Oxidative transition-metal-free cross-coupling of secondary phosphine chalcogenides and alcohols or phenols: A facile, expedient synthesis of phosphinochalcogenoic O-esters

Article abstract of DOI:10.1055/s-0030-1260227

Oxidative transition-metal-free, cross-coupling reaction between secondary phosphine chalcogenides and alcohols or phenols proceeds in the carbon tetrachoride/triethylamine system under mild conditions (20-52 C, 1-12 h) to give phosphinochalcogenoic O-est

Full text of DOI:10.1055/s-0030-1260227

PAPER
3723
Oxidative Transition-Metal-Free Cross-Coupling of Secondary Phosphine
Chalcogenides and Alcohols or Phenols: A Facile, Expedient Synthesis of
Phosphinochalcogenoic O-Esters
S
ynthesis of Phosp
i
hinoch
n
a
lcogenoic
O
a
-Esters K. Gusarova, Pavel A. Volkov, Nina I. Ivanova, Ludmila I. Larina, Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk,
Russian Federation
Fax +7(3952)419346; E-mail: boris_trofimov@irioch.irk.ru
Received 28 July 2011; revised 11 August 2011
ture.8 One example deals with the preparation of the O-
isopropyl ester of bis(2-cyanoethyl)phosphinic acid in
16% yield from bis(2-cyanoethyl)phosphine oxide and
propan-2-ol in the system carbon tetrachloride/dibutyl-
amine.8a Another example is the synthesis of the O-iso-
propyl ester of dibutylphosphinothioic acid in 7% yield
from dibutylphosphine sulfide and propan-2-ol.8b To the
best of our knowledge, data on the cross-coupling be-
tween secondary phosphine selenides and alcohols or phe-
nols are absent from the literature.
Abstract: Oxidative transition-metal-free, cross-coupling reaction
between secondary phosphine chalcogenides and alcohols or phe-
nols proceeds in the carbon tetrachoride/triethylamine system under
mild conditions (20–52 °C, 1–12 h) to give phosphinochalcogenoic
O-esters in 70–95% yields.
Key words: secondary phosphine chalcogenides, alcohols, phe-
nols, phosphinochalcogenoic O-esters
The chemistry of phosphinochalcogenoic O-esters has un-
dergone intensive development during recent decades.1–5
These compounds are used as drug precursors,1 ligands
for the design of metal complexes2 (including supramo-
lecular complexes2e), flame retardants for polymeric ma-
terials,3 red fluorescent probes for detecting mercury ions
and O2C– in biological systems and drinking water,4 as
well as building blocks in organic and elementoorganic
synthesis.1g,h,k,5
A great diversity of transition-metal-induced cross-cou-
pling reactions are now successfully employed in modern
organic synthesis.9,10 Apart from the well-known coupling
reactions featured in the 2011 Nobel prize,10 modification
of classic reactions, such as Williamson,11 Ullman,12 and
the like, using transition-metal catalysis have now re-
ceived a new boost, which affects not only carbon–carbon
but also carbon–heteroatom couplings.9a,l–n Despite the
obvious advantages of transition-metal-catalyzed synthe-
ses, their commonly recognized drawbacks and limita-
tions (cost, ecology, toxicity, and other issues) compel the
synthetic community to look for transition-metal-free al-
ternatives.
For instance, esters of phosphinic and phosphinothioic
acids, containing the indole moieties, possess excellent
potency against wild-type HIV-1.1k Some functional esters
of phosphinic and phosphinothioic acids are involved into
the synthesis of antibiotics, e.g., ( )-6-epithienamycin,1a
inhibitors of bacterial ureases,1j and new safe chemother-
apeutic and chemoprophylactic agents against American
trypanosomiasis.1e Phosphinochalcogenoic O-esters are
known to exhibit anti-inflammatory and analgesic ac-
tion.1c
The objective of this paper is the development of a new
general strategy for the facile and effective synthesis of
phosphinochalcogenoic O-esters by oxidative transition-
metal-free cross-coupling of available secondary phos-
phine chalcogenides with diverse alcohols or phenols us-
ing the carbon tetrachloride/triethylamine system.
At the same time the known syntheses of phosphinochal-
cogenoic O-esters are laborious and utilize moisture- and
air-sensitive phosphorus halides and chalcogenolates of
alkali metals.2e,f,h–j,3a,4a,c,5a,b,6
The starting secondary phosphine oxides, sulfides, and se-
lenides 2, 3, 5, and 6 are easily prepared by a halogen-free
method from red phosphorus, styrenes, and elemental
chalcogens (Scheme 1).13
A promising approach to the synthesis of phosphinochal-
cogenoic O-esters is the oxidative cross-coupling reaction
between secondary phosphine chalcogenides and alcohols
or phenols under conditions similar to those of the
Atherton–Todd reaction, which has been systematically
elaborated mainly for dialkyl phosphites;7 reactions of
this type involving secondary phosphine oxides and phos-
phine sulfides have been seldom discussed in the litera-
Our systematic experiments has shown that secondary
phosphine oxides 1, 2, phosphine sulfide 3, and phosphine
selenides 4–6 undergo cross-coupling with alcohols 7–13,
phenol 14, and 1-naphthol 15 in the carbon tetrachloride/
triethylamine system at 20–52 °C for 1–12 hours under an
argon blanket to afford phosphinochalcogenoic O-esters
16a–r in 70–95% isolated yields (Table 1).
As shown in Table 1, primary and secondary alcohols,
prop-2-yn-1-ol, amino alcohols, furfuryl alcohols, as well
as phenols react readily with secondary phosphine chalco-
SYNTHESIS 2011, No. 22, pp 3723–3729
Advanced online publication: 14.09.2011
x
x.
x
x
.
2
0
1
1
DOI: 10.1055/s-0030-1260227; Art ID: Z74111SS
© Georg Thieme Verlag Stuttgart · New York

3724
N. K. Gusarova et al.
PAPER
R
R
R
R
Ph
KOH/DMSO
Ph
Ph
Ph
Ph
X
H
Xn
KOH, H2O
toluene
R
Pred
PH3/H2
P
P
H
C6H6
Xn = O2, S8, Se;
R = H, Me
2,3,5,6
Scheme 1 Halogen-free synthesis of secondary phosphine chalcogenides 2, 3, 5, and 6
genides, which supports the generality of this transition- ride D and the –CCl3 carbanion (step iii). The latter is pro-
metal-free cross-coupling reaction.
tonated by a triethylammonium cation that leads to
regeneration of triethylamine and formation of chloro-
form (step iv). The reaction between chloride D and an al-
cohol (or a phenol) in the presence of triethylamine leads
to the final products, phosphinochalcogenoic O-ester and
triethylammonium chloride (step v). In support of this
mechanism, triethylammonium chloride is always isolat-
ed from the reaction mixture (by filtration) and chloro-
form has been identified by gas chromatography–mass
spectrometry. Also, according to the two first steps of the
The mechanism of the reaction is assumed to include the
following steps (Scheme 2). P,X-Ambidentate chalco-
genophosphinite anion A, resulting from the deprotona-
tion of
a secondary phosphine chalcogenide by
triethylamine (step i), participates in the one-electron
transfer towards carbon tetrachloride (oxidizer) to give
the free radical of secondary phosphine chalcogenide B
and anion radical C (step ii). Then the interconversion of
the species B and C affords phosphinochalcogenoic chlo-
Table 1 Synthesis of Phosphinochalcogenoic O-Esters 16a–ra
R1
R1
R1
R1
X
H
X
CCl4, Et3N, 20–52 °C
HOR2
P
P
+
OR2
1–6
7–15
16a–r
Entry
R1 P(X)H R1
1–6
X
HOR2
7–15
R2
Temp
(°C)
Time
(h)
Product
16a–r
Yield
(%)
2
1
2
1
2
3
3
3
3
4
5
6
5
5
5
6
Ph
O
14
14
7
Ph
20–22
50–52
20–22
20–22
20–22
20–22
20–22
20–22
20–22
50–52
50–52
20–22
20–22
4
4
16a
16b
16c
16d
16e
16f
78
85
80
70
95
87
76
82
95
70
75
80
80
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
Ph
O
Ph
3
S
Me
4.5
6
4
S
8
Et
5
S
14
15
15
7
Ph
1.5
4.5
2
6
S
1-naphthyl
1-naphthyl
Me
7
Se
Se
Se
Se
Se
Se
Se
16g
16h
16i
8
(CH2)2Ph
CH2CH(Me)Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
CH2CH(Me)Ph
2.5
10
10
4
9
7
Me
10
11
12
13
9
i-Pr
16j
10
11
11
CH2C≡CH
(CH2)2NMe2
(CH2)2NMe2
16k
16l
1
7.5
16m
14
15
5
5
(CH2)2Ph
(CH2)2Ph
Se
Se
12
13
20–22
20–22
4.5
8
16n
16o
81
80
O
O
16
17
18
5
5
6
(CH2)2Ph
Se
Se
Se
14
15
15
Ph
20–22
20–22
50–52
1
3
16p
16q
16r
87
82
84
(CH2)2Ph
1-naphthyl
1-naphthyl
CH2CH(Me)Ph
12
a CCl4 (4 mL) and Et3N (1 mmol) were used.
Synthesis 2011, No. 22, 3723–3729 © Thieme Stuttgart · New York

PAPER
Synthesis of Phosphinochalcogenoic O-Esters
3725
carrier He, flow rate 0.7 mL min–1, temperature of injector and ion
source 250 °C, pressure 300 kPa; temperature programming from
70 to 250 °C, at 10 °C per min. Melting points were recorded on a
Stuart melting point apparatus and are uncorrected.
suggested mechanism (the deprotonation of phosphine
chalcogenide and the oxidation of the anion A thus
formed), the ease of the cross-coupling should increase in
the order: selenide > sulfide > oxide, which is consistent
with the experiment data (Table 1, cf. entries 2, 5, and 16).
Additionally, the mechanism implies that the more acidic
starting hydroxy compound, the more facile the reaction
should be (step v), which is also the case (Table 1, cf. en-
tries 4 and 5).
Phosphinochalcogenoic O-Esters 16a–r; General Procedure
A mixture of secondary phosphine chalcogenide 1–6 (1.0 mmol)
and Et3N (1.0 mmol) in CCl4 (4 mL) was stirred at 20–22 °C for 10
min. The alcohol 7–13 (1.0 mmol) or phenol 14, 15 (1.0 mmol) was
added, and the mixture was stirred at 20–52 °C for 1–12 h (see also
Table 1). The solvent was removed under the reduced pressure, and
1,4-dioxane (3 mL) was added. The precipitated white solid
(Et3NHCl) was filtered, and 1,4-dioxane was evaporated under vac-
uum. Then Et2O–hexane (1:1, 3 mL) (for compounds 16a–e) or hex-
ane (3 mL) (for compounds 16h–p,r) was added to the residue
obtained, and the resulting mixture was allowed to stand at 0–1 °C
for 12 h. The soln was removed from the precipitate by decantation,
the solvent was evaporated and the residue was dried under vacuum
to give esters 16a–e,h–p,r. In the case of esters 16f,g,q the residue
(after 1,4-dioxane was evaporated under vacuum) was washed with
hexane (3 × 1 mL) and dried in vacuum to afford 16f,g,q.
(i)
(ii)
R1
R1
R1
R1
X
H
Et3N
R1
R1
CCl4
P
X
X
P
CCl4
+
P
- e–
+
_ Et3HN
A
B
C
R1
R1
X
P
Cl
(iii)
–
B
+
CCl3
C
+
D
(iv)
–
+
CCl3
+
Et3N
+
CHCl3
Et3HN
Diphenylphosphinic O-Phenyl Ester (16a)
White powder; yield: 230 mg (78%); mp 134–135 °C (benzene–
hexane) (Lit.16 135–136 °C).
IR (KBr): 1222 (P–O–C), 1166 cm–1 (P=O).
(v)
Et3N
R1
R1
X
+
HOR2
P
[Et3NH]Cl
D
+
OR2
1H NMR (400.13 MHz, CDCl3): d = 7.05 (m, 1 H, Hp, OPh), 7.16–
7.22, 7.43–7.47, 7.50–7.54 (m, 10 H, Ph, OPh), 7.85–7.91 (m, 4 H,
Ho, Ph, OPh).
X = O, S, Se
Scheme 2 A tentative mechanism for the formation phosphinochal-
cogenoic O-esters 16a–r
3
13C NMR (100.61 Hz, CDCl3): d = 120.60 (d, JPC = 4.8 Hz, Co,
OPh), 124.46 (Cp, OPh), 128.46 (d, 3JPC = 13.6 Hz, Cm, Ph), 129.50
1
In summary, the oxidative transition-metal-free cross-
coupling reaction between secondary phosphine oxides,
sulfides, and selenides and various alcohols and phenols
using the carbon tetrachloride/triethylamine system under
mild conditions affords hitherto essentially unknown
phosphinochalcogenoic O-esters in high yields. The poly-
functional compounds synthesized are prospective
(Cm, OPh), 130.84 (d, JPC = 138.2 Hz, Ci, Ph), 131.66 (d,
2JPC = 10.3 Hz, Co, Ph), 132.32 (d, 4JPC = 3.0 Hz, Cp, Ph), 150.77 (d,
2JPC = 8.5 Hz, Ci, OPh).
31P NMR (161.98 Hz, CDCl3): d = 30.5.
Anal. Calcd for C18H15O2P: C, 73.46; H, 5.14; P, 10.53. Found: C,
73.38; H, 5.09; P, 10.47.
ligands for the preparation of metal complexes, precursors Bis(2-phenylethyl)phosphinic O-Phenyl Ester (16b)
Waxy product; yield: 298 mg (85%).
IR (neat): 1203 (P–O–C), 1163 cm–1 (P=O).
1H NMR (400.13 MHz, CDCl3): d = 2.07–2.25 (m, 4 H, CH2P),
2.88–3.05 (m, 4 H, PhCH2), 7.16–7.39 (m, 15 H, Ph, OPh).
for the design of biologically active compounds and build-
ing blocks for elementoorganic synthesis of novel organ-
ophosphorus compounds.
13C NMR (100.61 Hz, CDCl3): d = 27.90 (d, 2JPC = 2.8 Hz, PhCH2),
29.96 (d, 1JPC = 87.1 Hz, CH2P), 120.57 (d, 3JPC = 4.0 Hz, Co, OPh),
124.78 (Cp, OPh), 126.42 (Cp, Ph), 127.96 (Co, Ph), 128.58 (Cm, Ph),
All reactions were carried out under an argon atmosphere. All sol-
vents were dried and/or purified according to standard procedures.14
Ph2P(O)H (1) was
a commercial product (Aldrich, 2010).
3
Ph2P(Se)H (4) was prepared by oxidation of commercially available
Ph2PH (Aldrich) with grey selenium.15 Secondary phosphine chal-
cogenides 2, 3, 5, 6 were prepared from styrene or a-methylstyrene
and elemental phosphorus (Scheme 1).13
129.79 (Cm, OPh), 140.38 (d, JPC = 14.8 Hz, Ci, Ph), 150.75 (d,
2JPC = 8.8 Hz, Ci, OPh).
31P NMR (161.98 Hz, CDCl3): d = 55.9.
Anal. Calcd for C22H23O2P: C, 75.41; H, 6.62; P, 8.84. Found: C,
75.48; H, 6.67; P, 8.61.
The reaction was monitored using 31P NMR spectra by the disap-
pearance of peaks of the initial secondary phosphine chalcogenides
1–6 and appearance of new peaks corresponding to phosphinochal-
cogenoic O-esters 16a–r. The 1H, 13C, 15N, 31P, and 77Se NMR spec-
tra were recorded on a Bruker DPX 400 and Bruker AV-400
spectrometers (400.13, 100.61, 40.56, 161.98, and 76.31 MHz, re-
spectively) in CDCl3 soln and referenced to TMS (1H, 13C),
CH3NO2 (15N), H3PO4 (31P), and Me2Se (77Se).15N Chemical shifts
Bis(2-phenylethyl)phosphinothioic O-Methyl Ester (16c)
Waxy product; yield: 259 mg (80%).
IR (neat): 1043 (P–O–C), 620 cm–1 (P=S).
1H NMR (400.13 MHz, CDCl3): d = 2.11–2.31 (m, 4 H, CH2P),
2.82–3.00 (m, 4 H, PhCH2), 3.62 (d, 3JPH = 13.3 Hz, 3 H, Me), 7.16–
7.21, 7.24–7.29 (m, 10 H, Ph).
1
were determined to within 0.1 ppm using the 2D H-15N NMR
HMBC technique. IR spectra were run on a Bruker IFS 25 instru-
ment. Mass spectra (electron ionization, 70 eV) were obtained on a
Shimadzu GCMS–QP5050A instrument (quadruple mass analyzer,
the range of detected mass was from 34 to 650 Da). Chromatograph
with capillary column SPB–5ms (60 m × 0.25 mm × 0.25 mm), gas
13C NMR (100.61 Hz, CDCl3): d = 28.91 (PhCH2), 35.62 (d,
2
1JPC = 67.9 Hz, CH2P), 51.37 (d, JPC = 6.4 Hz, Me), 126.37 (Cp),
128.15 (Co), 128.56 (Cm), 140.50 (d, 3JPC = 14.8 Hz, Ci).
31P NMR (161.98 Hz, CDCl3): d = 104.2.
Synthesis 2011, No. 22, 3723–3729 © Thieme Stuttgart · New York

3726
N. K. Gusarova et al.
PAPER
3
Anal. Calcd for C17H21OPS: C, 67.08; H, 6.95; P, 10.18; S, 10.53. 13C NMR (100.61 MHz, CDCl3): d = 115.70 (d, JPC = 6.4 Hz,
Found: C, 66.87; H, 6.96; P, 9.85; S, 10.58.
C2Naphthyl), 121.78 (C6Naphthyl), 124.14 (C4Naphthyl), 124.64
(C3Naphthyl), 125.65 (C8Naphthyl), 126.05 (C7Naphthyl), 127.23 (d,
3JPC = 4.8 Hz, C9Naphthyl), 127.32 (C5Naphthyl), 128.18 (d, 3JPC = 13.6
Hz, Cm), 130.99 (d, JPC = 11.9 Hz, Co), 131.77 (d, JPC = 3.2 Hz,
Cp), 134.34 (C10Naphthyl), 134.47 (d, 1JPC = 98.3 Hz, Ci), 146.76 (d,
3JPC = 9.2 Hz, C1Naphthyl).
Bis(2-phenylethyl)phosphinothioic O-Ethyl Ester (16d)
Waxy product; yield: 223 mg (70%).
IR (neat): 1036 (P–O–C), 610 cm–1 (P=S).
2
4
1H NMR (400.13 MHz, CDCl3): d = 1.31 (t, JHH = 7.1 Hz, 3 H,
3
31P NMR (161.98 MHz, CDCl3): d = 86.0 (s) (+ d satellite,
Me), 2.17–2.34 (m, 4 H, CH2P), 2.88–3.06 (m, 4 H, PhCH2), 4.07
1JPSe = 829.8 Hz).
(dq, 3JPH = 9.8 Hz, 3JHH = 7.1 Hz, 2 H, OCH2), 7.21–7.34 (m, 10 H,
Ph).
77Se NMR (76.31 MHz, CDCl3): d = –238.9 (d, 1JPSe = 829.8 Hz).
3
13C NMR (100.61 Hz, CDCl3): d = 16.53 (d, JPC = 6.6 Hz, Me), Anal. Calcd for C22H17OPSe: C, 64.87; H, 4.21; P, 7.60; Se, 19.39.
2
1
28.78 (d, JPC = 2.2 Hz, PhCH2), 36.30 (d, JPC = 67.5 Hz, CH2P), Found: C, 64.79; H, 4.19; P, 7.41; Se, 18.97.
2
60.99 (d, JPC = 6.6 Hz, OCH2), 126.45 (Cp), 128.26 (Co), 128.66
(Cm), 140.71 (d, 3JPC = 15.1 Hz, Ci).
Bis(2-phenylethyl)phosphinoselenoic O-Methyl Ester (16h)
Waxy product; yield: 288 mg (82%).
IR (neat): 1041 (P–O–C), 581 cm–1 (P=Se).
1H NMR (400.13 MHz, CDCl3): d = 2.31–2.40 (m, 4 H, CH2P),
2.88–3.01 (m, 4 H, PhCH2), 3.62 (d, 3JPH = 13.9 Hz, 3 H, Me), 7.18–
7.23, 7.28–7.31 (m, 10 H, Ph).
31P NMR (161.98 Hz, CDCl3): d = 101.6.
Anal. Calcd for C18H23OPS: C, 67.90; H, 7.28; P, 9.73; S, 10.07.
Found: C, 67.75; H, 7.23; P, 9.68; S, 9.95.
Bis(2-phenylethyl)phosphinothioic O-Phenyl Ester (16e)
Waxy product; yield: 348 mg (95%).
IR (neat): 1201 (P–O–C), 630 cm–1 (P=S).
13C NMR (100.61 MHz, CDCl3): d = 28.87 (PhCH2), 36.65 (d,
1
1JPC = 57.8 Hz, CH2P), 52.53 (d, JPC = 6.3 Hz, Me), 126.18 (Cp),
127.94 (Co), 128.34 (Cm), 139.98 (d, 3JPC = 15.5 Hz, Ci).
1H NMR (400.13 MHz, CDCl3): d = 2.31–2.47 (m, 4 H, CH2P),
2.87–3.08 (m, 4 H, PhCH2), 7.16–7.23, 7.26–7.35 (m, 15 H, Ph, 31P NMR (161.98 MHz, CDCl3): d = 105.3 (s) (+ d satellite,
OPh).
1JPSe = 776.5 Hz).
13C NMR (100.61 Hz, CDCl3): d = 28.83 (PhCH2), 36.22 (d, 77Se NMR (76.31 MHz, CDCl3): d = –308.1 (d, 1JPSe = 776.5 Hz).
1JPC = 66.3 Hz, CH2P), 121.67 (d, JPC = 4.0 Hz, Co, OPh), 125.01
3
Anal. Calcd for C17H21OPSe: C, 58.12; H, 6.03; P, 8.82; Se, 22.48.
(Cp, OPh), 126.46 (Cp, Ph), 128.17 (Co, Ph), 128.61 (Cm, Ph), 129.40
Found: C, 58.09; H, 6.07; P, 8.78; Se, 22.43.
(Cm, OPh), 140.26 (d, 3JPC = 15.6 Hz, Ci, Ph), 150.47 (d, 2JPC = 9.6
Hz, Ci, OPh).
31P NMR (161.98 Hz, CDCl3): d = 103.8.
Bis(2-phenylpropyl)phosphinoselenoic O-Methyl Ester (16i)
Waxy product; yield: 360 mg (95%).
Anal. Calcd for C22H23OPS: C, 72.11; H, 6.33; P, 8.45; S, 8.75. IR (neat): 1051 sh, 1038, 1028 (P–O–C), 534 cm–1 (P=Se).
Found: C, 72.09; H, 6.27; P, 8.31; S, 8.90.
1H NMR (400.13 MHz, CDCl3): d = 1.25, 1.32, and 1.34 (3 d,
3JHH = 7.1 Hz, 3JHH = 8.1 Hz, 3JHH = 7.2 Hz, 6 H, MeCH, respective-
Bis(2-phenylethyl)phosphinothioic O-1-Naphthyl Ester (16f)
White powder; yield: 361 mg (87%); mp 86–88 °C (hexane).
IR (KBr): 1229 (P–O–C), 616 cm–1 (P=S).
ly), 1.77–1.84, 1.94–2.03, 2.08–2.27, 2.34–2.43 (m, 4 H, CH2P),
2.87, 3.20, and 3.26 (3 d, 3JPH = 14.2 Hz, 3JPH = 14.1 Hz, 3JPH = 14.2
Hz, 3 H, OMe, respectively), 3.56–3.48 (m, 2 H, PhCH), 7.15–7.21,
7.24–7.31 (m, 10 H, Ph).
1H NMR (400.13 MHz, CDCl3): d = 2.45–2.61 (m, 4 H, CH2P),
2.95–3.15 (m, 4 H, PhCH2), 7.16–7.17, 7.21–7.32 (m, 10 H, Ph), 13C NMR (100.61 Hz, CDCl3): d = 23.38 (d, JPC = 10.4 Hz,
3
7.44 (dd, JHH = 8.1 Hz, JHH = 7.7 Hz, 1 H, H3Naphthyl), 7.53–7.55 MeCH), 23.56 (d, 3JPC = 11.2 Hz, MeCH), 24.27 (d, 3JPC = 12.0 Hz,
3
3
(m, 2 H, H5, H8Naphthyl), 7.65–7.70 (m, 2 H, H2, H4Naphthyl), 7.87– MeCH), 24.30 (d, 3JPC = 12.4 Hz, MeCH), 35.13 (d, 2JPC = 4.0 Hz,
2
2
7.89 (m, 1 H, H7Naphthyl), 8.06–8.08 (m, 1 H, H6Naphthyl).
PhCH), 35.24 (d, JPC = 3.2 Hz, PhCH), 35.32 (d, JPC = 1.6 Hz,
2
1
PhCH), 35.41 (d, JPC = 2.4 Hz, PhCH), 43.45 (d, JPC = 57.1 Hz,
13C NMR (100.61 Hz, CDCl3): d = 28.70 (d, 2JPC = 2.8 Hz, PhCH2),
1
1
CH2P), 43.79 (d, JPC = 58.3 Hz, CH2P), 44.17 (d, JPC = 57.5 Hz,
1
3
36.32 (d, JPC = 65.9 Hz, CH2P), 115.97 (d, JPC = 5.2 Hz,
C2Naphthyl), 121.15 (C6Naphthyl), 124.33 (C4Naphthyl), 124.99
(C3Naphthyl), 125.87 (C5Naphthyl, C8Naphthyl), 126.16 (Cp), 127.63
1
3
CH2P), 44.64 (d, JPC = 59.5 Hz, CH2P), 51.71 (d, JPC = 6.4 Hz,
3
3
OMe), 52.15 (d, JPC = 6.4 Hz, OMe), 52.31 (d, JPC = 6.4 Hz,
OMe), 126.08–126.24, 126.55–126.88, 128.11–128.25 (m, Co, Cm,
Cp), 145.50–145.80 (m, Ci).
(C7Naphthyl
, C10Naphthyl), 127.84 (Co), 128.30 (Cm), 134.51
3
2
(C9Naphthyl), 139.92 (d, JPC = 15.6 Hz, Ci), 146.47 (d, JPC = 10.4
Hz, C1Naphthyl).
31P NMR (161.98 Hz, CDCl3): d = 104.5.
31P NMR (161.98 Hz, CDCl3): d = 105.0 (s) (+ d satellites,
1JPSe = 769.8 Hz), 107.2 (s) (+ d satellites, 1JPSe = 773.8 Hz), 107.8
(s) (+ d satellites; 1JPSe = 768.7 Hz).
Anal. Calcd for C26H25OPS: C, 74.97; H, 6.05; P, 7.44; S, 7.70.
Found: C, 74.89; H, 5.92; P, 7.23; S, 7.65.
77Se NMR (76.31 Hz, CDCl3): d = –296.0 (d, JPSe = 770.5 Hz),
1
–297.2 (d, 1JPSe = 772.1 Hz), –303.8 (d, 1JPSe = 774.7 Hz).
Diphenylphosphinoselenoic O-1-Naphthyl Ester (16g)
White powder; yield: 310 mg (76%); mp 120–122 °C (hexane).
Anal. Calcd for C19H25OPSe: C, 60.16; H, 6.64; P, 8.17; Se, 20.82.
Found: C, 60.07; H, 6.59; P, 8.02; Se, 20.69.
IR (KBr): 1221 (P–O–C), 566 cm–1 (P=Se).
Bis(2-phenylethyl)phosphinoselenoic O-Isopropyl Ester (16j)
Waxy product; yield: 266 mg (70%).
IR (neat): 1105 (P–O–C), 581 cm–1 (P=Se).
1H NMR (400.13 MHz, CDCl3): d = 7.70 (d, JHH = 7.6 Hz, 1 H,
3
H2Naphthyl), 7.26 (dd, 3JHH = 8.3 Hz, 3JHH = 7.6 Hz, 1 H, H3Naphthyl),
7.45–7.57 (m, 8 H, H5Naphthyl, H8Naphthyl, Hm, Hp), 7.62 (d, 3JHH = 8.3
Hz, 1 H, H4Naphthyl), 7.81–7.83 (m, 1 H, H7Naphthyl), 8.08–8.13 (m, 5 1H NMR (400.13 MHz, CDCl3): d = 1.34 (d, JHH = 6.1 Hz, 6 H,
3
H, H6Naphthyl, Ho).
Me), 2.29–2.45 (m, 4 H, CH2P), 2.88–3.08 (m, 4 H, PhCH2), 4.89
Synthesis 2011, No. 22, 3723–3729 © Thieme Stuttgart · New York

PAPER
Synthesis of Phosphinochalcogenoic O-Esters
3727
(septet, 3JHH = 6.1 Hz, 1 H, OCH), 7.22–7.28, 7.32–7.35 (m, 10 H,
Ph).
MeCH), 24.62 (d, 3JPC = 12.5 Hz, MeCH), 35.27 (d, 2JPC = 4.0 Hz,
PhCH), 35.45 (d, 2JPC = 3.7 Hz, PhCH), 35.61 (m, PhCH), 43.94 (d,
1
1JPC = 57.2 Hz, CH2P), 44.35 (d, JPC = 57.6 Hz, CH2P), 44.46 (d,
13C NMR (100.61 MHz, CDCl3): d = 24.01 (d, 3JPC = 4.4 Hz, Me),
1
1JPC = 58.7 Hz, CH2P), 45.04 (d, JPC = 58.3 Hz, CH2P), 45.64,
1
29.25 (PhCH2), 38.21 (d, JPC = 58.7 Hz, CH2P), 71.34 (d,
45.71 and 45.76 (3 s, NMe), 58.74, 58.98, and 59.01 (3 d, 3JPC = 7.7
Hz, CH2N), 63.25 (d, 2JPC = 6.6 Hz, OCH2), 63.57 (d, 2JPC = 6.9 Hz,
OCH2), 63.69 (d, 2JPC = 6.6 Hz, OCH2), 126.43–128.74 (m, Co, Cm,
2JPC = 6.4 Hz, OCH), 126.43 (Cp), 128.24 (Co), 128.70 (Cm), 140.49
(d, 3JPC = 16.0 Hz, Ci).
31P NMR (161.98 MHz, CDCl3): d = 99.6 (s) (+ d satellite,
1JPSe = 768.3 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –307.9 (d, 1JPSe = 768.3 Hz).
3
3
Cp), 146.03 (d, JPC = 7.3 Hz, Ci), 146.15 (d, JPC = 8.1 Hz, Ci),
146.19 (d, 3JPC = 6.6 Hz, Ci).
31P NMR (161.98 Hz, CDCl3): d = 102.8 (s) (+ d satellites,
1JPSe = 765.4 Hz), 105.3 (s) (+ d satellites, 1JPSe = 769.2 Hz), 105.8
(s) (+ d satellites, 1JPSe = 762.2 Hz).
Anal. Calcd for C19H25OPSe: C, 60.16; H, 6.64; P, 8.17; Se, 20.82.
Found: C, 59.88; H, 6.59; P, 8.08; Se, 20.66.
15N NMR (40.56 Hz, CDCl3): d = –358.8.
77Se NMR (76.31 Hz, CDCl3): d = –290.9 (d, JPSe = 767.1 Hz),
–292.9 to –293.2, –303.0 to –303.3 (2 m, P=Se).
Bis(2-phenylethyl)phosphinoselenoic O-Prop-2-ynyl Ester
(16k)
Waxy product; yield: 281 mg (75%).
1
Anal. Calcd for C22H32NOPSe: C, 60.54; H, 7.39; N, 3.21; P, 7.10;
Se, 18.09. Found: C, 60.44; H, 7.37; N, 3.18; P, 7.01; Se, 17.99.
IR (neat): 1031 (P–O–C), 582 cm–1 (P=Se).
1H NMR (400.13 MHz, CDCl3): d = 3.21–3.31 (m, 4 H, CH2P),
3.39 (s, 1 H, ≡CH), 3.76–3.88 (m, 4 H, PhCH2), 5.52 (d, 3JPH = 14.1
Hz, 2 H, OCH2), 8.04–8.07, 8.14–8.17 (m, 10 H, Ph).
Bis(2-phenylethyl)phosphinoselenoic O-2-Furylmethyl Ester
(16n)
Waxy product; yield: 338 mg (81%).
IR (neat): 1150 (P–O–C), 581 cm–1 (P=Se).
13C NMR (100.61 MHz, CDCl3): d = 29.08 (PhCH2), 37.59 (d,
2
1JPC = 56.4 Hz, CH2P), 53.73 (d, JPC = 4.8 Hz, OCH2), 75.57
(≡CH), 78.85 (d, 3JPC = 5.9 Hz, CH2C≡), 126.51 (Cp), 128.26 (Co),
1H NMR (400.13 MHz, CDCl3): d = 2.16–2.35 (m, 4 H, CH2P),
128.65 (Cm), 140.21 (d, 3JPC = 15.8 Hz, Ci).
3
2.72–2.93 (m, 4 H, PhCH2), 4.97 (d, JPH = 12.8 Hz, 2 H, OCH2),
31P NMR (161.98 MHz, CDCl3): d = 109.5 (s) (+ d satellite,
1JPSe = 785.6 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –305.2 (d, 1JPSe = 785.6 Hz).
3
3
6.33 (dd, JHH = 3.2 Hz, JHH = 1.3 Hz, 1 H, H4furyl), 6.43 (d,
3JPH = 3.2 Hz, 1 H, H3furyl), 7.08–7.17, 7.14–7.17, 7.21–7.25 (m, 10
H, Ph), 7.39 (d, 3JHH = 1.3 Hz, 1 H, H5furyl).
13C NMR (100.61 MHz, CDCl3): d = 29.10 (PhCH2), 37.71 (d,
Anal. Calcd for C19H21OPSe: C, 60.81; H, 5.64; P, 8.25; Se, 21.04.
Found: C, 60.92; H, 5.59; P, 8.21; Se, 20.93.
2
1JPC = 57.1 Hz, CH2P), 59.91 (d, JPC = 5.9 Hz, OCH2), 110.78
(C4furyl), 111.27 (C3furyl), 126.51 (Cp), 128.32 (Co), 128.69 (Cm),
140.41 (d, 3JPC = 15.8 Hz, Ci), 143.56 (C5furyl), 150.17 (d, 3JPC = 5.5
Hz, C2furyl).
Bis(2-phenylethyl)phosphinoselenoic O-2-(Dimethylamino)eth-
yl Ester (16l)
Waxy product; yield: 327 mg (80%).
IR (neat): 1034 (P–O–C), 581 cm–1 (P=Se).
31P NMR (161.98 MHz, CDCl3): d = 105.6 (s) (+ d satellite,
1JPSe = 778.6 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –302.8 (d, 1JPSe = 778.6 Hz).
1H NMR (400.13 MHz, CDCl3): d = 2.29 (s, 6 H, Me), 2.37–2.46
(m, 4 H, CH2P), 2.55 (t, 3JHH = 5.6 Hz, 2 H, 2 H, CH2N), 2.92–3.03
(m, 4 H, PhCH2), 4.05–4.10 (dt, 3JPH = 10.3 Hz, 3JHH = 5.6 Hz, 2 H,
OCH2), 7.20–7.24, 7.28–7.33 (m, 10 H, Ph).
Anal. Calcd for C21H23O2PSe: C, 60.44; H, 5.55; P, 7.42; Se, 18.92.
Found: C, 60.36; H, 5.53; P, 7.29; Se, 18.87.
13C NMR (100.61 MHz, CDCl3): d = 29.12 (PhCH2), 37.43 (d,
Bis(2-phenylethyl)phosphinoselenoic O-(Tetrahydro-2-fur-
yl)methyl Ester (16o)
Waxy product; yield: 337 mg (80%).
IR (neat): 1031 (P–O–C), 582 cm–1 (P=Se).
1H NMR (400.13 MHz, CDCl3): d = 1.53–1.63 (m, 1 H, H3THF),
1.81–1.95 (m, 3 H, H4THF, H3THF), 2.26–2.43 (m, 4 H, CH2P), 2.83–
3.07 (m, 4 H, PhCH2), 3.72–3.85 (m, 3 H, H5THF, OCH2), 3.96–4.07
(m, 2 H, H2THF, H5THF), 7.14–7.18, 7.21–7.26 (m, 10 H, Ph).
1JPC = 58.3 Hz, CH2P), 45.78 (Me), 59.31 (d, 3JPC = 6.7 Hz, CH2N),
2
64.13 (d, JPC = 6.5 Hz, OCH2), 126.43 (Cp), 128.25 (Co), 128.62
(Cm), 140.38 (d, 3JPC = 15.6 Hz, Ci).
31P NMR (161.98 MHz, CDCl3): d = 105.0 (s) (+ d satellite,
1JPSe = 775.2 Hz).
15N NMR (40.56 MHz, CDCl3): d = –358.5.
77Se NMR (76.31 MHz, CDCl3): d = –308.3 (d, 1JPSe = 775.2 Hz).
13C NMR (100.61 MHz, CDCl3): d = 25.76 (C3THF), 27.69 (C4THF),
Anal. Calcd for C20H28NOPSe: C, 58.82; H, 6.91; N, 3.43; P, 7.58;
Se, 19.34. Found: C, 58.69; H, 6.89; N, 3.41; P, 7.49; Se, 19.27.
29.02, 29.30 (2 s, PhCH2), 37.41 (d, 1JPC = 58.7 Hz, CH2P), 38.64
1
2
(d, JPC = 57.1 Hz, CH2P), 68.34 (d, JPC = 6.8 Hz, OCH2), 68.52
(C5THF), 77.56 (d, 3JPC = 7.2 Hz, C2THF), 126.52 (Cp), 128.35 (Co),
128.71 (Cm), 140.48 (d, 3JPC = 15.2 Hz, Ci).
Bis(2-phenylpropyl)phosphinoselenoic O-2-(Dimethylami-
no)ethyl Ester (16m)
Waxy product; yield: 349 mg (80%).
IR (neat): 1035 (P–O–C), 543 sh, 534 cm–1 (P=Se).
31P NMR (161.98 MHz, CDCl3): d = 105.0 (s) (+ d satellite,
1JPSe = 778.4 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –302.9 (d, 1JPSe = 778.4 Hz).
1H NMR (400.13 MHz, CDCl3): d = 1.23, 1.26, 1.33, and 1.37 (4 d,
3
3
3
3JHH = 7.1 Hz, JHH = 7.0 Hz, JHH = 7.1 Hz, JHH = 7.0 Hz, 6 H,
MeCH, respectively), 1.67–1.74, 1.98–2.07, 2.14–2.45 (m, 6 H,
CH2P, CH2N), 2.11, 2.18 and 2.21 (3 s, 6 H, NMe), 3.20–3.36,
3.38–3.53, 3.74–3.86 (m, 4 H, PhCH, OCH2), 7.17–7.36 (m, 10 H,
Ph).
Anal. Calcd for C21H27O2PSe: C, 59.86; H, 6.46; P, 7.35; Se, 18.74.
Found: C, 59.78; H, 6.44; P, 7.29; Se, 18.68.
Bis(2-phenylethyl)phosphinoselenoic O-Phenyl Ester (16p)
Waxy product; yield: 360 mg (87%).
IR (neat): 1198 (P–O–C), 583 cm–1 (P=Se).
3
13C NMR (100.61 Hz, CDCl3): d = 23.79 (d, JPC = 11.0 Hz,
MeCH), 23.83 (d, 3JPC = 11.7 Hz, MeCH), 24.58 (d, 3JPC = 12.5 Hz,
Synthesis 2011, No. 22, 3723–3729 © Thieme Stuttgart · New York

3728
N. K. Gusarova et al.
PAPER
1H NMR (400.13 MHz, CDCl3): d = 2.49–2.58 (m, 4 H, CH2P),
2.97–3.09 (m, 4 H, PhCH2), 7.18–7.23, 7.28–7.37 (m, 15 H, Ph,
OPh).
Anal. Calcd for C28H29OPSe: C, 68.43; H, 5.95; P, 6.30; Se, 16.07.
Found: C, 68.29; H, 5.91; P, 6.18; Se, 15.98.
13C NMR (100.61 MHz, CDCl3): d = 29.11 (PhCH2), 37.37 (d,
Acknowledgment
3
1JPC = 56.4 Hz, CH2P), 121.82 (d, JPC = 4.1 Hz, Co, OPh), 125.22
(Cp, OPh), 126.58 (Cp, Ph), 128.28 (Co, Ph), 128.69 (Cm, Ph), 129.48
(Cm, OPh), 140.08 (d, 3JPC = 15.5 Hz, Ci, Ph), 150.52 (d, 2JPC = 9.6
Hz, Ci, OPh).
This work was supported by the President of the Russian Federation
(program for the support of leading scientific schools, grant no.
NSh-3230.2010.3 and young Russian scientists MK-629.2010.3).
31P NMR (161.98 MHz, CDCl3): d = 104.3 (s) (+ d satellite,
1JPSe = 803.1 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –246.8 (d, 1JPSe = 803.1 Hz).
References
(1) (a) Bateson, J. H.; Robins, A. M.; Southgate, R. J. Chem.
Soc., Perkin Trans. 1 1991, 29. (b) Tawata, S.; Taira, S.;
Kobamoto, N.; Ishihara, M.; Toyama, S. Biosci. Biotechnol.
Biochem. 1996, 60, 1643. (c) Beznosko, B. K.; Usanova, V.
M.; Zhuravleva, L. V.; Baulin, V. E.; Yarkevich, A. N.;
Syundyukova, V. Ch.; Tsvetkov, E. N. Pharm. Chem. J.
(Engl. Transl.) 1997, 31, 638. (d) Li, Y.; Aubert, S. D.;
Maes, E. G.; Raushel, F. M. J. Am. Chem. Soc. 2004, 126,
8888. (e) Ravaschino, E. L.; Docampo, R.; Rodriguez, J. B.
J. Med. Chem. 2006, 49, 426. (f) Vassiliou, S.; Xeilari, M.;
Yiotakis, A.; Grembecka, J.; Pawełczak, M.; Kafarski, P.;
Mucha, A. Bioorg. Med. Chem. 2007, 15, 3187. (g) Yang,
Y.; Coward, J. K. J. Org. Chem. 2007, 72, 5748.
Anal. Calcd for C22H23OPSe: C, 63.93; H, 5.61; P, 7.49; Se, 19.10.
Found: C, 63.89; H, 5.59; P, 7.43; Se, 18.92.
Bis(2-phenylethyl)phosphinoselenoic O-1-Naphthyl Ester (16q)
Gray solid; yield: 380 mg (82%); mp 95–97 °C (hexane).
IR (KBr): 1228 (P–O–C), 587 cm–1 (P=Se).
1H NMR (400.13 MHz, CDCl3): d = 2.64–2.72 (m, 4 H, CH2P),
2.97–3.16 (m, 4 H, PhCH2), 7.17–7.20 (m, 4 H, Hp), 7.23–7.33 (m,
6 H, Ho, Hm), 7.45 (dd, 3JHH = 8.1 Hz, 3JHH = 7.8 Hz, 1 H, H3Naphthyl),
7.53–7.56 (m, 2 H, H5, H8Naphthyl), 7.69–7.72 (m, 2 H, H2,
H4Naphthyl), 7.87–7.89 (m, 1 H, H7Naphthyl), 8.05–8.08 (m, 1 H,
H6Naphthyl).
(h) Klimek-Ochab, M.; Żymańczyk-Duda, E.; Brzezińska-
Rodak, M.; Majewska, P.; Lejczak, B. Tetrahedron:
Asymmetry 2008, 19, 450. (i) Majewska, P.; Doskocz, M.;
Lejczak, B.; Kafarski, P. Tetrahedron: Asymmetry 2009, 20,
1568. (j) Vassiliou, S.; Kosikowska, P.; Grabowiecka, A.;
Yiotakis, A.; Kafarski, P.; Berlicki, Ł. J. Med. Chem. 2010,
53, 5597. (k) Alexandre, F.-R.; Amador, A.; Bot, S.; Caillet,
C.; Convard, T.; Jakubik, J.; Musiu, C.; Poddesu, B.; Vargiu,
L.; Liuzzi, M.; Roland, A.; Seifer, M.; Standring, D.; Storer,
R.; Dousson, C. B. J. Med. Chem. 2011, 54, 392.
13C NMR (100.61 MHz, CDCl3): d = 29.54 (PhCH2), 38.01 (d,
1JPC = 58.6 Hz, CH2P), 116.30 (d, 3JPC = 5.5 Hz, C2Naphthyl), 121.62
(C6Naphthyl), 124.84 (C4Naphthyl), 125.24 (C3Naphthyl), 126.26 (C5,
C8Naphthyl), 126.59 (Cp), 128.02 (C7, C10Naphthyl), 128.25 (Co),
3
128.69 (Cm), 134.85 (C9Naphthyl), 140.03 (d, JPC = 15.8 Hz, Ci),
147.09 (d, 3JPC = 11.0 Hz, C1Naphthyl).
31P NMR (161.98 MHz, CDCl3): d = 105.1 (s) (+ d satellite,
1JPSe = 804.2 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –236.4 (d, 1JPSe = 804.2 Hz).
(2) (a) Abbas, S.; Beagley, B.; Godfrey, S. M.; Kelly, D. G.;
McAuliffe, C. A.; Pritchard, R. G. J. Chem. Soc., Dalton
Trans. 1992, 1915. (b) Lukin, O.; Vysotsky, M. O.;
Kalchenko, V. I. J. Phys. Org. Chem. 2001, 14, 468.
(c) Cauzzi, D.; Graiff, C.; Pattacini, R.; Predieri, G.;
Tiripicchio, A.; Kahlal, S.; Saillard, J.-Y. Eur. J. Inorg.
Chem. 2004, 1063. (d) Eisler, D. J.; Puddephatt, R. J. Inorg.
Chem. 2006, 45, 7295. (e) Reger, D. L.; Semeniuc, R. F.;
Smith, M. D. Dalton Trans. 2008, 2253. (f) Adati, R. D.;
Davolos, M. R.; Jafelicci, M.; Lima, S. A. M.; Viegas, C.
Phys. Status Solidi C 2009, 6, 542. (g) Li, C.; Pattacini, R.;
Braunstein, P. Inorg. Chim. Acta 2010, 363, 4337.
Anal. Calcd for C26H25OPSe: C, 67.39; H, 5.44; P, 6.68; Se, 17.04.
Found: C, 67.31; H, 5.46; P, 6.59; Se, 16.98.
Bis(2-phenylpropyl)phosphinoselenoic O-1-Naphthyl Ester
(16r)
Waxy product; yield: 413 mg (84%).
IR (neat): 1228 (P–O–C), 568 cm–1 (P=Se).
1H NMR (400.13 MHz, CDCl3): d = 1.27, 1.33, and 1.41 (3 d,
3JHH = 7.1 Hz, 6 H, MeCH), 1.98–2.06, 2.27–2.67 (m, 4 H, CH2P),
3.33–3.62 (m, 2 H, PhCH), 6.84 (dd, 3JHH = 7.5 Hz, 3JHH = 0.9 Hz,
1 H, H4Naphthyl), 7.11–7.42, 7.44–7.54 (m, 13 H, Ph, H3Naphthyl
,
(h) Kozlov, V. A.; Aleksanyan, D. V.; Nelyubina, Y. V.;
Lyssenko, K. A.; Vasil’ev, A. A.; Petrovskii, P. V.; Odinets,
I. L. Organometallics 2010, 29, 2054. (i) Aleksanyan, D.
V.; Kozlov, V. A.; Nelyubina, Y. V.; Lyssenko, K. A.;
Puntus, L. N.; Gutsul, E. I.; Shepel, N. E.; Vasil’ev, A. A.;
Petrovskii, P. V.; Odinets, I. L. Dalton Trans. 2011, 40,
1535. (j) Kozlov, V. A.; Aleksanyan, D. V.; Vasil’ev, A. A.;
Petrovskii, P. V.; Odinets, I. L. Phosphorus, Sulfur Silicon
Relat. Elem. 2011, 186, 626.
H5Naphthyl, H8Naphthyl), 7.60–7.66, 7.73–7.76 (m, 1 H, H2Naphthyl),
7.82–7.88 (m, 1 H, H7Naphthyl), 8.21–8.25 (m, 1 H, H6Naphthyl).
3
13C NMR (100.61 Hz, CDCl3): d = 23.73 (d, JPC = 11.2 Hz,
MeCH), 24.09 (d, 3JPC = 12.8 Hz, MeCH), 24.34 (d, 3JPC = 10.8 Hz,
MeCH), 24.50 (d, 3JPC = 10.8 Hz, MeCH), 35.54 (d, 2JPC = 4.4 Hz,
2
PhCH), 35.76 (d, JPC = 2.0 Hz, PhCH), 35.98 (PhCH), 44.27 (d,
1
1JPC = 54.7 Hz, CH2P), 44.71 (d, JPC = 55.5 Hz, CH2P), 45.25 (d,
1JPC = 53.1 Hz, CH2P), 108.71 (C4Naphthyl), 114.78 (d, 3JPC = 6.0 Hz,
C2Naphthyl), 115.73 (d, 3JPC = 5.9 Hz, C2Naphthyl), 116.01 (d, 3JPC = 6.0
Hz, C2Naphthyl), 120.46 (C3Naphthyl), 121.72 (C6Naphthyl), 121.75
(C10Naphthyl), 124.28–124.51, 125.15, 125.90–126.03, 126.37–
(3) (a) Noetzel, S.; Jastrow, H.; Uebe, R. US 4111900, 1978.
(b) Howell, B. A.; Carter, K. E. J. Therm. Anal. Calorim.
2010, 102, 493.
(4) (a) Xu, K.; Liu, X.; Tang, B.; Yang, G.; Yang, Y.; An, L.
Chem. Eur. J. 2007, 13, 1411. (b) Xu, K.; Liu, X.; Tang, B.
ChemBioChem 2007, 8, 453. (c) Tang, B.; Ding, B.; Xu, K.;
Tong, L. Chem. Eur. J. 2009, 15, 3147.
(5) (a) Chen, B.-Q.; Kameyama, A.; Nishikubo, T. J. Polym.
Sci., Part A: Polym. Chem. 1999, 37, 1009. (b) Clive, D. L.
J.; Kang, S. J. Org. Chem. 2001, 66, 6083. (c) Dunne, K. S.;
Bisaro, F.; Odell, B.; Paris, J.-M.; Gouverneur, V. J. Org.
128.24, 128.41–128.77 (m, Co, Cp, Cm; C5Naphthyl, C7Naphthyl
C8Naphthyl), 134.81 (d, JPC = 3.5 Hz, C9Naphthyl), 145.47–145.61,
145.92–146.11, 146.93–147.20 (m, Ci), 151.62 (C1Naphthyl).
31P NMR (161.98 Hz, CDCl3): d = 102.1 (s) (+ d satellites,
1JPSe = 787.6 Hz), 105.2 (s) (+ d satellites, 1JPSe = 797.4 Hz), 107.1
(s) (+ d satellites, 1JPSe = 799.6 Hz).
,
3
1
77Se NMR (76.31 Hz, CDCl3): d = –222.8 (d, JPSe = 795.3 Hz),
–217.8 (d, 1JPSe = 796.9 Hz), –206.3 (d, 1JPSe = 794.8 Hz).
Synthesis 2011, No. 22, 3723–3729 © Thieme Stuttgart · New York

PAPER
Chem. 2005, 70, 10803. (d) Um, I.-H.; Shin, Y.-H.; Han,
Synthesis of Phosphinochalcogenoic O-Esters
3729
F.; Wang, J.-X. Tetrahedron 2011, 67, 4914. (k) Perez, F.;
Minatti, A. Org. Lett. 2011, 13, 1984. (l) Anokhin, M. V.;
Averin, A. D.; Buryak, A. K.; Beletskaya, I. P. Mendeleev
Commun. 2011, 21, 132. (m) Beletskaya, I. P.; Ananikov, V.
P. Chem. Rev. 2011, 111, 1596. (n) Huang, Y.-B.; Yang, C.-
T.; Yi, J.; Deng, X.-J.; Fu, Y.; Liu, L. J. Org. Chem. 2011,
76, 800.
J.-Y.; Mishima, M. J. Org. Chem. 2006, 71, 7715. (e) Um,
I.-H.; Akhtar, K.; Shin, Y.-H.; Han, J.-Y. J. Org. Chem.
2007, 72, 3823. (f) Cheruku, P.; Gohil, S.; Andersson, P. G.
Org. Lett. 2007, 9, 1659. (g) Harvey, J. S.; Malcolmson, S.
J.; Dunne, K. S.; Meek, S. J.; Thompson, A. L.; Schrock, R.
R.; Hoveyda, A. H.; Gouverneur, V. Angew. Chem. Int. Ed.
2009, 48, 762. (h) Lam, K.; Markó, I. E. Org. Lett. 2011, 13,
406.
(10) See, for example: (a) Kienle, M.; Knochel, P. Org. Lett.
2010, 12, 2702. (b) Petrović, Z. D.; Simijonović, D.;
Petrović, V. P.; Marković, S. J. Mol. Catal. A: Chem. 2010,
327, 45. (c) Ren, G.; Cui, X.; Yang, E.; Yang, F.; Wu, Y.
Tetrahedron 2010, 66, 4022. (d) Zhou, J.; Li, X.; Sun, H.
J. Organomet. Chem. 2010, 695, 297. (e) Srinivas, P.;
Srinivas, K.; Likhar, P. R.; Sridhar, B.; Mohan, K. V.;
Bhargava, S.; Kantam, M. L. J. Organomet. Chem. 2011,
696, 795. (f) Wang, J.; Song, G.; Peng, Y. Tetrahedron Lett.
2011, 52, 1477. (g) Tanaka, M.; Hikawa, H.; Yokoyama, Y.
Tetrahedron 2011, 67, 5897. (h) Zhang, T.; Gao, X.; Wood,
H. B. Tetrahedron Lett. 2011, 52, 311.
(11) (a) Nguyen, V. T. H.; Appel, B.; Langer, P. Tetrahedron
2006, 62, 7674. (b) Maślińska-Solich, J.; Kukowka, S.;
Markowski, P. React. Funct. Polym. 2008, 68, 544.
(c) Trujillo, A.; Fuentealba, M.; Carrillo, D.; Manzur, C.;
Hamon, J.-R. J. Organomet. Chem. 2009, 694, 1435.
(12) (a) Venkatraman, S.; Li, C.-J. Tetrahedron Lett. 2000, 41,
4831. (b) Schaarschmidt, D.; Lang, H. Organometallics
2010, 29, 4196. (c) Chen, W.; Wang, M.; Li, P.; Wang, L.
Tetrahedron 2011, 67, 5913.
(6) (a) Stuebe, C.; LeSuer, W. M.; Norman, G. R. J. Am. Chem.
Soc. 1955, 77, 3526. (b) Balakrishna, M. S.; Panda, R.;
Mague, J. T. J. Chem. Soc., Dalton Trans. 2002, 4617.
(c) Marosi, G.; Toldy, A.; Parlagh, G.; Nagy, Z.; Ludányi,
K.; Anna, P.; Keglevich, G. Heteroat. Chem. 2002, 13, 126.
(d) Balakrishna, M. S.; George, P. P.; Mobin, S. M.
Polyhedron 2005, 24, 475. (e) Kimura, T.; Murai, T. J. Org.
Chem. 2005, 70, 952. (f) Baysal, A.; Aydemir, M.; Durap,
F.; Gümgüm, B.; Özkar, S.; Yildirim, T. L. Polyhedron
2007, 26, 3373. (g) Williams, D. B. G.; Netshiozwi, T. E.
Tetrahedron 2009, 65, 9973. (h) Zhou, Y.; Wang, G.; Saga,
Y.; Shen, R.; Goto, M.; Zhao, Y.; Han, L.-B. J. Org. Chem.
2010, 75, 7924.
(7) Hassner, A.; Stumer, C. In Tetrahedron Organic Chemistry
Series, Vol. 22; Elsevier: New York, 2002, 443.
(8) (a) Rauhut, M. M.; Currier, H. A. J. Org. Chem. 1961, 26,
4628. (b) Peters, G. J. Org. Chem. 1962, 27, 2198.
(c) Wang, G.; Shen, R.; Xu, Q.; Goto, M.; Zhao, Y.; Han,
L.-B. J. Org. Chem. 2010, 75, 3890.
(9) See, for example: (a) Bravo-Altamirano, K.; Huang, Z.;
Montchamp, J.-L. Tetrahedron 2005, 61, 6315. (b) Alonso,
F.; Beletskaya, I. P.; Yus, M. Tetrahedron 2008, 64, 3047.
(c) He, C.-Y.; Fan, S.; Zhang, X. J. Am. Chem. Soc. 2010,
132, 12850. (d) Cahiez, G.; Moyeux, A. Chem. Rev. 2010,
110, 1435. (e) Ishizuka, K.; Seike, H.; Hatakeyama, T.;
Nakamura, M. J. Am. Chem. Soc. 2010, 132, 13117.
(f) Zhou, Z.-Z.; Liu, F.-S.; Shen, D.-S.; Tan, C.; Luo, L.-Y.
Inorg. Chem. Commun. 2011, 14, 659. (g) Kitamura, M.;
Sakata, R.; Okauchi, T. Tetrahedron Lett. 2011, 52, 1931.
(h) Zhong, R.; Wang, Y.-N.; Guo, X.-Q.; Hou, X.-F.
J. Organomet. Chem. 2011, 696, 1703. (i) He, Y.; Cai, C.
Catal. Commun. 2011, 12, 678. (j) Du, Z.; Zhou, W.; Wang,
(13) (a) Arbuzova, S. N.; Gusarova, N. K.; Trofimov, B. A.
ARKIVOC 2006, (v), 12. (b) Trofimov, B. A.; Gusarova, N.
K. Mendeleev Commun. 2009, 19, 295. (c) Malysheva, S.
F.; Artem’ev, A. V.; Gusarova, N. K.; Timokhin, B. V.;
Tatarinova, A. A.; Trofimov, B. A. Russ. J. Gen. Chem.
(Engl. Transl.) 2009, 79, 1617.
(14) Armarego, W. L. E.; Chai, C. L. L. Purification of
Laboratory Chemicals, 5th ed.; Elsevier Science: New York,
2003.
(15) Maier, L. Helv. Chim. Acta 1966, 49, 1000.
(16) Berlin, K. D.; Austin, T. N.; Nagadhushanam, M. J. Org.
Chem. 1965, 30, 1267.
Synthesis 2011, No. 22, 3723–3729 © Thieme Stuttgart · New York