the preparation
1
2
of functional polymer materials, precursors for design of pharmaceuticals and convenient building
3
4
blocks for the synthesis of, in particular, hemilabile mono- and diphosphine ligands. The vinyl ethers
5
6
as substrates can participate in many reactions such as cycloadditions, metathesis, Claisen
7
8
9
rearrangement, metallation, addition of diverse X-H-acids (X = O, N, S, etc.) and Heck-type
10
arylation. One of the most powerful and atom-economic methods for functionalization of vinyl ethers
1
1
is electrophilic addition of OH-compounds, for example, various acids to the vinyloxy group. This
reaction usually proceeds under the mild conditions and creates real prerequisites for direct and
controlled modification of vinyl ethers by diverse functional moieties. For instance, the electrophilic
1
2
13
addition of carboxylic acids and their thio-analogs to vinyl ethers is shown to provide a direct,
efficient and facile short-cut to acetals including functional and optically active ones.
However, little is known about the addition of organophosphorus acids and its thio- or
2
selenoanalogs to vinyl ethers. Phosphinic acids, R P(O)OH, do not add to the vinyloxy group,
nevertheless, dithiophosphinic and -phosphoric acids easily react with vinyl ethers (room temperature,
without catalyst and solvent) to give regioselectively the corresponding Markovnikov-type adducts in
1
4
quantitative yields (Scheme 1).
Scheme 1. Electrophilic addition of dithiophosphinic and -phosphoric acids to vinyl ethers.
*
Corresponding author. Tel.: +7 3952422423; fax: +7 395241 93 46; e-mail: gusarova@irioch.irk.ru
2

ACCEPTED MANUSCRIPT
15
Recently, it has been shown that diselenophosphinic acids, generated in situ from secondary
o
phosphines (or their selenides) and elemental selenium (90 C, 1,4-dioxane), add to a diverse array of
vinyl ethers to afford previously unknown diselenophosphinic esters in high yields (Scheme 2).
Scheme 2. One-pot synthesis of Se-[1-(organyloxy)ethyl]diselenophosphinates.
At the same time, precedent for the addition of thioselenophosphinic acids, R
2
P(Se)SH or
R P(S)SeH, to vinyl ethers is absent in the literature. It is pertinent to note that until recently only two
2
examples of such acids, namely Ph
acidification of the corresponding salts with HCl). Murai et al. have demonstrated that Ph
acids add selectively to methyl vinyl ketone or ethyl propiolate in an anti-Markovnikov fashion to
2
P(Se)SH and t-Bu(Ph)P(Se)SH, have been prepared (both by
1
6
2
P(Se)SH
1
6
afford Se-esters with a small amount of the S-isomers (up to 7%), Scheme 3.
Scheme 3. Nucleophilic addition of thioselenophosphinic acids to methyl vinyl ketone and ethyl
propiolate.
In the present work we have implemented for first time the electrophilic addition of
thioselenophosphinic acids to alkenes (on example of vinyl ethers). For this purpose, we have studied
the reaction of secondary phosphine sulfides with selenium in the presence of vinyl ethers aiming at (i)
the development of an atom-economic route to a thioselenophosphinic esters and (ii) the investigation
of the competition between thioselenophosphinic S- and Se-esters formation.
2
. Results and Discussion
We have found that the thioselenophosphinic esters may be successfully synthesized via the
three-component reaction between secondary phosphine sulfides, elemental selenium and vinyl ethers.
Experiments have shown that the thioselenophosphinic acids, R P(Se)SH, generated in situ from
2
secondary phosphine sulfides 1a-f and elemental selenium, easily add to various vinyl ethers 2a-j in a
o
Markovnikov fashion (1,4-dioxane, 100 C, up to 40 min) to give a mixture of thioselenophosphinic S-
3

ACCEPTED MANUSCRIPT
31
and Se-esters 3a-n in high yield ( P NMR data). The isolated yields of the products 3a-n and ratio of
S- and Se-esters in the reaction mixtures are presented in Table 1.
Table 1
One-pot synthesis of thioselenophosphinic S- and Se-esters 3a-n
Phosphine
sulfide
1
Molar ratio a Overall
Entry
1
R
Vinyl ether
Product
b
of S-/Se-ester yield (%)
1a
Cy
Cy
3a
58:42
93
93
(
2a)
5
0:50
0:30
2
1a
3b
(
2b)
7
90
95
3
4
1b
1b
(CH ) Ph
3c
2
2
(
2a)
(CH
2
)
2
Ph
3d
63:37
75:25
(
2c)
5
6
1c
1c
(CH
2
2
)
2
2
(4-MeOC
(4-MeOC
6
6
H
H
4
4
)
)
3e
3f
73
90
(
2d)
7
2:28
2:38
(CH
)
(
2e)
6
7
8
1c
1c
(CH
2
2
)
2
2
(4-MeOC
(4-MeOC
6
6
H
H
4
4
)
)
3g
3h
93
91
(
2f)
F
(CH
)
61:39
53:47
O
(2g)
2h)
9
1c
(CH
2
)
2
(4-MeOC
6
H
4
)
3i
3j
80
81
(
10
1d
(CH
(CH
2
)
2
2
(4-ClC
6
6
H
H
4
4
)
69:31
(
2i)
1
1
2
1d
1e
2
)
(4-ClC
)
3k
3l
80:20
73:27
82
93
(
2j)
1
(CH ) (2-Furyl)
2
2
(
2a)
13
1f
Ph
3m
64:36
90
(
2f)
4

ACCEPTED MANUSCRIPT
14
1f
Ph
3n
69:31
83
(
2h)
a
1
31
Determined by H and P NMR.
Isolated yield.
b
The results (Table 1) reveal that this reaction is applicable for a diverse range of aryl- and alkyl
vinyl ethers as well as a secondary phosphine sulfides bearing alkyl, aralkyl, hetaralkyl and aryl groups.
Indeed, a variety of substituents (Me, Ph, naphth, F, Cl and OMe), including acid-sensitive groups (2-
furyl), tolerates to reaction conditions.
Apparently, the mechanism of thioselenophosphinates 3a-n formation in the present three-
component reaction involves oxidation of the corresponding trivalent tautomeric form A of secondary
phosphine sulfides 1 by elemental selenium. The resulting thioselenophosphinic S-acid B (or its
tautomeric form B') adds to electron-rich double bond of vinyl ether to give the S- and Se-esters 3
(Scheme 4). Certainly, this type of addition is electrophilic in nature and proceeds regioselectively in
2
agreement with the Markovnikov’s rule that allows thioselenophosphinates 3 with the XCH(OR )Me
(X = S or Se) structural unit to be prepared. Therefore, the equimolar mixture of secondary phosphine
sulfide with elemental selenium in this three-component reaction acts as synthetic equivalent of the
thioselenophosphinic acids.
Scheme 4. Proposed mechanism for the three-component reaction between secondary phosphine
sulfides, vinyl ethers and selenium.
1
8
The mechanism proposed is in compliance with our recent finding that secondary phosphine
o
sulfides 1a-e react with elemental selenium in equimolar ratio (100 C, 30-40 min) to give selectively
thioselenophosphinic S-acids 4a-e in a yield of up to 90% (Scheme 5). Notably, in solution these acids
17
exist solely as SH-tautomers (NMR data).
Scheme 5. Synthesis of thioselenophosphinic S-acids 4a-e.
5

ACCEPTED MANUSCRIPT
The thioselenophosphinic S-acids 4a-c, prepared in this way (Scheme 5), readily react with vinyl
o
ethers 2a, e under exceptionally mild conditions (20-25 C, 1,4-dioxane, 10 min) to give S- and Se-
adducts 3a, c, f (with a predominance of S-esters) in high yields (Table 2). Analysis of the crude
1
31
reaction mixtures by H and P NMR spectroscopy indicates nearly the same ratio of the S- and Se-
esters 3a, c, f as in the three-component reaction (Table 1).
Table 2
Electrophilic addition of thioselenophosphinic S-acids 4a-c to vinyl ethers 2a, e
Molar ratio a Overall
Entry
1
Acid
Ether
Product
b
of S-/Se-esters yield (%)
3
a
c
57:43
70:30
84
81
(
2a)
2a)
(
4a)
3
2
(
(
4b)
3
f
79:21
79
3
(2e)
(4c)
a
31
Determined by P NMR.
Isolated yield.
b
It is noteworthy that the employment of a one-pot protocol (Table 1) significantly facilitates the
preparation of thioselenophosphinic esters because it allows avoiding handling thioselenophosphinic
16,17
acids 4a-e, which are air-sensitive and unstable compounds.
With regard to the ratio of S- and Se-isomer, in almost all the cases (Tables 1 and 2) the major
isomer is S-ester. The only exception is the addition of di(cyclohexyl)thioselenophosphinic acid (4a),
2
generated from Cy P(S)H (1a) and selenium, to (1-naphthyl)vinyl ether (2b), which results in the
formation of equimolar amounts of both isomeric esters 3b (Table 1, entry 2).
For a rational explanation of the observed outcome we have analyzed the local philicity
1
8
α
+
indexes (ωk ) of model intermediates, i.e. [Cy
proton transfer from acid Cy PSeSH to phenyl vinyl ether (according to the electrophilic character of
the addition). The geometries of these ions have been optimized by the B3LYP/6-311++G(d,p) method
2
PSeS]¯ anion and Ме(PhO)HС cation, formed via the
2
1
9
20
for 1,4-dioxane solution (C-PCM). The calculated [HF/6-31G(d)] NBO values of the local
−
−
nucleophilicity indexes, ωk (Equation S1 in Supporting Materials), for sulfur ( ωS = 0.180) and
6

ACCEPTED MANUSCRIPT
−
Se
+
selenium (
ω
2
= 0.053) atoms of [Cy PSeS]¯ as well as local electrophilicity index, ωk , for cationic
+
+
+
−
+
−
Se
carbon ( ωC = 1.773) in Ме(PhO)HС unambiguously ( ωC
-
ωS
<
ωC
-
ω
) indicate that this
carbocation predominantly will be attacked by the S atom of S,Se-ambident [Cy PSeS]¯ anion.
2
Moreover, the Gibbs free energy calculations [MP2/6-311++G(d,p)//B3LYP/6-311++G(d,p)] of two
2 2
model isomers, i.e. Cy P(Se)SCH(Me)OPh and Cy P(S)SeCH(Me)OPh, have confirmed that the S-
ester is more stable than the Se-isomer by 1.28 kcal/mol. Interestingly, the alkylation of the ambident
¯
[
R
2
PSeS] thioselenophosphinate anions (in form of alkali metal salts) by diverse organic halides takes
1
6,21
place exclusively at the Se atom to afford corresponding Se-esters in high yields.
1
The structures of isomeric S- and Se-esters 3a-n have been unambiguously established by the H,
1
3
31
77
C, P and Se NMR techniques as well as by X-ray diffraction analysis. Some characteristic NMR
3
1
properties of the selected esters (3a, f, n) are summarized in Table 3. In the P NMR spectra of S-
esters, the resonance of phosphorus atoms is observed as a sharp singlet at 52.68-85.93 ppm flanked by
7
7
1
single set of Se satellites with JPSe = 756-789 Hz indicating the presence of the P=Se double bond.
7
7
1
The Se NMR spectra of the S-esters comprise of a downfield doublet at (−367)-(−196) ppm ( JPSe
=
31
7
56-789 Hz). The P NMR spectra of Se-esters show a sharp singlet at 50.89-85.90 ppm flanked by
77
1
77
one set of Se satellites ( JPSe = 347-362 Hz), while the Se NMR spectra contain a doublet at 230-
31
77
3
97 ppm with characteristic one-bond P- Se coupling of 347-362 Hz.
Table 3
The selected NMR data of S- and Se-esters 3a, f, n
δ, ppm
1JPSe
δ(MeCH), ppm
δ(OCHCh), ppm
,
Compound
3
1
77
Hz
1
a
13
b
1
c
13
d
P NMR
Se NMR
H NMR
C NMR
H NMR
C NMR
8
4.62
5.91
−367
762
352
1.86
25.2
5.86
86.9
3a
8
230
2.06
1.75
26.8
25.3
5.94
5.34
85.2
89.9
6
0.38
1.14
−266
762
3
f
6
319
362
789
1.93
1.98
26.9
25.1
5.54
5.79
91.5
89.2
52.68
3
n
−206
7

ACCEPTED MANUSCRIPT
51.09
397
369
2.13
25.8
6.01
88.6
a
b
c
3
A doublet with JHH = 6.0-6.2 Hz.
3
A doublet with JCP = 2.4-4.8 Hz.
A multiplet.
A singlet.
d
The molecular structures of S- and Se-esters 3b, which form co-crystals (1:1), have been
2
2
determined by single-crystal X-ray diffraction analysis (Figure 1). It appears that the sulfur and
selenium atoms of the co-crystallized esters 3b are disordered over the two positions with
Se1/S2:Se2/S1 occupancy ratio of 0.580:0.420(2).
Figure 1. Perspective view of molecular structure of the esters S-3b and Se-3b in its co-crystal (30%
thermal ellipsoid).
o
Esters 3a-n are stable up to ~ 110 C (at this temperature, the molar ratio of the isomeric S- and
o
Se-esters does not change). We have found S- and Se-3c decompose upon heating up to 150 C (in
vacuo, 1 Torr) to give phenol and 1,1-bis(phenoxy)ethane as well as a complex mixture of
2 2
organophosphorus compounds. Among the latter, selenoanhydrides, (R P=S) Se and
3
1
(R
2
P=S)Se(Se=PR
2
), were detectable ( P NMR).
2
Notably, the esters 3e-g, j, k, m bearing aliphatic R substituents are quite easily hydrolyzed. So,
the storage of thioselenophosphinates S-3e and Se-3e solution (their ratio is ca. 75:25) in wet ether
o
(
20-25 C, 1 week) yields co-crystals (1:1) of selenides 5a, b (Scheme 6). Apparently, the formation of
these selenides proceeds via hydrolysis of the esters 3e followed by the intermolecular condensation of
the generated SH- and/or SeH-acids A.
C H13-i
6
Se
P
O
R
S
Me
S-3e
R
S
S
Se S
H O
R
R
Se
R
R
SeH
S
2
+
P
P
P
P
+
P
P
R
o
R
R
R
R
R
R
Et O, 20-25 C
SH
[- H Se]
2
Se
Se
5b
C H13-i
2
6
R
S
P
O
[-H S]
A
2
5
a
R
Se Me
R
R = (CH2)2(4-MeOC6H4)
Se-3e
Scheme 6. Hydrolysis of thioselenophosphinates S-3e and Se-3e.
8

ACCEPTED MANUSCRIPT
The molecular structures of the selenides 5a, b are supported by X-ray diffraction analysis of
23
their co-crystal (Figure 2). The sulfur and selenium atoms in the co-crystal are disordered over two
positions with Se1/S2:Se2/S1 occupancy ratio of 0.776:0.224(5). Also, the disordering one of the
bridging CH
.65:0.35(1).
2
groups over the two positions is observed, the С30:С30А occupancy ratio being
0
Figure 2. Perspective view of molecular structures of the selenides 5a, b in its co-crystal (30% thermal
ellipsoid).
Our numerous attempts to isolate the individual S- and Se-esters 3a-n from their mixtures by
chromatographic methods (such as column and TLC) were unsuccessful. According to experimental
f
data, both S- and Se-esters 3a, d, g, n have virtually identical R values without reference to polarity of
the eluent used. Apparently, the similarity of physical proprieties of individual S- and Se-esters makes
it impossible to separate these isomers.
3
. Conclusion
In summary, we have disclosed for the first time that the electrophilic addition of
thioselenophosphinic acids, readily generated from secondary phosphine sulfides and elemental
selenium, to a diverse range of vinyl ethers. The reaction proceeds with the formation of Markovnikov
adducts, i.e. S- and Se-esters of thioselenophosphinic acids, in high yields. In practically all examples,
the major isomers were S-esters, the ratio of which depends on the structures of the initial vinyl ethers
and thioselenophosphinic acids.
4
4
. Experimental section
.1. General
All reactions were performed under an atmosphere of dry argon. 1,4-Dioxane was dried and freshly
distilled over sodium/benzophenone prior to use. Dicyclohexilphosphine sulfide (1a) and
diphenylphosphine sulfide (1f) were prepared by oxidation of commercially available phosphines
(Aldrich) with powdered sulfur (S
8
) in an ethanol solution. Phosphine sulfides 1b-e were prepared
according to known procedure from red phosphorus, elemental sulfur and styrene, 4-methoxystyrene,
24
25
4
-chlorostyrene or 2-vinylfuran. Vinyl ethers 2a-j were prepared according to a published method.
1
13
31
77
The H, C, P and Se NMR spectra were recorded in CDCl
3
solutions on a Bruker DPX 400 and
9

ACCEPTED MANUSCRIPT
Bruker AV-400 spectrometers (400.13, 100.62, 161.98 and 76.31 MHz, respectively) Chemical shifts
1
13
31
were reported in δ (ppm) relative to CDCl
3
( H, C) as internal standard or H
3 4 2
PO ( P) and Me Se
7
7
(
Se NMR) as external standard. Infrared (IR-FT) spectra were taken on a Bruker Vertex 70
spectrometer. The microanalyses were performed on a Flash EA 1112 Series elemental analyzer.
The crystallographic data were obtained on a Bruker Kappa Apex II CCD diffractometer using
α
φ,ω-scans of narrow (0.5°) frames with MoK radiation (λ = 0.71073 Å) and a graphite
monochromator. The structure was solved by direct methods and refined by full-matrix least-squares
2
26
method against all F in anisotropic approximation using the SHELX-97 programs set. The hydrogen
atoms positions were calculated with the riding model. Absorption correction was applied empirically
2
7
using SADABS programs.
CCDC 894978 (co-crystal of S-3b and Se-3b) and 901600 (co-crystal of 5a, b) contain the
supplementary crystallographic data for this paper. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/cgi-bin/catreq.cgi, or from the Cambridge Crystallographic Data Centre,
1
2
Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223 336 033; or e-mail:
deposit@ccdc.cam.ac.uk.
4
4
2
.2. Synthesis
.2.1. (1-Phenoxyethyl)dicyclohexylphosphinoselenothioate (3a). Dicyclohexylphosphine sulfide (1a;
30 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0 mmol) were added consecutively to a
solution of phenyl vinyl ether (2a; 120 mg, 1.0 mmol) in 1,4-dioxane (5 mL) at ambient temperature
o
(
in argon atmosphere). The suspension was stirred at 100 C until dissolution of selenium residue to
give a light yellow transparent solution. The solvent was removed under reduced pressure (1 Torr, 40-
o
4
3
5 C), and the residue was purified by flash-chromatography (3 cm of neutral Al O ; CHCl -hexane,
2
3
3
:1) to give compound 3a as yellowish powder (isomeric mixture of the S- and Se-esters, the molar
ratio being 58:42). Yield: 399 mg (93%); IR (KBr) 3055, 2996, 2929, 2873, 2852, 1592, 1497, 1445,
1
8
372, 1343, 1326, 1293, 1268, 1249, 1223, 1178, 1112, 1091, 1073, 1046, 1029, 1014, 1002, 930, 895,
–1
85, 850, 819, 794, 753, 691, 644, 630, 602, 566, 541, 514, 466, 457, 438, 406 cm . Anal. Calcd for
C
20
H31OPSSe (429.46): C, 55.93; H, 7.28; P, 7.21; S, 4.47; Se, 18.39. Found: C, 56.01; H, 7.45; P,
1
7
.28; S, 4.87; Se, 17.98; (S-3a): H NMR (400.13 MHz, CDCl
3
) δ 7.31-7.27 (m, 2 H, PhO), 7.10-7.00
3
(
m, 3 H, PhO), 5.86 (m, 1 H, CHS), 2.03-1.96 (m, 2 H, Cy), 1.96-1.86 (m, 2 H, Cy), 1.86 (d, JHH=6.0
Hz, 3 H, MeCH), 1.82-1.69 (m, 4 H, Cy), 1.67-1.58 (m, 2 H, Cy), 1.58-1.42 (m, 2 H, Cy), 1.31-1.14 (m,
13
1
3,5
2,6
1
3
0 H, Cy); C NMR (100.62 MHz, CDCl ) δ 156.0 (C in PhO), 129.2 (C in PhO), 122.5 (C in
4
1
1
PhO), 118.3 (C in PhO), 86.9 (CHS), 42.1 (d, JPC=39.2 Hz, CHP), 40.0 (d, JPC=41.9 Hz, CHP), 26.3,
3
31
2
6.2, 26.1, 25.7, 25.6 (Cy), 25.2 (d, J =4.8 Hz, MeCH); P NMR (161.98 MHz, CDCl ) δ 84.62 (s,
PC 3
1
77
1
1
J
P=Se=762 Hz); Se NMR (76.31 MHz, CDCl
3
) δ −367 (d, JP=Se=762 Hz); (Se-3a): H NMR (400.13
MHz, CDCl
3
) δ 7.31-7.27 (m, 2 H, PhO), 7.10-7.00 (m, 3 H, PhO), 5.94 (m, 1 H, CHSe), 2.06 (d,
3
J
HH=6.0 Hz, 3 H, MeCH), 2.03-1.96 (m, 2 H, Cy), 1.96-1.86 (m, 2 H, Cy), 1.82-1.68 (m, 4 H, Cy),
1
0

ACCEPTED MANUSCRIPT
1
3
1
.67-1.58 (m, 2 H, Cy), 1.58-1.42 (m, 2 H, Cy), 1.31-1.14 (m, 10 H, Cy); C NMR (100.62 MHz,
1
3,5
2,6
4
3
CDCl ) δ 156.0 (C in PhO), 129.1 (C in PhO), 122.4 (C in PhO), 117.9 (C in PhO), 85.2 (CHSe),
1
3
31
4
2.4 (d, JPC=41.9 Hz, CHP), 26.8 (d, JPC=2.6 Hz, MeCH), 26.3, 26.2, 26.1, 25.7, 25.6 (Cy); P NMR
1
77
1
(
161.98 MHz, CDCl ) δ 85.91 (s, J =352 Hz); Se NMR (76.31 MHz, CDCl ) δ 230 (d, JP-Se=352
3 P-Se 3
Hz).
4
.2.2. [1-(1-Naphthhyloxy)ethyl]dicyclohexylphosphinoselenothioate (3b). Dicyclohexylphosphine
sulfide (1a; 230 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0 mmol) were added
consecutively to a solution of 1-naphthyl vinyl ether (2b; 170 mg, 1.0 mmol) in 1,4-dioxane (5 mL) at
o
ambient temperature (in argon atmosphere). The suspension was stirred at 100 C until dissolution of
selenium residue to give a light yellow transparent solution. The solvent was removed under reduced
o
pressure (1 Torr, 40-45 C), and the residue was purified by flash-chromatography (3 cm of neutral
Al
2 3 3
O ; CHCl -hexane, 3:1) to give compound 3b as yellowish solid (isomeric mixture of the S- and Se-
esters, the molar ratio being 50:50). Yield: 446 mg (93%); IR (KBr) 3010, 2954, 2930, 2850, 1596,
1
1
4
576, 1507, 1461, 1448, 1394, 1376, 1344, 1301, 1292, 1267, 1240, 1178, 1157, 1099, 1047, 1017.
002, 962, 926, 894, 884, 848, 818, 793, 775, 752, 734, 691, 642, 629, 571, 562, 541, 513, 505, 475,
–
1
65, 437, 419, 400 cm . Anal. Calcd for C24
H33OPSSe (479.52): C, 60.11; H, 6.94; P, 6.69; S, 6.69;
1
Se, 16.47. Found: C, 60.42; H, 6.60; P, 6.72; S, 6.78; Se, 16.21; (S-3b): H NMR (400.13 MHz,
3
CDCl
3
) δ 8.18 (m, 1 H, naphth), 7.77 (m, 1 H, naphth), 7.49-7.44 (m, 3 H, naphth), 7.38 (t, JHH=7.9
3
3
Hz, 1 H, naphth), 7.29 (t, JHH=7.9 Hz, 1 H, naphth), 6.08 (m, 1 H, CHS), 1.96 (d, JHH=6.0 Hz, 3 H,
MeCH), 1.91-1.82 (m, 4 H, Cy), 1.76-1.64 (m, 4 H, Cy), 1.63-1.58 (m, 2 H, Cy), 1.56-1.48 (m, 2 H,
1
3
3
Cy), 1.28-1.17 (m, 6 H, Cy), 1.12-0.98 (m, 4 H, Cy); C NMR (100.62 MHz, CDCl ) δ 151.5, 134.5,
1
1
4
28.8, 126.1, 125.6, 125.3 (naphth), 122.2-121.8, 111.0 (m), 87.0 (CHS), 41.9 (d, JPC=41.9 Hz, CHP),
1
3
31
1.0 (d, J =41.6 Hz, CHP), 26.3, 26.2, 26.1 (Cy), 25.5 (d, J =4.8 Hz, MeCH); P NMR (161.98
PC
PC
1
77
1
3 3
MHz, CDCl ) δ 85.93 (s, JP=Se=762 Hz); Se NMR (76.31 MHz, CDCl ) δ −366 (d, JP=Se=762 Hz);
1
(
Se-3b): H NMR (400.13 MHz, CDCl
3
) δ 8.18 (m, 1 H, naphth), 7.77 (m, 1 H, naphth), 7.49-7.44 (m,
3
3
3
H, naphth), 7.38 (t, JHH=7.9 Hz, 1 H, naphth), 7.29 (t, JHH=7.9 Hz, 1 H, naphth), 6.13 (m, 1 H,
3
CHSe), 2.17 (d, JHH=6.0 Hz, 3 H, MeCH), 1.91-1.82 (m, 4 H, Cy), 1.76-1.64 (m, 4 H, Cy), 1.63-1.58
1
3
(
m, 2 H, Cy), 1.56-1.48 (m, 2 H, Cy), 1.28-1.17 (m, 6 H, Cy), 1.12-0.98 (m, 4 H, Cy); C NMR
100.62 MHz, CDCl ) δ 151.5, 134.5, 128.8, 126.1, 125.6, 125.3 (naphth), 122.2-121.8 (m), 110.7,
4.9 (CHSe), 42.8-40.7 (m, CHP), 26.3, 26.2, 26.1 (Cy), 25.2 (d, JPC=2.8 Hz, MeCH); P NMR
(
3
3
31
8
1
77
1
(
3 3
161.98 MHz, CDCl ) δ 86.81 (s, JP-Se=352 Hz); Se NMR (76.31 MHz, CDCl ) δ 241 (d, JP-Se=352
Hz).
4
.2.3. 1-Phenoxyethyl diphenethylphosphinoselenothioate (3c). Diphenethylphosphine sulfide (1b;
2
74 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0 mmol) were added consecutively to a
1
1

ACCEPTED MANUSCRIPT
solution of phenyl vinyl ether (2a; 120 mg, 1.0 mmol) in 1,4-dioxane (5 mL) at ambient temperature
o
(
in argon atmosphere). The suspension was stirred at 100 C until dissolution of selenium residue to
give a light yellow transparent solution. The solvent was removed under reduced pressure (1 Torr, 40-
o
4
3
5 C), and the residue was purified by flash-chromatography (3 cm of neutral Al O ; CHCl -hexane,
2
3
3
:1) to give compound 3c as yellowish oil (isomeric mixture of the S- and Se-esters, the molar ratio
being 70:30). Yield: 426 mg (90%); IR (KBr) 3104, 3085, 3062, 3027, 3001, 2973, 2926, 2859, 1597,
1
9
591, 1496, 1442, 1396, 1376, 1333, 1291, 1220, 1173, 1155, 1128, 1112, 1089, 1071, 1028, 1013,
–1
45, 928, 907, 797, 753, 696, 636, 614, 576, 550, 526, 494, 434, 415 cm . Anal. Calcd for
C
24
H27OPSSe (473.47): C, 60.88; H, 5.75; P, 6.54; S, 6.77; Se, 16.68. Found: C, 60.71; H, 5.60; P,
1
6
6
2
.72; S, 6.78; Se, 17.01; (S-3c): H NMR (400.13 MHz, CDCl
3
) δ 7.20-7.08 (m, 12 H, Ph, PhO), 6.99-
Ph),
2
P), 1.86 (d, JHH=6.2 Hz, 3 H, MeCH); C NMR (100.62 MHz,
3
2
.94 (m, 3 H, PhO), 5.96 (dq, 1 H, JHH=6.1 Hz, JPH=11.4 Hz, CHS), 3.04-2.83 (m, 4 H, CH
2
3
13
.41-2.29 and 2.27-2.14 (m, 4 H, CH
1
3
3,5
CDCl
3
) δ 155.6 (C in PhO), 139.8 (d, JPC=16.8 Hz, i-C, Ph), 129.3 (C in PhO), 128.5, 128.4, 128.1,
2,4,6
1
1
28.0, 126.3, 126.2 (o-, m-, p-C, Ph), 122.8, 118.2 (C
in PhO), 86.6 (CHS), 39.5 (d, JPC=40.0 Hz,
1
3
31
CH P), 38.6 (d, J =43.1 Hz, CH P), 29.3, 29.2 (CH Ph), 24.5 (d, J =4.8 Hz, MeCH); P NMR
2
PC
2
2
PC
1
77
(161.98 MHz, CDCl
3
) δ 63.45 (s, JP=Se=766 Hz); Se NMR (76.31 MHz, CDCl
3
) δ −268 (d,
1
1
J
P=Se=766 Hz); (Se-3c): H NMR (400.13 MHz, CDCl
3
) δ 7.20-7.08 (m, 12 H, Ph, PhO), 6.99-6.94 (m,
Ph), 2.41-2.29 and
.27-2.14 (m, 4 H, CH P), 2.07 (d, J =6.1 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl ) δ 155.8
3
2
3
2
H, PhO), 6.07 (dq, 1 H, JHH=6.1 Hz, JPH=8.8 Hz, CHSe), 3.04-2.83 (m, 4 H, CH
2
3
13
2
HH
3
1
3
3,5
(
C in PhO), 139.9 (d, JPC=16.8 Hz, i-C, Ph), 129.2 (C in PhO), 128.5, 128.4, 128.1, 128.0, 126.3,
2
,4,6
1
1
26.2 (o-, m-, p-C, Ph), 122.8, 118.0 (C
2
in PhO), 86.1 (CHSe), 40.2 (d, JPC=41.2 Hz, CH P), 39.6
1
3
31
(
d, J = 44.3 Hz, CH P), 29.2, 28.9 (CH Ph), 26.4 (d, J =2.8 Hz, MeCH); P NMR (161.98 MHz,
PC
2
2
PC
1
77
1
3 3
CDCl ) δ 64.45 (s, JP-Se=350 Hz); Se NMR (76.31 MHz, CDCl ) δ 317 (d, JP-Se=350 Hz).
4
.2.4. [1-(2-Naphthhyloxy)ethyl] diphenethylphosphinoselenothioate (3d). Diphenethylphosphine
sulfide (1b; 274 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0 mmol) were added
consecutively to a solution of 2-naphthyl vinyl ether (2c; 170 mg, 1.0 mmol) in 1,4-dioxane (5 mL) at
o
ambient temperature (in argon atmosphere). The suspension was stirred at 100 C until dissolution of
selenium residue to give a light yellow transparent solution. The solvent was removed under reduced
o
pressure (1 Torr, 40-45 C), and the residue was purified by flash-chromatography (3 cm of neutral
Al
2 3 3
O ; CHCl -hexane, 3:1) to give compound 3d as yellowish oil (isomeric mixture of the S- and Se-
esters, the molar ratio being 63:37). Yield: 497 mg (95%); IR (KBr): 3084, 3060, 3026, 3001, 2955,
2
1
6
5
925, 2853, 1629, 1600, 1510, 1496, 1466, 1454, 1442, 1389, 1377, 1357, 1333, 1288, 1254, 1211,
180, 1121, 1180, 1121, 1109, 1082, 1029, 1007, 966, 946, 932, 887, 874, 850, 812, 748, 698, 638,
–1
23, 613, 576, 551, 527, 494, 476, 434, 414 cm . Anal. Calcd for C28
H29OPSSe (523.53): C, 64.24; H,
1
.58; P, 5.92; S, 6.12; Se, 15.08. Found: C, 64.41; H, 5.49; P, 6.05; S, 5.93; Se, 15.38; (S-3d): H NMR
1
2

ACCEPTED MANUSCRIPT
3
(
400.13 MHz, CDCl ) δ 7.88-7.85 (m, 1 H, naphth), 7.81 (d, J =8.7 Hz, 2 H, naphth), 7.70 (s, 1 H,
3
HH
naphth), 7.51-7.40 (m, 2 H, Ph), 7.34-7.22 (m, 6 H, Ph, naphth), 7.17-7.15 (m, 3 H, Ph), 6.81 (m, 2 H,
3
2
naphth), 6.20 (dq, 1 H, JHH=6.1 Hz, JPH=11.9 Hz, CHS), 3.11-2.98 and 2.83-2.70 (m, 4 H, CH
2
Ph),
3
13
2
.50-2.44 and 2.31-2.26 (m, 4 H, CH P), 2.03 (d, J =6.1 Hz, 3 H, MeCH); C NMR (100.62 MHz,
2
HH
2
3
3
CDCl ) δ 153.6 (C in naphth), 140.1 (d, JPC=16.9 Hz, i-C, Ph), 134.2, 130.0, 129.6 (naphth), 128.8,
1
28.5 (o-, m-C, Ph), 127.7, 127.3, 126.6 (naphth), 126.3 (p-C, Ph), 124.6, 119.8, 112.8 (naphth), 86.6
1
1
(
CHS), 39.9 (d, J =43.6 Hz, CH P), 38.1 (d, J =43.1 Hz, CH P), 29.8, 29.5 (CH Ph), 25.0 (d,
PC
2
PC
2
2
3
31
1
77
J
PC=4.8 Hz, MeCH); P NMR (161.98 MHz, CDCl
3
) δ 62.45 (s, JP=Se=766 Hz); Se NMR (76.31
1
1
MHz, CDCl
3
3
) δ −266 (d, JP=Se=758 Hz); (Se-3d): H NMR (400.13 MHz, CDCl ) δ 7.88-7.85 (m, 1 H,
3
Naphth), 7.81 (d, JHH=8.7 Hz, 2 H, naphth), 7.74 (s, 1 H, naphth), 7.51-7.40 (m, 2 H, Ph), 7.34-7.22
(m, 6 H, Ph, naphth), 7.17-7.15 (m, 3 H, Ph), 6.81 (m, 2 H, naphth), 6.30 (m, 1 H, CHSe), 3.11-2.98
3
and 2.83-2.70 (m, 4 H, CH
2
Ph), 2.50-2.44 and 2.31-2.26 (m, 4 H, CH
2
P), 2.25 (d, JHH=6.1 Hz, 3 H,
13
2
3
MeCH); C NMR (100.62 MHz, CDCl ) δ 153.7 (C in naphth), 139.8 (d, J =16.8 Hz, i-C, Ph),
3
PC
1
1
34.2, 130.0, 129.5 (naphth), 128.5, 128.4 (o-, m-C, Ph), 127.7, 127.5, 126.6 (naphth), 126.3 (p-C, Ph),
1
1
2
24.6, 119.78, 112.6 (naphth), 85.8 (CHSe), 40.5 (d, JPC=43.5 Hz, CH P), 39.9 (d, JPC=43.5 Hz,
3
31
CH P), 29.3, 29.2 (CH Ph), 26.8 (d, J =2.6 Hz, MeCH); P NMR (161.98 MHz, CDCl ) δ 63.52 (s,
2
2
PC
3
1
77
1
J
3
P-Se=356 Hz); Se NMR (76.31 MHz, CDCl ) δ 319 (d, JP-Se=356 Hz).
4
.2.5.
[1-(2-Ethylbutoxy)ethyl] bis(4-methoxyphenethyl)phosphinoselenothioate (3e). Bis(4-
methoxyphenethyl)phosphine sulfide (1c; 334 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0
mmol) were added consecutively to a solution of 2-ethylbutyl vinyl ether (2d; 128 mg, 1.0 mmol) in
1
,4-dioxane (5 mL) at ambient temperature (in argon atmosphere). The suspension was stirred at 100
o
C until dissolution of selenium residue to give a light yellow transparent solution. The solvent was
o
removed under reduced pressure (1 Torr, 40-45 C), and the residue was purified by flash-
chromatography (3 cm of neutral Al
2
O
3
3
; CHCl -hexane, 3:1) to give compound 3e as yellowish oil
(isomeric mixture of the S- and Se-esters, the molar ratio being 75:25). Yield: 395 mg (73%); IR (KBr)
3
162, 3126, 3100, 3061, 3030, 2995, 2959, 2931, 2874, 2834, 1612, 1584, 1513,1464, 1441, 1397,
–
1
374, 1301, 1265, 1247, 1178, 1119, 1103, 1036, 948, 874, 820, 796, 735, 636, 621, 611, 550, 518 cm
1
.
Anal. Calcd for C24
H35OPSSe (541.59): C, 57.66; H, 7.26; P, 5.72; S, 5.92; Se, 14.58. Found: C,
1
5
6
3
7.78; H, 7.32; P, 5.84; S, 5.74; Se, 14.43; (S-3e): H NMR (400.13 MHz, CDCl
3
) δ 7.10-7.08 and
3
2
.83-6.80 (m, 8 H, in Ar), 5.30 (dq, JHH=6.0 Hz, JPH=11.0 Hz, 1 H, CHS), 3.77 (c, 6 H, OMe), 3.66-
.62 and 3.46-3.38 (m, each 1 H, OCH
2
), 3.05-2.78 (m, 4 H, CH
2
2
Ar), 2.56-2.31 (m, 4 H, CH P), 1.74
3
3
(
d, JHH=6.0 Hz, 3 H, MeCH), 1.47-1.39 (m, 1 H, CH), 1.38-1.27 (m, 4 H, CH
2
), 0.86 (t, JHH=7.0 Hz,
1
3
1
3
1
6
1
3
H, Me); C NMR (100.62 MHz, CDCl
3
) δ 158.3 (C in Ar), 132.1 (d, JPC=15.6 Hz, C in Ar), 129.3,
2
,3,4,6
1
14.2, (C
in Ar), 90.4 (CHS), 67.9 (OCH
2
), 55.2 (OMe), 40.8 (CH), 40.8 (d, JPC=36.0 Hz, CH
2
P),
1
3
9.4 (d, J = 42.3 Hz, CH P), 28.2 (CH Ar), 25.2 (d, J =4.4 Hz, MeCH), 23.3 (CH ), 11.0 (Me);
PC
2
2
PC
2
1
3

ACCEPTED MANUSCRIPT
3
1
1
1
77
3 3
P NMR (161.98 MHz, CDCl ) δ 60.77 (s, JP=Se=762 Hz); Se NMR (76.31 MHz, CDCl ) δ −262 (d,
1
JP=Se=763 Hz); (Se-3e): H NMR (400.13 MHz, CDCl ) δ 7.10-7.08 and 6.83- 6.80 (m, 8 H, in Ar),
3
3
2
5
.50 (dq, 1 H, JHH=6.0 Hz, JPH=8.6 Hz, CHSe), 3.77 (c, 6 H, OMe), 3.66-3.62 and 3.46-3.38 (m, each
3
1
H, OCH
2
), 3.05-2.78 (m, 4 H, CH
2
Ar), 2.56-2.31 (m, 4 H, CH
2
P), 1.93 (d, JHH=6.0 Hz, 3 H, MeCH),
3
13
1
.47-1.39 (m, 1 H, CH), 1.38-1.27 (m, 4 H, CH
2
), 0.87 (t, JHH=6.9 Hz, 6 H, Me); C NMR (100.62
4
3
1
2,3,4,6
MHz, CDCl
3
) δ 158.21 (C in Ar); 131.7 (d, JPC=14.4 Hz, C in Ar), 129.2, 114.0 (C
in Ar), 91.4
1
1
(
CHSe), 71.1 (OCH
CH), 28.7 (CH
2
), 55.2 (OMe), 43.5 (d, JPC=43.6 Hz, CH
2
2
P), 41.0 (d, JPC=39.5 Hz, CH P), 40.8
3
31
(
2
Ar), 26.6 (d, JPC=2.4 Hz, MeCH), 26.1, 23.3 (CH
2
), 11.0 (Me); P NMR (161.98
1
77
1
3 3
MHz, CDCl ) δ 61.56 (s, JP-Se=362 Hz); Se NMR (76.31 MHz, CDCl ) δ 316 (d, JP-Se=362 Hz).
4
.2.6.
[1-(Heptyloxy)ethyl] bis(4-methoxyphenethyl)phosphinoselenothioate (3f). Bis(4-
methoxyphenethyl)phosphine sulfide (1c; 334 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0
mmol) were added consecutively to a solution of heptyl vinyl ether (2e; 142 mg, 1.0 mmol) in 1,4-
o
dioxane (5 mL) at ambient temperature (in argon atmosphere). The suspension was stirred at 100 C
until dissolution of selenium residue to give a light yellow transparent solution. The solvent was
o
removed under reduced pressure (1 Torr, 40-45 C), and the residue was purified by flash-
chromatography (3 cm of neutral Al
2
O
3
3
; CHCl -hexane, 3:1) to give compound 3f as yellowish oil
(isomeric mixture of the S- and Se-esters, the molar ratio being 72:28). Yield: 501 mg (90%); IR (KBr)
3
1
061, 3030, 2995, 2953, 2930, 2856, 2835, 1612, 1584, 1513, 1465, 1441, 1421, 1397, 1373, 1301,
–1
247, 1178, 1118, 1037, 947, 888, 872, 847, 820, 795, 734, 622, 550, 517, 460 cm . Anal. Calcd for
C
17
H
41
O
3
PSSe (555.61): C, 58.37; H, 7.44; P, 5.57; S, 5.77; Se, 14.21. Found: C, 58.18; H, 7.60; P,
1
5
.72; S, 5.78; Se, 14.43; (S-3f): H NMR (400.13 MHz, CDCl ) δ 7.11-7.08 and 6.83-6.81 (m, 8 H, in
3
3
2
Ar), 5.34 (dq, JHH=6.1 Hz, JPH=11.1 Hz, 1 H, CHS), 3.78 (c, 6 H, OMe), 3.77-3.61 and 3.45-3.38 (m,
3
2
H, OCH
2
), 3.01-2.81 (m, 4 H, CH
2
Ar), 2.56-2.46 and 2.44-2.34 (m, 4 H, CH
2
P), 1.75 (d, JHH=6.2
3
Hz, 3 H, MeCH), 1.59-1.53 (m, 2 H, CH
2
), 1.30-1.26 (m, 8 H, CH
2
), 0.87 (t, JHH=6.9 Hz, 3 H, Me);
1
3
1
3
1
C NMR (100.62 MHz, CDCl
3
) δ 158.4 (C in Ar), 132.2 (d, JPC=16.8 Hz, C in Ar), 129.3, 114.2
2
,3,4,6
1
(
1
C
in Ar), 89.9 (CHS), 68.9 (OCH
2
2
), 55.3 (OMe), 40.0 (d, JPC=39.9 Hz, CH
2
P), 39.4 (d,
),
3
J
PC=41.9 Hz, CH
2
P), 31.8, 29.5, 29.1 (CH
), 28.8 (CH
2
Ar), 25.3 (d, JPC=4.1 Hz, MeCH), 22.63 (CH
2
31
1
77
1
3
4.1 (Me); P NMR (161.98 MHz, CDCl ) δ 60.38 (s, JP=Se=762 Hz); Se NMR (76.31 MHz,
1
1
3 3
CDCl ) δ −266 (d, JP=Se=762 Hz); (Se-3f): H NMR (400.13 MHz, CDCl ) δ 7.11-7.08 and 6.83-6.81
3
2
(
m, 8 H, in Ar), 5.54 (dq, JHH=6.1 Hz, JPH=8.7 Hz, 1 H, CHSe), 3.78 (c, 6 H, OMe), 3.77-3.61 and
3
.45-3.38 (m, 2 H, OCH
2
), 3.01-2.81 (m, 4 H, CH
2
2
Ar), 2.56-2.46 and 2.44-2.34 (m, 4 H, CH P), 1.93
3
3
(
d, JHH=6.1 Hz, 3 H, MeCH), 1.59-1.53 (m, 2 H, CH
2
), 1.30-1.26 (m, 8 H, CH
2
), 0.87 (t, JHH=6.9 Hz,
13
4
3
1
3
H, Me); C NMR (100.62 MHz, CDCl ) δ 158.4 (C in Ar), 132.5 (d, J =16.8 Hz, C in Ar), 129.3,
3
PC
2
,3,4,6
1
1
14.2 (C
in Ar), 91.5 (CHSe), 70.2 (OCH
2
2
), 55.3 (OMe), 41.0 (d, JPC=42.3 Hz, CH P), 40.5 (d,
1
3
J
PC=42.3 Hz, CH
2
P), 31.8, 29.5, 29.1, (CH
2
), 28.5 (CH
2
Ar), 26.9 (d, JPC=2.4 Hz, MeCH), 26.1, 22.6
1
4

ACCEPTED MANUSCRIPT
31
1
77
(
CH ), 14.1 (Me); P NMR (161.98 MHz, CDCl ) δ 61.14 (s, J =362 Hz); Se NMR (76.31 MHz,
2
3
P-Se
1
3
CDCl ) δ 319 (d, JP-Se=362 Hz).
4
.2.7. 1-[(2,2,3,3,4,4,5,5-Octafluoropentyl)oxy]ethyl bis(4-methoxyphenethyl)phosphino-selenothioate
(3g). Bis(4-methoxyphenethyl)phosphine sulfide (1c; 334 mg, 1.0 mmol) and powdered grey selenium
(79 mg, 1.0 mmol) were added consecutively to a solution of 2,2,3,3,4,4,5,5-octafluoropentyl vinyl
ether (2f; 258 mg, 1.0 mmol) in 1,4-dioxane (5 mL) at ambient temperature (in argon atmosphere). The
o
suspension was stirred at 100 C until dissolution of selenium residue to give a light yellow transparent
o
solution. The solvent was removed under reduced pressure (1 Torr, 40-45 C), and the residue was
purified by flash-chromatography (3 cm of neutral Al
yellowish oil (isomeric mixture of the S- and Se-esters, the molar ratio being 62:38). Yield: 624 mg
93%); IR (KBr) 3061, 3031, 2997, 2954, 2935, 2913, 2861, 2837, 1612, 1584, 1513, 1466, 1443,
2 3 3
O ; CHCl -hexane, 3:1) to give compound 3g as
(
1
5
4
420, 1400, 1378, 1301, 1248, 1178. 1131, 1036, 991, 955, 903, 874, 848, 819, 759, 736, 637, 611,
–1
48, 519, 463 cm . Anal. Calcd for C25
H
29
F
8
O
3
PSSe (671.48): C, 44.72; H, 4.35; F, 22.63; P, 4.61; S,
1
.78; Se, 11.76. Found: C, 44.71; F, 22.64; H, 3.60; P, 4.78; S, 4.58; Se, 12.01; (S-3g): H NMR
2
3
(400.13 MHz, CDCl
3
) δ 7.13-7.09 and 6.86-6.83 (m, 8 H, in Ar), 6.05 (tt, JHF=52.0 Hz, JHF=5.7 Hz,
3
2
CHF
2
), 5.46 (dq, JHH=6.2 Hz, JPH=12.1 Hz, 1 H, CHS), 4.24-4.11 (m, 2 H, OCH
2
), 3.80 (c, 6 H,
3
OMe), 3.06-2.92 and 2.90-2.77 (m, 4 H, CH Ar), 2.55-2.35 (m, 4 H, CH P), 1.81 (d, J =6.2 Hz, 3 H,
2
2
HH
13
1
3
4
MeCH); C NMR (100.62 MHz, CDCl
3
) δ 155.4 (C in Ar), 132.1 (d, JPC=16.0 Hz, C in Ar), 129.3,
2,3,5,6
1
2
1
14.2 (C
2 3 2
in Ar), 113.5-110.1 [m, (CF ) ], 107.6 (tt, JCF=254.0 Hz, JCF=31.9 Hz, CHF ), 89.9
3
1
1
(
CHS), 64.9 (t, J =26.3 Hz, OCH ), 55.3 (OMe), 39.9 (d, J =40.8 Hz, CH P), 39.3 (d, J =42.8
CF
2
PC
2
PC
3
31
Hz, CH
2
P), 28.8 (CH
2
Ar), 24.6 (d, JPC=4.8 Hz, MeCH); P NMR (161.98 MHz, CDCl
3
) δ 63.30 (s,
1
77
1
1
J
P=Se=766 Hz); Se NMR (76.31 MHz, CDCl
3
) δ −259 (d, JP=Se=761 Hz); (Se-3g): H NMR (400.13
2
3
MHz, CDCl
3
) δ 7.13-7.09 and 6.86-6.83 (m, 8 H, in Ar), 6.05 (tt, JHF=52.0 Hz, JHF=5.7 Hz, CHF
2
),
3
2
5
2
.61 (dq, JHH=6.3 Hz, JPH=9.5 Hz, 1 H, CHSe), 4.24-4.11 (m, 2 H, OCH
2
), 3.80 (c, 6 H, Me), 3.06-
3
.92 and 2.90-2.77 (m, 4 H, CH
2
2
Ar), 2.55-2.35 (m, 4 H, CH P), 1.98 (d, JHH = 6.3 Hz, 3 H, MeCH);
1
3
1
3
4
C NMR (100.62 MHz, CDCl
3
) δ 155.4 (C in Ar), 131.8 (d, JPC=14.7 Hz, C in Ar), 129.3, 114.2
2
,3,5,6
1
2
(C
in Ar), 113.5-110.1 [m, (CF
2
)
3
], 107.6 (tt, JCF=254.0 Hz, JCF=31.9 Hz, CHF
2
), 89.4 (CHSe),
3
1
1
6
5.8 (t, JCF=26.4 Hz, OCH
2
), 55.3 (OMe), 41.2 (d, JPC=43.5 Hz, CH
2
P), 40.4 (d, JPC=43.1 Hz,
3
31
1
CH
2
P), 28.4 (CH
2
Ar), 26.0 (d, JPC=2.6 Hz, MeCH); P NMR (161.98 MHz, CDCl
3
) δ 63.69 (s, JP-
77
1
Se=343 Hz); Se NMR (76.31 MHz, CDCl
3
) δ 321 (d, JP-Se=347 Hz).
4
.2.8.
[1-(4-Fluorophenoxy)ethyl] bis(4-methoxyphenethyl)phosphinoselenothioate (3h). Bis(4-
methoxyphenethyl)phosphine sulfide (1c; 334 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0
mmol) were added consecutively to a solution of 4-fluorophenyl vinyl ether (2g; 138 mg, 1.0 mmol) in
1
,4-dioxane (5 mL) at ambient temperature (in argon atmosphere). The suspension was stirred at 100
1
5

ACCEPTED MANUSCRIPT
o
C until dissolution of selenium residue to give a light yellow transparent solution. The solvent was
o
removed under reduced pressure (1 Torr, 40-45 C), and the residue was purified by flash-
chromatography (3 cm of neutral Al
2
O
3
3
; CHCl -hexane, 3:1) to give compound 3h as yellowish oil
(isomeric mixture of the S- and Se-esters, the molar ratio being 61:39). Yield: 502 mg (91%); IR (KBr)
3
1
064, 3031, 2996, 2953, 2932, 2910, 2858, 2835, 1611, 1584, 1513, 1465, 1441, 1421, 1367, 1377,
–
1
301, 1247, 1178. 1130, 1081, 1036, 1010, 933, 915, 873, 822, 747, 735, 635, 611, 551, 518, 461 cm .
Anal. Calcd for C H FO PSSe (551.51): C, 56.62; H, 5.48; P, 5.62; S, 5,81; Se, 14.32; F, 3.44.
26
30
3
1
3
Found: C, 56.71; H, 5.60; P, 5.94; S, 5.78; Se, 14.01; F, 3.44; (S-3h): H NMR (400.13 MHz, CDCl )
3
δ 7.16-7.12 (m, 4 H, Ar), 7.04-6.98 (m, 4 H, in Ar), 6.88-6.82 (m, 4 H, C
6
H
4
F), 5.96 (dq, 1 H, JHH=6.1
2
Hz, JPH=12.4 Hz, CHS), 3.83 (s, 6 H, MeO), 3.05-2.87 and 2.83-2.64 (m, 4 H, CH
2
Ar), 2.45-2.35 and
3
13
2
.29-2.18 (m, 4 H, CH
2
P), 1.92 (d, JHH=6.1 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl
3
) δ 158.7
1
4
4
1
3
1
(
d, JCF = 241.7 Hz, C -F), 158.4 (C in Ar), 151.9 (C in C
6
H
4
F), 131.9 (d, JPC=15.6 Hz, C in Ar),
2
,6
3
2,6
2
3,5
1
29.3 (C in Ar), 120.1 (d, JCF=8.0 Hz, C in C
6
H
4
F), 116.0 (d, JCF=23.2 Hz, C in C
6
4
H F), 114.2
3
,5
1
1
(C
in Ar), 87.6 (CHS), 55.3 (OMe), 38.9 (d, JPC=38.7 Hz, CH
2
P), 38.1 (d, JPC=42.3 Hz, CH
2
P),
3
31
2
9.0, 28.6 (CH Ar), 24.7 (d, J =4.8 Hz, MeCH); P NMR (161.98 MHz, CDCl ) δ 62.52 (s,
2 PC 3
1
77
1
1
J
P=Se=765 Hz); Se NMR (76.31 MHz, CDCl
) δ 7.16-7.12 (m, 4 H, in Ar), 7.04-6.98 (m, 4 H, in Ar), 6.88-6.82 (m, 4 H, C
m, 1 H, CHSe), 3.82 (s, 6 H, MeO), 3.05-2.87 and 2.83-2.64 (m, 4 H, CH Ar), 2.45-2.35 and 2.29-
3
) δ −265 (d, JP=Se=765 Hz); (Se-3h): H NMR (400.13
MHz, CDCl
3
6 4
H
F), 6.06
(
2
3
13
2
.18 (m, 4 H, CH P), 2.14 (d, J =6.1 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl ) δ 158.7 (d,
2
HH
3
1
4
4
1
3
1
J
CF = 241.7 Hz, C -F), 158.3 (C in Ar), 152.1 (C in C
6
H
4
F), 132.2 (d, JPC=14.8 Hz, C in Ar), 129.2
2
,6
3
2,6
2
3,5
3,5
(C
in Ar), 119.7 (d, JCF=8.0 Hz, C in C
6
H
4
6 4
F), 115.9 (d, JCF=23.2 Hz, C in C H F), 114.1 (C
1
1
in Ar), 87.1 (CHSe), 55.3 (OMe), 40.7 (d, J =42.8 Hz, CH P), 40.0 (d, J =43.5 Hz, CH P), 28.6,
PC
2
PC
2
3
31
1
2
8.3 (CH
2
Ar), 26.6 (d, JPC=2.4 Hz, MeCH); P NMR (161.98 MHz, CDCl
3
) δ 63.49 (s, JP-Se=349
77
1
Hz); Se NMR (76.31 MHz, CDCl
3
) δ 317 (d, JP-Se=349 Hz).
4
.2.9. [1-(2,6-Dimethylphenoxy)ethyl] bis(4-methoxyphenethyl)phosphinoselenothioate (3i). Bis(4-
methoxyphenethyl)phosphine sulfide (1c; 334 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0
mmol) were added consecutively to a solution of 2,6-dimethylphenyl vinyl ether (2h; 148 mg, 1.0
mmol) in 1,4-dioxane (5 mL) at ambient temperature (in argon atmosphere). The suspension was
o
stirred at 100 C until dissolution of selenium residue to give a light yellow transparent solution. The
o
solvent was removed under reduced pressure (1 Torr, 40-45 C), and the residue was purified by flash-
chromatography (3 cm of neutral Al
2
O
3
3
; CHCl -hexane, 3:1) to give compound 3i as colorless oil
(isomeric mixture of the S- and Se-esters, the molar ratio being 53:47). Yield: 331 mg (80%); IR (KBr)
3
1
6
125, 3100, 3061, 3029, 2995, 2953, 2929, 2858, 2834, 1612, 1584, 1513, 1465, 1441, 1397, 1375,
318, 1301, 1247, 1193, 1178, 1131, 1079, 1036, 1009, 949, 917, 866, 847, 818, 772, 733, 696, 678,
–1
37, 610, 572, 546, 517, 466 cm . Anal. Calcd for C H OPSSe: Anal. Calcd for C H O PSSe
28
35
28 35
3
1
6

ACCEPTED MANUSCRIPT
(413.37): C, 59.89; H, 6.28; P, 5.52; S, 5.71; Se, 14.06. Found: C, 60.01; H, 5.80; P, 5.50; S, 5.78; Se,
1
1
4.01; (S-3i): H NMR (400.13 MHz, CDCl
3
) δ 7.16-7.00 and 6.91-6.85(m, each 4 H, in Ar), 6.80-
3
2
6
.75 (m, 3 H, C
6
H
3
O), 5.78 (dq, JHH=6.2 Hz, JPH=12.3 Hz, 1 H, CHS), 3.05-2.76 (m, 4 H, CH
2
Ar),
3
13
2
.47-2.28 and 2.27-2.14 (m, 4 H, CH P), 1.94 (d, J =6.2 Hz, 3 H, MeCH); C NMR (100.62 MHz,
2 HH
4
1
3
1
2,6
3 6 3
CDCl ) δ 157.6 (C in Ar), 152.7 (C in C H O), 131.7 (d, JPC=15.3 Hz, C in Ar), 130.8 (C in
2
,6
3,5
4
3,5
C
6
H
3
O), 128.6 (C in Ar), 128.5 (C in C
6
H
3
6 3
O), 124.2 (C in C H O), 113.2 (C in Ar), 90.4 (CHS),
1
1
5
4.6 (OMe), 40.2 (d, J =41.8 Hz, CH P), 39.8 (d, J =38.7 Hz, CH P), 28.0, 27.9 (CH Ar), 25.0 (d,
PC
2
PC
2
2
3
31
1
77
J
3
PC=4.3 Hz, MeCH), 17.0 (Me); P NMR (161.98 MHz, CDCl ) δ 63.52 (s, JP=Se=767 Hz); Se
1
1
NMR (76.31 MHz, CDCl
3
3
) δ −266 (d, JP=Se=767 Hz); (Se-3i): H NMR (400.13 MHz, CDCl ) δ 7.16-
3
2
7
.00 and 6.91-6.85 (m, each 4 H, in Ar), 6.80-6.75 (m, 3 H, C
6
H
3
O), 6.00 (dq, JHH=6.2 Hz, JPH=9.5
Hz, 1 H, CHSe), 3.05-2.76 (m, 4 H, CH
2
2
Ar), 2.47-2.28 and 2.27-2.14 (m, 4 H, CH P), 2.11 (d,
3
13
4
1
J
HH=6.2 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl
3
) δ 157.8 (C in Ar), 152.3 (C in C
6
H
3
O),
3
1
2,6
2,6
3,5
1
1
31.6 (d, J =16.2 Hz, C in Ar), 130.4 (C in C H O), 128.6 (C in Ar), 128.4 (C in C H O),
PC 6 3 6 3
4
3,5
1
6 3 2
24.1 (C in C H O), 113.4 (C in Ar), 89.8 (CHSe), 54.6 (OMe), 38.3 (d, JPC=45.2 Hz, CH P), 36.8
1
3
31
(
d, JPC=43.3 Hz, CH
2
2
P), 27.6, 27.5 (CH Ar), 25.8 (d, JPC=3.4 Hz, MeCH), 16.9 (Me); P NMR
1
77
1
(
161.98 MHz, CDCl ) δ 63.34 (s, J =351 Hz); Se NMR (76.31 MHz, CDCl ) δ 325 (d, JP-Se=351
3
P-Se
3
Hz).
4
.2.10. 1-[(2,2,3,3-Tetrafluoropropyl)oxy]ethyl bis(4-chlorophenethyl)phosphinoselenothioate (3j).
Bis(4-chlorophenethyl)phosphine sulfide (1d; 343 mg, 1.0 mmol) and powdered grey selenium (79 mg,
1
1
.0 mmol) were added consecutively to a solution of 2,2,3,3-tetrafluoropropyl vinyl ether (2i; 158 mg,
.0 mmol) in 1,4-dioxane (5 mL) at ambient temperature (in argon atmosphere). The suspension was
o
stirred at 100 C until dissolution of selenium residue to give a light yellow transparent solution. The
o
solvent was removed under reduced pressure (1 Torr, 40-45 C), and the residue was purified by flash-
chromatography (3 cm of neutral Al
2
O
3
3
; CHCl -hexane, 3:1) to give compound 3j as yellowish oil
(isomeric mixture of the S- and Se-esters, the molar ratio being 69:31). Yield: 470 mg (81%); IR (KBr)
3
1
7
4
5
099, 3084, 3062, 3041, 3026, 3008, 2985, 2926, 2904, 2891, 2850, 1492, 1435, 1407, 1395, 1352,
276, 1255, 1237, 1205, 1183, 1131, 1117, 1045, 1014, 991, 972, 941, 904, 873, 836, 811, 771, 736,
–1
2 4
05, 685, 653, 601, 549, 532, 509, 489, 464, 400 cm . Anal. Calcd for C21H23Cl F PSSe (580.31): C,
3.46; H, 3.99; Cl, 12.22; P, 5.34; S, 5.53; Se, 13.61. Found: C, 43.71; H, 3.65; Cl, 12.51; P, 5.70; S,
1
.79; Se, 16.21; (S-3j): H NMR (400.13 MHz, CDCl
3
) δ 7.23-7.19 and 7.11-7.04 (m, 8 H, in Ar), 5.83
2
3
3
2
(
2
tt, JHF=53.0 Hz, JHF=4.6 Hz, 1 H, CHF ), 5.37 (dq, JHH=6.2 Hz, JPH=9.8 Hz, 1 H, CHS), 4.02 and
2
3
3
.93 (dt, JHH=12.6 Hz, JHF=12.4 Hz, 2 H, OCH
2
), 3.04-2.88 and 2.84-2.73 (m, 4 H, CH
2
Ar), 2.49-
) δ 138.1 (d,
2
in Ar), 114.5 (m, CF ), 109.0 (tt,
3
13
2
.27 (m, 4 H, PCH
2
), 1.72 (d, JHH=6.2 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl
3
3
1
4
2,3,5,6
J
PC=16.8 Hz, C in Ar), 132.5 (C in Ar), 129.5, 128.5 (C
1
2
3
1
J =249.6 Hz, J =34.1 Hz, CHF ), 89.8 (CHS), 64.8 (t, J =29.1 Hz, OCH ), 39.2 (d, J =41.8 Hz,
CF
CF
2
CF
2
PC
1
7

ACCEPTED MANUSCRIPT
1
2
3
CH P), 39.0 (d, J =42.2 Hz, CH P), 29.0 (d, J =11.9 Hz, CH Ar), 24.1 (d, J =5.0 Hz, MeCH);
2
PC
2
PC
2
PC
3
1
1
77
P NMR (161.98 MHz, CDCl
3
) δ 62.72 (s, JP=Se=769 Hz); Se NMR (76.31 MHz, CDCl
3
) δ −263 (d,
1
1
J
P=Se = 769 Hz); (Se-3j): H NMR (400.13 MHz, CDCl
3
) δ 7.23-7.19 and 7.11-7.04 (m, 8 H, in Ar),
2
3
3
2
5
2
.83 (tt, JHF=53.0 Hz, JHF=4.6 Hz, 1 H, CHF ), 5.50 (dq, JHH=6.2 Hz, JPH=9.8 Hz, 1 H, CHSe), 4.02
2
3
and 3.93 (dt, JHH=12.6 Hz, JHF=12.4 Hz, 2 H, OCH
2
2
), 3.04-2.88 and 2.84-2.73 (m, 4 H, CH Ar),
3
13
2
.49-2.27 (m, 4 H, PCH
2
), 1.90 (d, JHH=6.2 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl
3
) δ 138.3
3
1
4
2,3,5,6
(
d, JPC=16.5 Hz, C in Ar), 132.46 (C in Ar), 129.5, 128.5 (C
in Ar), 114.5 (m, CF
2
), 109.0 (tt,
1
2
3
1
J
CF=249.6 Hz, JCF=34.1 Hz, CHF
2
), 89.8 (CHSe), 65.9 (t, JCF=28.4 Hz, OCH
2
), 40.5 (d, JPC=44.9
1
2
3
Hz, CH
2
P), 40.1 (d, JPC=44.5 Hz, CH
2
P), 28.6 (d, JPC=13.0 Hz, CH
2
Ar), 25.8 (d, JPC=3.8 Hz,
31
1
77
3 3
MeCH); P NMR (161.98 MHz, CDCl ) δ 62.72 (s, JP-Se=348 Hz); Se NMR (76.31 MHz, CDCl ) δ
1
3
21 (d, JP-Se=348 Hz).
4
.2.11. 1-(2-Furylmethoxy)ethyl bis(4-chlorophenethyl)phosphinoselenothioate (3k). Bis(4-
chlorophenethyl)phosphine sulfide (1d; 343 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0
mmol) were added consecutively to a solution of 2-furylmethyl vinyl ether (2j; 124 mg, 1.0 mmol) in
1
,4-dioxane (5 mL) at ambient temperature (in argon atmosphere). The suspension was stirred at 100
o
C until dissolution of selenium residue to give a light yellow transparent solution. The solvent was
o
removed under reduced pressure (1 Torr, 40-45 C), and the residue was purified by flash-
chromatography (3 cm of neutral Al O ; CHCl -hexane, 3:1) to give compound 3k as yellowish oil
2
3
3
(isomeric mixture of the S- and Se-esters, the molar ratio being 80:20). Yield: 448 mg (82%); IR (KBr)
3
1
5
5
117, 3085, 3026, 2960, 2914, 2889, 2854, 1492, 1453, 1445, 1408, 1366, 1333, 1289, 1254, 1225,
218, 1180, 1150, 1121, 1083, 1048, 1015, 949, 937, 914, 888, 874, 847, 807, 744, 706, 656, 613, 600,
–1
14, 491, 449, 396 cm . Anal. Calcd for C23
H25Cl
2
O
2
PSSe (546.35): C, 50.56; H, 4.61; Cl, 12.98; P,
1
.67; S, 5.87; Se, 14.45. Found: C, 50.74; H, 4.90; P, 5.73; S, 5.71; Se, 13.99; (S-3k): H NMR (400.13
5
MHz, CDCl
3
) δ 7.29 (br s, 1 H, CH in Fur), 7.22-7.18 and 7.10-7.04 (m, 8 H, in Ar), 6.31 and 6.27
3
3,4
3
2
(
each d, JHH=3.0 Hz, 2 H, CH in Fur), 5.39 (dq, JHH=6.2 Hz, JPH=12.4 Hz, 1 H, CHS), 4.60 (dd,
2
3
J
HH=12.5 Hz, JPH=19.4 Hz, 2 H, OCH
2
2 2
), 3.03-2.79 (m, 4 H, CH Ar), 2.57-2.28 (m, 4 H, CH P), 1.71
3
13
2
5
(
d, JHH=6.2 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl ) δ 150.4 (C in Fur), 142.9 (C in Fur),
3
3
1
4
2,3,5,6
3,4
1
38.4 (d, JPC=16.8 Hz, C in Ar), 132.3 (C in Ar), 129.6, 128.7 (C
in Ar), 110.3, 109.9 (C in
1
1
Fur), 88.4 (CHS), 62.3 (OCH
2
), 39.3 (d, JPC=41.0 Hz, CH
2
P), 38.6 (d, JPC=42.5 Hz, CH
2
P), 29.2,
3
31
1
2
8.9 (CH
2
Ar), 24.5 (d, JPC=5.0 Hz, MeCH); P NMR (161.98 MHz, CDCl
3
) δ 59.31 (s, JP=Se=768
77
1
1
Hz); Se NMR (76.31 MHz, CDCl ) δ −264 (d, J =766 Hz); (Se-3k): H NMR (400.13 MHz,
3
P=Se
5
3
CDCl ) δ 7.32 (br s, 1 H, CH in Fur), 7.22-7.18 and 7.10-7.04 (m, 8 H, Ar), 6.35 and 6.24 (each d,
3
3,4
3
2
2
JHH=3.0 Hz, 2 H, CH in Fur), 5.57 (dq, J =6.2 Hz, J =9.0 Hz, 1 H, CHSe), 4.50 (dd, J =12.5
HH
PH
HH
3
Hz, JPH=12.5 Hz, 2 H, OCH
2
), 3.03-2.79 (m, 4 H, CH
2
Ar), 2.57-2.28 (m, 4 H, CH
2
P), 1.90 (d,
3
13
2
5
J
HH=6.2 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl
3
) δ 150.4 (C in Fur), 142.9 (C in Fur),
1
8

ACCEPTED MANUSCRIPT
3
1
4
2,3,5,6
3,4
1
38.4 (d, J =16.8 Hz, C in Ar), 132.3 (C in Ar), 129.6, 128.7 (C
in Ar), 110.2, 110.0 (C in
PC
1
1
Fur), 89.9 (CHSe), 63.4 (OCH
2
), 40.4 (d, JPC=44.5 Hz, CH
2
P), 40.2 (d, JPC=43.7 Hz, CH
2
P), 28.8,
3
31
1
2
8.6 (CH
2
Ar), 26.4 (d, JPC=3.4 Hz, MeCH); P NMR (161.98 MHz, CDCl
3
) δ 59.75 (s, JP-Se=358
77
1
Hz); Se NMR (76.31 MHz, CDCl ) δ 309 (d, J
= 359 Hz).
P-Se
3
4
.2.12. (1-Phenoxy)ethyl bis(2-furylethyl)phosphinoselenothioate (3l). Bis[2-(2-furyl)ethyl]phosphine
sulfide (1e; 254 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0 mmol) were added
consecutively to a solution of phenyl vinyl ether (2a; 120 mg, 1.0 mmol) in 1,4-dioxane (5 mL) at
o
ambient temperature (in argon atmosphere). The suspension was stirred at 100 C until dissolution of
selenium residue to give a light yellow transparent solution. The solvent was removed under reduced
o
pressure (1 Torr, 40-45 C), and the residue was purified by flash-chromatography (3 cm of neutral
Al
2 3 3
O ; CHCl -hexane, 3:1) to give compound 3l as yellowish oil (isomeric mixture of the S- and Se-
esters, the molar ratio being 73:27). Yield: 421 mg (93%); IR (KBr) 3146, 3115, 3062, 3040, 2974,
2
1
920, 2851, 1596, 1506, 1488, 1454, 1437, 1400, 1378, 1334, 1291, 1218, 1174, 1147, 1112, 1089,
–1
071, 1008, 951, 936, 916, 885, 851, 799, 754, 732, 692, 637, 612, 599, 528, 460 cm . Anal. Calcd for
20 23 2
C H O
PSSe (453.40): C, 52.98; H, 5.11; P, 6.83; S, 7.07; Se, 17.42. Found: C, 52.70; H, 5.03; P,
1
5
6
7
3
.72; S, 6.78; Se, 17.11; (S-3l): H NMR (400.13 MHz, CDCl ) δ 7.30-7.24 (m, 4 H, PhO, CH in Fur),
4
3
.12-7.10 and 7.04-7.00 (m, 3 H, PhO), 6.27-6.23 (m, 2 H, CH in Fur), 6.10-6.01 (m, 1 H, CH in Fur),
3
5
.98-5.89 (m, 2 H, CHS, CH in Fur), 3.09-2.68 (m, 4 H, CH
2
2
Fur), 2.49-2.19 (m, 4 H, CH P), 1.87 (d,
3
13
1
J
HH=6.1 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl
3
) δ 155.84 (C in PhO), 153.16 (d,
3
2
5
J =18.4 Hz, C in Fur), 141.50, 141.37 (C in Fur), 129.50, 123.12, 118.48 (PhO), 110.97, 110.93,
PC
3
,4
1
1
1
05.97, 105.93 (C in Fur), 86.94 (CHS), 36.43 (d, JPC=42.0 Hz, CH
2
P), 34.20 (d, JPC=45.2 Hz,
3
2
31
CH
2
P), 24.65 (d, JPC=4.6 Hz, MeCH), 22.66 (d, JPC=30.8 Hz, CH
2
Fur); P NMR (161.98 MHz,
1
77
1
CDCl
3
) δ 61.55 (s, JP=Se=762 Hz); Se NMR (76.31 MHz, CDCl
3
) δ −268 (d, JP=Se=762 Hz); (Se-3l):
1
5
H NMR (400.13 MHz, CDCl
3
) δ 7.30-7.24 (m, 4 H, PhO, CH in Fur), 7.12-7.10 and 7.04-7.00 (m, 3
4
3
H, PhO), 6.27-6.23 (m, 2 H, CH in Fur), 6.10-6.01 (m, 1 H, CH in Fur), 5.98-5.89 (m, 2 H, CHSe,
3
3
CH in Fur), 3.09-2.68 (m, 4 H, CH
2
2
Fur), 2.49-2.19 (m, 4 H, CH P), 1.99 (d, JHH=6.1 Hz, 3 H,
1
3
1
3
2
MeCH); C NMR (100.62 MHz, CDCl
3
) δ 156.02 (C in PhO), 153.16 (d, JPC=18.4 Hz, C in Fur),
5
3,4
1
8
41.50, 141.37 (C in Fur), 129.45, 123.18, 118.27 (PhO), 110.97, 110.93, 105.89, 105.83 (C in Fur),
1
1
3
6.53 (CHSe), 39.86 (d, JPC=45.5 Hz, CH
2
P), 36.13 (d, JPC=46.3 Hz, CH
2
P), 26.60 (d, JPC=2.6 Hz,
2
31
1
MeCH), 21.17 (d, JPC=23.0 Hz, CH
2
Fur); P NMR (161.98 MHz, CDCl
3
) δ 61.85 (s, JP=Se=352 Hz);
7
7
1
Se NMR (76.31 MHz, CDCl
3
) δ 323 (d, JP=Se=352 Hz).
4
.2.13.
1-[(2,2,3,3-Tetrafluoropropyl)oxy]ethyl
diphenylphosphinoselenothioate
(3m).
Diphenylphosphine sulfide (1f; 218 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0 mmol)
were added consecutively to a solution of 2,2,3,3,4,4,5,5-octafluoropentyl vinyl ether (2f; 258 mg, 1.0
1
9

ACCEPTED MANUSCRIPT
mmol) in 1,4-dioxane (5 mL) at ambient temperature (in argon atmosphere). The suspension was
o
stirred at 100 C until dissolution of selenium residue to give a light yellow transparent solution. The
o
solvent was removed under reduced pressure (1 Torr, 40-45 C), and the residue was purified by flash-
chromatography (3 cm of neutral Al O ; CHCl -hexane, 3:1) to give compound 3m as yellowish oil
2
3
3
(isomeric mixture of the S- and Se-esters, the molar ratio being 64:36). Yield: 499 mg (90%); IR (KBr)
3
1
075, 3057, 2962, 2929, 2890, 2856, 1481, 1454, 1437, 1403, 1378, 1333, 1308, 1288, 1255, 1225,
–1
129, 1046, 1027, 998, 975, 958, 902, 890, 874, 809, 747, 716, 690, 648, 615, 561, 520, 482, 440 cm .
Anal. Calcd for C19
H
17
F
8
OPSSe (555.33): C, 41.09; H, 3.09; F, 27.37; P, 5.58; S, 5.77; Se, 14.22.
1
Found: C, 41.31; H, 2.60; P, 5.72; S, 5.78; Se, 14.10; (S-3m): H NMR (400.13 MHz, CDCl
3
) δ 8.01-
), 5.46 (dq,
O), 1.71 (d, JHH=6.2 Hz, 3 H,
) δ 133.8 and 133.6 (d, JPC=75.1 and 76.6 Hz, i-C, Ph), 132.1
3
2
7
.88 (m, 4 H, Ph), 7.54-7.46 (m, 6 H, Ph), 6.00 (tt, JHH=5.6 Hz, JHF=52.0 Hz, 1 H, CHF
2
3
2
3
3
J
HH=6.2 Hz, JPH=12.4 Hz, 1 H, CHS), 3.93 (t, JHF=13.8 Hz, 2 H, CH
2
1
3
1
MeCH); C NMR (100.62 MHz, CDCl
3
4
2
3
(
d, JCP=3.0 Hz, p-C, Ph), 131.9 and 131.7 (d, JCP=13.4 Hz, o-C, Ph), 128.6 (d, JCP=13.4 Hz, m-C,
1
2
1
2
2 2
Ph), 114.9 (tt, JCF=255.7 Hz, JCF=31.4 Hz, CF ), 107.69 (tt, JCF=254.0 Hz, JCF=30.7 Hz, CHF ),
2
3
31
8
9.4 (CHS), 65.4 (t, J =25.7 Hz, CH O), 24.5 (d, J =5.4 Hz, MeCH); P NMR (161.98 MHz,
CF
2
PC
1
77
1
CDCl
3
) δ 53.18 (s, JP=S=784 Hz); Se NMR (76.31 MHz, CDCl
3
) δ −196 (d, JP=Se=784 Hz); (Se-
1
3
m): H NMR (400.13 MHz, CDCl
3
) δ 8.01-7.88 (m, 4 H, Ph), 7.54-7.46 (m, 6 H, Ph), 6.00 (tt,
3
2
3
2
J
HH=5.6 Hz, JHF=52.0 Hz, 1 H, CHF
2
), 5.61 (dq, JHH=6.2 Hz, JPH=9.4 Hz, 1 H, CHSe), 3.93 (t,
3
3
13
J =13.8 Hz, 2 H, CH O), 1.88 (d, J =6.2 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl ) δ
HF
2
HH
3
1
4
1
35.2 and 135.0 (d, JPC=78.2 and 79.0 Hz, i-C, Ph), 132.2 (d, JCP=3.0 Hz, p-C, Ph), 131.4 and131.3
2
3
1
2
(
d, JCP=13.4 Hz, o-C, Ph), 128.6 (d, JCP=13.4 Hz, m-C, Ph), 114.9 (tt, JCF =255.7 Hz, JCF =31.4 Hz,
1
2
2
CF ), 107.6 (tt, J =254.0 Hz, J =30.7 Hz, CHF ), 89.3 (CHSe), 66.1 (t, J =25.7 Hz, CH O),
2
CF
CF
2
CF
2
3
31
1
77
2
3
5.5 (d, JPC =4.6 Hz, MeCH); P NMR (161.98 MHz, CDCl ) δ 50.89 (s, JP-Se=359 Hz); Se NMR
1
(
76.31 MHz, CDCl
3
) δ 408 (d, JP-Se 359 Hz).
4
.2.14. [1-(2,6-Dimethylphenoxy)ethyl] diphenylphosphinoselenothioate (3n) Diphenylphosphine
sulfide (1f; 218 mg, 1.0 mmol) and powdered grey selenium (79 mg, 1.0 mmol) were added
consecutively to a solution of 2,6-dimethylphenyl vinyl ether (2h; 148 mg, 1.0 mmol) in 1,4-dioxane
o
(
5 mL) at ambient temperature (in argon atmosphere). The suspension was stirred at 100 C until
dissolution of selenium residue to give a light yellow transparent solution. The solvent was removed
o
under reduced pressure (1 Torr, 40-45 C), and the residue was purified by flash-chromatography (3 cm
2 3 3
of neutral Al O ; CHCl -hexane, 3:1) to give compound 3n as colorless oil (isomeric mixture of the S-
and Se-esters, the molar ratio being 69:31). Yield: 370 mg (83%); IR (KBr) 3144, 3055, 3020, 3044,
2
956, 2922, 2887, 2854, 1588, 1574, 1478, 1436, 1375, 1333, 1308, 1287, 1262, 1190, 1161, 1120,
–
1
093, 1027, 1009, 999, 918, 888, 874, 846, 815, 770, 746, 715, 689, 647, 615, 559, 519, 481, 438 cm
1
.
Anal. Calcd for C H OPSSe (445.42): C, 59.30; H, 5.02; P, 6.95; S, 7.20; Se, 17.73. Found: C,
22 23
2
0

ACCEPTED MANUSCRIPT
1
5
9.62; H, 5.02; P, 6.52; S, 7.78; Se, 17.54; (S-3n): H NMR (400.13 MHz, CDCl ) δ 7.73 (dd,
3
3
3
3
3
J
PН=14.4 Hz, JHН=7.5 Hz, 2 Н, Ph), 7.51 (dd, JPН=14.6 Hz, JHН=7.5 Hz, 2 Н, Ph), 7.46-7.34 (m, 4
2
3
H, Ph), 7.25-7.20 (m, 2 H, Ph), 6.83 (m, 3 H, OAr), 5.79 (dq, JPH=12.0 Hz, JHH=6.1 Hz, 1 H, CHS),
3
13
1
2
.21 (s, 6 H, Me), 1.98 (d, J =6.1 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl ) δ 152.1 (C in
HH 3
1
2
2,5
OAr), 132.7 (d, JPC=79.0 Hz, i-C, Ph), 131.1 (p-C, Ph), 130.7 (d, JCP=11.2 Hz, o-C, Ph), 128.3 (C
3
4
3
in OAr), 127.5 (d, JCP=13.4 Hz, m-C, Ph), 123.8 (C in OAr), 89.2 (CHS), 25.1 (d, JPC=3.4 Hz,
3
1
1
77
MeCH), 16.8 (Me); P NMR (161.98 MHz, CDCl ) δ 52.68 (s, JP=Se=789 Hz); Se NMR (76.31
3
1
1
MHz, CDCl ) δ −206 (d, J =789 Hz); (Se-3n): H NMR (400.13 MHz, CDCl ) δ 7.73 (dd,
3
P=Se
3
3
3
3
3
J
PН=14.4 Hz, JHН=7.5 Hz, 2 Н, Ph), 7.51 (dd, JPН=14.6 Hz, JHН=7.5 Hz, 2 Н, Ph), 7.46-7.34 (m, 4
H, Ph), 7.25-7.20 (m, 2 H, Ph), 6.83 (m, 3 H, OAr), 6.01 (m, 1 H, CHSe), 2.21 (s, 6 H, Me), 2.13 (d,
3
13
1
1
J
HH=6.1 Hz, 3 H, MeCH); C NMR (100.62 MHz, CDCl
3
) δ 152.5 (C in OAr), 133.9 (d, JPC=79.4
2
2,5
Hz, i-C, Ph), 131.2 (p-C, Ph), 130.7 (d, JCP=11.5 Hz, o-C, Ph), 128.4 (C in OAr), 127.8 (d,
3
4
3
31
J =13.4 Hz, m-C, Ph), 123.8 (C in OAr), 88.6 (CHSe), 25.8 (d, J =2.4 Hz, MeCH), 16.8 (Me); P
CP
PC
1
77
1
NMR (161.98 MHz, CDCl
Se=369 Hz).
3 3
) δ 51.09 (s, JP-Se=369 Hz); Se NMR (76.31 MHz, CDCl ) δ 397 (d, JP-
Electrophilic addition of thioselenophosphinic S-acid 4a-c to vinyl ethers 2a, e (Table 2). A
solution of secondary phosphine sulfide 1a-c (1.0 mmol) in 1,4-dioxane (5 mL) and amorphous grey
selenium (79 mg, 1.0 mmol) were placed into a vial filled with argon. The vial was sealed, and the
o
31
suspension stirred at 100 С until the dissolution of selenium residue (ca. 30-40 min). The P NMR
analysis of the resulting solution revealed the formation of thioselenophosphinic S-acid 4a-c in yields
up to 90%. To a prepared solution of acid 4a-c, the corresponding vinyl ether 2a, e (1.0 mmol) was
added and mixture was stirred at ambient temperature for 10 min. The solvent was removed under
o
reduced pressure (1 Torr, 40-45 C), and the residue was purified by flash-chromatography (3 cm of
2 3 3
neutral Al O ; CHCl -hexane, 3:1) to give compounds 3a, c, f.
Co-crystals (1:1) of selenides 5a, b. The thioselenophosphinates S-/Se-3e (271 mg, 0.5 mmol;
o
ratio was ca. 75:25) were stored in wet diethyl ether (20-25 C, 1 week). The solvent was distilled at
lowered pressure. The remaining yellow residue was triturated with hexane, decanted and dried in
vacuo (1 Torr) to give of selenides 5a, b (97 mg) as a light yellow solid. The co-crystals (1:1) of the
31
selenides were grown by the storage of their ether solution within a several days. P NMR (161.98
1
MHz, CDCl
3
): δ = 71.03 and 71.14 (s, JP-Se = 360 Hz) in ratio of ~ 1:3.
Supplementary Material
1
13
31
77
Supplementary data ( H, C, P and Se NMR spectra as well as computational details) associated
with this article can be found in the online version, at … .
2
1

ACCEPTED MANUSCRIPT
Acknowledgements
This work was supported by the Russian Foundation for Basic Research (grants №11-0300334-а and
12-03-31097mol_а) and the President of the Russian Federation (program for the support of leading
№
scientific schools, grant NSh-1550.2012.3).
References and notes
1.
(a) Shibata, T.; Kanaoka, S.; Aoshima, S. J. Am. Chem. Soc. 2006, 128, 7497-7504; (b) Shimomoto, H.; Fukami, D.;
Irita, T.; Katsukawa, K.-I.; Nagai, T.; Kanaoka, S.; Aoshima, S. J. Polymer Sci. A: Polymer Chem. 2012, 50, 1547-
1555.
2
3
.
.
Evano, G.; Blanchard, N.; Toumi, M. Chem. Rev. 2008, 108, 3054-3131.
(a) Trofimov, B. A.; Sukhov, B. G.; Malysheva, S. F.; Belogorlova, N. A.; Tantsirev, A. P.; Parshina, L. N.; Oparina,
L. A.; Tunik, S. P.; Gusarova, N. K. Tetrahedron Lett. 2004, 45, 9143-9145; (b) Gusarova, N. K.; Malysheva, S. F.;
Oparina, L. A.; Belogorlova, N. A.; Tantsyrev, A. P.; Parshina, L. N.; Sukhov, B. G.; Tlegenov, R. T.; Trofimov, B.
A. Arkivoc 2009, vii, 260-267; (c) Oparina, L. A.; Malysheva, S. F.; Gusarova, N. K.; Vysotskaya, O. V.; Stepanov,
A. V.; Belogorlova, N. A.; Albanov, A. I.; Trofimov, B. A. Synthesis 2009, 3427-3432.
4.
Oparina, L. A.; Gusarova, N. K.; Vysotskaya, O. V.; Kolyvanov, N. A.; Artem’ev, A. V.; Trofimov, B. A. Synthesis
2012, 2938-2946.
5.
6.
7.
8.
9.
Kranjc, K.; Kočevar, M. Synlett 2008, 2613-2616.
Marciniec, B.; Kujawa, M.; Pietraszuk, C. New J. Chem. 2000, 24, 671-675.
Castro, A. M. M. Chem. Rev. 2004, 104, 2939-3002.
Friesen, R. W. J. Chem. Soc., Perkin Trans. 1 2001, 1969-2001.
(a) Timokhin, B. V.; Golubin, A. I.; Vysotskaya, O. V.; Kron, V. A.; Oparina, L. A.; Gusarova, N. K.; Trofimov, B.
A. Chem. Heterocycl. Compd. 2002, 38, 981-985; (b) Oparina, L. A.; Vysotskaya, O. V.; Parshina, L. N.; Gusarova,
N. K.; Trofimov, B. A. Phosphorus Sulfur Silicon Relat. Elem. 2003, 178, 2087-2093; (c) Pahadi N. K.; Tunge, J. A.
Synlett 2009, 3135-3138.
10. The Mizoroki-Heck Reaction; Oestreich, M. Ed., Wiley & Sons: Hoboken, NJ, 2009.
11.
(a) Trofimov, B. A. Heteroatomic Derivatives of Acetylene. New Polyfunctional Monomers, Reagents and
Intermediates, Nauka: Moscow, 1981, 319 (in Russian); (b) Salvo, A. D.; David, M.; Crousse, B.; Bonnet-Delpon,
D. Adv. Synth. Catal. 2006, 348, 118-124.
1
1
1
1
2.
(a) Nedolya, N. A.; Zinov’eva, V. P.; Trofimov, B. A. J. Org. Chem. Rus. 1989, 25, 275-279; (b) Nedolya, N. A.;
Papsheva, N. P., Sarapulova, G. I., Afonin, A. V., Trofimov, B. A. Zh. Org. Khim. 1991, 27, 2060-2065.
3. Trofimov, B. A., Amosova, S. V., Ivanova, N. I., Tarasova, O. A., Al'pert, M. L., Dmitrieva, G. V., Sigalov, M. V. Zh.
Org. Khim. 1986, 22, 2145-2149.
4. (a) Kalabina, А. V.; Myn-in’, L.; Donskaya, N. V. Zh. Obshch. Khim. 1964, 34, 1117-1121; (b) Kalabina, А. V.; Myn-
in’, L.; Asalkhaeva, L. D. Zh. Obshch. Khim. 1964, 34, 1113-1117.
5. Gusarova, N. K.; Artem’ev, A. V.; Oparina, L. A.; Kolyvanov, N. A.; Malysheva, S. F.; Vysotskaya, O. V.; Trofimov,
B. A. Synthesis 2012, 431-438.
1
1
6. Kimura, T.; Murai, T.; Miwa, A.; Kurachi, D.; Yoshikawa, H.; Kato, S. J. Org. Chem. 2005, 70, 5611-5617.
7. Artem’ev, A. V.; Oparina, L. A.; Gusarova, N. K.; Kolyvanov, N. A.; Vysotskaya, O. V.; Bagryanskaya, I. Yu.;
Trofimov, B. A. Inorg. Chem. Comm. 2013, 30, 124-127.
18. Chattaraj, P. K.; Maiti, B.; Sarkar, U. J. Phys. Chem. A, 2003, 107, 4973-4975.
1
9. Gaussian 09, Revision A.02, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman,
J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.
P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.;
Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta,
J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand,
J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene,
M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.;
Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G.
A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski,
J.; Fox, D. J. Gaussian, Inc., Wallingford CT, 2009.
20. (a) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899-926; (b) NBO Version 3.1, Glendening, E. D.;
Reed, A. E.; Carpenter, J. E.; Weinhold, F. Theoretical Chemistry Institute, University of Wisconsin, Madison, WI,
1995.
21. Artem’ev, A. V.; Gusarova, N. K.; Bagryanskaya, I. Yu.; Doronina, E. P.; Verkhoturova, S. I.; Sidorkin, V. F.;
Trofimov, B. A. Eur. J. Inorg. Chem. 2013, 415-426.
2
2. Co-crystals of esters S-3b and Se-3b: C24
H
33OPSSe, M = 479.49, T = 150(2) K, monoclinic, space group P2
1
/c, a =
3
-3
1
µ
3.9744(8) Å, b = 10.4250(5) Å and c = 15.9755(8) Å, β = 94.959(2), V = 2318.6(2) Å , Z = 4, dcalc = 1.374 g/cm ,
–
1
(MoK
α
) = 1.791 mm , (θ)max = 60.22°, reflections collected 49847, independent reflections 6806 [R(int) = 0.0452],
= 0.0318, wR = 0.0692, final R indexes [all
data/restraints/parameters: 6806/0/272, final R indexes [I>=2σ (I)]: R
data]: R = 0.0471, wR = 0.0763.
1
2
1
2
2
2

ACCEPTED MANUSCRIPT
2
2
2
3. Co-crystals of selenides 5a and 5b: C H O P S1.77Se1.23, M = 754.27, T = 200(2) K, monoclinic, space group P2 /c,
3
6
42
4
2
1
3
a = 6.0832(3) Å, b = 31.8970(17) Å and c = 19.4135(11) Å, β = 96.163(2), V = 3745.1(3) Å , Z = 4, dcalc = 1.338
-
3
–1
g/cm ,
.0923], data/restraints/parameters 6744/0/426, final R indexes [I>=2σ (I)]: R
indexes [all data]: R = 0.0890, wR = 0.1672.
µ(MoK ) = 1.441 mm , (θ) = 50.76°, reflections collected 62160, independent reflections 6744 [R(int) =
α max
0
1 2
= 0.0512, wR = 0.1407, final R
1
2
4. (a) Sukhov, B. G.; Gusarova, N. K.; Ivanova, N. I.; Bogdanova, M. V.; Kazheva, O. N.; Alexandrov, G. G.;
Dyachenko, O. A.; Sinegovskaya, L. M.; Malysheva, S. F.; Trofimov, B.A. J. Struct. Chem. 2005, 46, 1066; (b)
Malysheva, S. F.; Artem’ev, A. V.; Gusarova, N. K.; Timokhin, B. V.; Tatarinova, A. A.; Trofimov, B. A. Russ. J.
Gen. Chem. 2009, 79, 1617-1621; (c) Malysheva, S. F.; Gusarova N. K.; Artem’ev, A. V.; Belogorlova, N. A.;
Smirnov, V. I.; Shagun, V. A.; Kuimov, V. A.; Trofimov, B. A. Synthetic Comm. 2012, 42, 1685.
5. (a) Trofimov, B. A.; Khil’ko, M. Ya.; Nedolya, N. A.; Demanov, Yu. K.; Vyalykh, E. P. Zhurnal Organicheskoi Khimii
1
1
982, 18, 744; (b) Lavrov, V. I.; Oparina, L. A.; Parshina, L. N.; Vins V. V.; Trofimov, B. A. Russ. J. Appl. Chem.
990, 63, 835; (c) Oparina, L. A.; Shaikhudinova, S. I.; Parshina, L. N.; Vysotskaya, O. V.; Preiss, Th.; Henkelmann,
J.; Trofimov, B. A. Russ. J. Org. Chem. 2005, 41, 656; (d) Oparina, L. A.; Vysotskaya, O. V.; Stepanov, A. V.;
Gusarova, N. K.; Trofimov, B. A. Russ. J. Org. Chem. 2009, 45, 134.
26. Sheldrick, G. M. // SHELX-97 – Programs for Crystal Structure Analysis (Release 97-2). – University of Göttingen,
Germany. – 1997.
27. Sheldrick, G. M. SADABS.Version 2.01. Bruker AXS Inc. Madison, Wisconsin, USA, 2004.
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Supporting Information
Three-component reaction between secondary phosphine sulfides, elemental
selenium and vinyl ethers: the first examples of Markovnikov addition of
thioselenophosphinic acids to double bond
a
a
a
a
Ludmila A. Oparina, Alexander V. Artem’ev, Oksana V. Vysotskaya, Nikita A. Kolyvanov,
b
a
a
Irina Yu. Bagryanskaya, Evgeniya P. Doronina and Nina K. Gusarova*
a
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1
Favorsky St., 664033 Irkutsk, Russian Federation
*
E-mail: gusarova@irioch.irk.ru. Tel: +7(3952)422436. Fax: +7(3952)419346.
b
N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of
Sciences, 9 Lavrentiev Ave., 630090 Novosibirsk, Russian Federation
Table of Contents
TnQTable1Computational
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References……………………………………………………………………………….. S32
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77
H, C, P and Se spectra of the synthesized products
(1-Phenoxyethyl)dicyclohexylphosphinoselenothioate (3a)
Se
P
O
S
P
O
S
Me
Se
Me
S-3a
Se-3a
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[1-(1-Naphthhyloxy)ethyl]dicyclohexylphosphinoselenothioate (3b)
Se
P
O
S
P
O
S
Me
Se
Me
S-3b
Se-3b
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-Phenoxyethyl diphenethylphosphinoselenothioate (3c)
Se
P
O
S
P
O
S
Me
Se
Me
S-3c
Se-3c
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