Stereoselective free-radical addition of secondary phosphine selenides to aromatic acetylenes

Article abstract of DOI:10.1016/j.jorganchem.2008.11.043

Free-radical addition (AIBN, 65-70 °C, 5-7 h) of secondary phosphine selenides to arylacetylenes proceeds stereoselectively to give anti-Markovnikov adducts of predominantly Z-configuration (up to 97%) in 60-80% isolated yields, thus representing a rare e

Full text of DOI:10.1016/j.jorganchem.2008.11.043

Journal of Organometallic Chemistry 694 (2009) 677–682
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Stereoselective free-radical addition of secondary phosphine
selenides to aromatic acetylenes
*
Boris A. Trofimov , Nina K. Gusarova, Svetlana N. Arbuzova, Nina I. Ivanova, Alexander V. Artem’ev,
Pavel A. Volkov, Igor’ A. Ushakov, Svetlana F. Malysheva, Vladimir A. Kuimov
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., Irkutsk 664033, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 1 October 2008
Received in revised form 19 November 2008
Accepted 21 November 2008
Available online 30 November 2008
Free-radical addition (AIBN, 65–70 °C, 5–7 h) of secondary phosphine selenides to arylacetylenes pro-
ceeds stereoselectively to give anti-Markovnikov adducts of predominantly Z-configuration (up to 97%)
in 60–80% isolated yields, thus representing a rare example of stereoselective free-radical addition to
the triple bond. Microwave irradiation (600 W) of the reactants with the same content of AIBN reduces
the reaction time to 8 min though compromises the stereoselectivity. Under UV-initiation the reaction
loses its stereoselectivity due to isomerization of the primary Z-adducts. In this reaction, a specific facil-
itating and Z-configuration-controlling effect of aromatic substituents at the triple bond has been
revealed.
Keywords:
Free-radical addition
Secondary phosphine selenides
Acetylenes
Ó 2008 Elsevier B.V. All rights reserved.
Microwave activation
1. Introduction
[4], thiols [4e], phosphines [5], and carbanion [6] species) and
other [7] reactants to afford functional phosphine chalcogenides.
Stereoselective addition of diverse compounds to substituted
acetylenes is a subject of continuous attention of synthetic com-
munity [1]. A lot of efforts keep being undertaken to effect the
addition as selective as possible. To meet this goal, particularly
productive is application of transition metal catalysts [1a–c, f–h].
However, the reliable control of stereoselective addition to the tri-
ple bond still remains a synthetic challenge and the investigations
in this area are being extended. In numerous publications concern-
ing this important issue, the free-radical addition to the triple bond
is still almost neglected, since it is accepted as a common place
that such processes are not stereoselective. Among rare exceptions
is our recent short communication [2] about stereoselective addi-
tion of secondary phosphine sulfides to aryl- and hetarylacetyl-
enes. This finding stimulates us to pay closer attention to the
free-radical addition to acetylenes as a prospective source of iso-
merically pure 1,2-substituted alkenes. Therefore, we have studied
the free-radical addition of available [3] secondary phosphine sel-
enides to acetylenes. Apart from addressing the steroselectivity is-
sue which could have an impact on wide circles of organic
chemists, we have also followed the straight synthetic goal to de-
velop a short-cut to a novel family of alkenylphosphine selenides.
Alkenylphosphine chalcogenides are highly reactive building
blocks which interact readily with different nucleophilic (amines
The latter are widely applied as hemilabile ligands for the design
of advanced catalysts [8], flame retardants [9], extractants of rare
earth and transuranic elements [10], precursors and coordinating
solvents for the synthesis of conductive nanomaterials [11].
2. Results and discussion
We found that in the presence of azaisobutyronitrile (AIBN) at
65–70 °C (5–7 h, no solvent) secondary phosphine selenides 1–4
added to phenylacetylene 5 (3-fold molar excess) to give anti-
Markovnikov adducts 6a-d of Z-configuration predominantly in
60–80% isolated yield (Table 1). The only exclusion was the result
obtained for the most bulky phosphine selenide
3 (R = 4-t-
BuC6H4CH2CH2), when the Z-selectivity dropped (Z-isomer content
in the adduct mixture was 75%), obviously due to steric compres-
sion. Despite the remarkable difference in the phosphine selenide
1-4 structure, no noticeable substituents effect on the adduct yield
was observed (the yield ranges 70–80%). Only in the case of the
compound 4 with 2-pyridylethyl moieties the yield decreased to
60% at a longer reaction time (7 h), that was likely associated with
a lower stability of both PH-reagent 4 and adduct 6d.
The microwave irradiation (600 W) of the reaction mixture
(equimolar ratio of the reactants, AIBN, dioxane as a solvent) accel-
erated the addition dramatically: in 50 s the conversion of the ini-
tial phosphine selenide 2 was 60% (NMR 31P), the Z-selectivity
retaining 90%. At a longer microwave irradiation (8 min), the com-
plete conversion of 2 was reached (the isolated yield of adduct 6b
* Corresponding author. Fax: +7 3952 419346.
E-mail address: boris_trofimov@irioch.irk.ru (B.A. Trofimov).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.11.043

678
B.A. Trofimov et al. / Journal of Organometallic Chemistry 694 (2009) 677–682
Table 1
Stereoselective addition of secondary phosphine selenides to phenylacetylenea.
R1
R1
R1
Se
AIBN (2 mass %)
65-70 oC, 5-7 h
P
Ph
P
Ph
+
Se
6a-d
R1
H
1-4
5
Initial phosphine selenide
R1
Time, h
Adduct 6
Yield, %
Z-isomer contentd, %
b
c
1
2
3
Ph
Ph(CH2)2
5
5
5
a
b
c
90
86
85
75
70
80
97
91
75
(CH2)2
4
7
d
75
60
95
(CH2)2
N
a
All experiments were carried out under argon atmosphere. Molar ratio of reactants 1–4:5 = 1:3.
b
c
Calculated based on 31P NMR spectra of the crude products.
Isolated yield (based on the quantity of phosphine selenide 1-4 charged), conversion of the latter is 100%.
d
Determined by 31P NMR spectra of the crude products.
was 70%), though the addition selectivity was lost (Z:E = 52:48),
Scheme 1.
proved to be practically inactive in the addition studied. For exam-
ple, in the case of 1-hexyne and phosphine selenide 2 under the
above conditions (AIBN, 65–70 °C) the conversion of 2 was 14%
only (31P NMR), though the reaction time was 2.4 times longer
(12 h). Another substituted alkyne, 2-propyne-1-ol (phosphine sel-
enide 2, AIBN, 65–70 °C, 25 h or UV-irradiation, 20 h), turned out to
be completely inactive in this addition.
Therefore, it is the aromatic or heteroaromatic substituent at
the triple bond that makes the addition both possible and
stereoselective.
The strong activation influence of aromatic and heteroaromatic
substituents on rate and stereoselectivity of the addition can be
rationalized as follows (Scheme 3): the initial radical-adduct A is
capable of stabilizing by electronic interaction with adjacent aro-
matic (or heteroaromatic) ring to distribute the radical center over
the aromatic system (form B). The further through-space spin
interaction with the P@Se moiety closes the 6-membered ring rad-
ical C. Such an intra-molecular single-electron bonding should se-
cure substituents of the adducts formed in the cis (Z) disposition.
It is pertinent to note that secondary phosphines show low
reactivity in the reactions of radical addition to the triple bond.
For example, the heating (65–70 °C, 5 h) of bis(2-phenyl-
ethyl)phosphine with phenylacetylene in the presence of AIBN
gave phosphine 9 in 12% yield, the conversion of initial phosphine
being 15% (31P NMR). At the same time we managed to obtain
phosphine 9 (as a mixture Z:E = 80:20) in almost quantitative
It clearly shows that microwave activation facilitates both the
addition reaction and the Z- to E- isomerization. Despite this disad-
vantage the microwave assistance of the free-radical addition of
secondary phosphine selenides to acetylenes can be successfully
used when the isomer composition of the adduct is not of primary
importance.
The same was true for the UV-initiated addition of secondary
phosphine selenides to acetylenes which proved to be almost as
effective as that initiated by AIBN (when the adduct yields were
concerned). In this case the yields of the adducts ranged from
53% to 80%, while the reaction lasted 4–6 h. However, as expected,
UV-irradiation caused the rapid Z- to E-isomerization of the ad-
ducts and hence the stereoselectivity was breached (Table 2).
The easy Z- to E-isomerization of the adducts under the action
of UV-irradiation was illustrated by the photochemical (the same
UV-source, 7 h) conversion of Z-adduct 6a (Z-isomer content
97%) to the mixture of Z- and E-isomers in ꢀ1:1 ratio (Scheme 2).
From the comparison of the adduct yields for phenylacetylene
(adduct 6a, yield 88%) and 2-naphtylacetylene (adduct 6e, yield
60%), it may be concluded that the steric requirements are impor-
tant for the photochemical version of the addition (Table 2).
However, a key contribution to the substituent effect on this
reaction belongs to electronic and specific interaction in the inter-
mediate radical adduct. It follows from the fact that alkynes were
Se
H
AIBN (2 mass %)
MW (600 W)
P
P
+
Ph
Ph
Se
5
2
6b
50 sec: conversion of 2 = 60%; 6b, Z : E = 90 : 10
8 min: conversion of 2 = 100%; 6b, Z : E = 52 : 48
Scheme 1. Reaction of phosphine selenide 2 with phenylacetylene 5 under microwave irradiation.

B.A. Trofimov et al. / Journal of Organometallic Chemistry 694 (2009) 677–682
679
Table 2
Addition of secondary phosphine selenides to acetylenes under UV-initiationa.
R1
Se
R1
R1
UV
R2
P
P
R2
+
Se
R1
H
4-6 h
1-3
5, 7, 8
6a, c, e-g
Initial phosphine selenide
Acetylene
R2
Time, h
Adduct 6
Yield, %
Z:Ed, %
b
c
1
1
5
7
Ph
4
4
a
e
88
60
80
53
60:40
60:40
2
2
7
8
5
5
6
4
f
77
65
68
74
60
65
50:50
35:65
60:40
g
c
O
3
Ph
a
UV-irradiation (200-W Hg arc lamp), quartz ampoule, solvent – dioxane, argon atmosphere, molar ratio of reactants 1–3:5,7,8 = 1:1.
Calculated based on 31P NMR spectra of the crude products.
b
c
Isolated yield (based on the quantity of phosphine selenide 1–3 charged), conversion of the latter was 100%.
d
Determined by 31P NMR spectra of the crude products.
yield by the reduction of Z-isomer of the corresponding phosphine
selenide 6b with metal sodium in toluene (reflux, 0.5 h) (Scheme
4).
Ph
Ph
Ph
Ph
Ph
UV
7 h
3. Conclusions
6a
P
+
P
Ph
Se
Se
In summary, a facile stereoselective free-radical addition of avail-
able3 secondary phosphine selenides to aromatic and heteroaro-
matic acetylenes has been found. A specific effect of an aromatic
substituent in acetylenes that facilitates the reaction and fixes
Z-configuration of the adducts has been observed. The results
presented contribute to fundamental and synthetic chemistry of
Z-isomer
content 97%
50%
:
50%
Scheme 2. Z- to E-isomerization of the adducts under UV-initiation (200-W Hg arc
lamp, quartz ampoule, solvent – dioxane).
+
P
Se
P
P
P
Se
Se
C
Se
A
B
Scheme 3.
Na, toluene
reflux, 0.5 h
- Na2Se
Ph
P
6b
Z-isomer
+
Ph
P
9
80%
:
20%
Scheme 4.

680
B.A. Trofimov et al. / Journal of Organometallic Chemistry 694 (2009) 677–682
phosphorus, selenium and acetylenes, particularly to the controlling
the addition selectivity to acetylenes. The reaction studied paves a
short way to a rare family of isomerically pure alkenes bearing phos-
phine selenide and aromatic (or heteroaromatic) substituents, po-
tent building blocks for organic and elementoorganic synthesis.
7.32; Se, 18.65. Found: C, 67.82; H, 6.01; P, 7.05; Se, 18.94%. Z-iso-
mer: is colorless solid, mp 84–86 °C (hexane). 1H NMR (400.13
MHz, CDCl3): d 2.25 (m, 4H, CH2P), 2.77 (m, 4H, CH2Ph), 5.98 (dd,
3
2JHP = 18.1 Hz, JHH = 13.5 Hz, 1H, @CHP), 6.92 (m, Ho, 4H, PhCH2),
7.16 (m, Hp, 2H, PhCH2), 7.21 (m, Hm, 4H, PhCH2), 7.29 (dd,
3
3JHP = 41.0 Hz, JHH = 13.5 Hz, 1H, @CHPh), 7.36 (m, Hp, 1H, PhC@),
7.42 (m, Hm, 2H, PhC@), 7.82 (m, Ho, 2H, PhC@). 13C NMR
2
4. Experimental
(100.69 MHz, CDCl3): d 29.58 (d, JCP = 2.3 Hz, CH2Ph), 33.17 (d,
1
1JCP = 46.2 Hz, CH2P), 121.57 (d, JCP = 62.9 Hz, @CP), 126.54 (Cp,
The 1H, 13C, 31P and 77Se NMR spectra were recorded on a Bru-
ker DPX 400 and Bruker AV-400 spectrometer (400.13, 100.69,
161.98 and 76.31 MHz, respectively) in CDCl3 solutions and refer-
PhCH2), 128.25 (Co, PhCH2), 128.61 (Cm, PhC@), 128.68 (Cm, PhCH2),
3
129.45 (Cp, PhC@), 129.67 (Co, PhC@), 135.85 (d, JCP = 6.5 Hz, Ci,
PhC@), 140.48 (d, 3JCP = 15.3 Hz, Ci, PhCH2), 145.55 (d, 2JCP = 2.7 Hz,
@CPh). 31P NMR (161.98 MHz, CDCl3): d 20.71 (1JSeP = 688.3 Hz).
NMR for E-isomer: 1H NMR (400.13 MHz, CDCl3): d 2.38 (m, 4H,
CH2P), 2.87 (m, 4H, CH2Ph), 6.31 (dd, 2JHP = 21.8 Hz, 3JHH = 16.6 Hz,
1H, @CHP), 7.15–7.23 (m, 10H, PhCH2), 7.36 (m, Hm, Hp, 3H, PhC@),
enced to HMDS (1H NMR, 13C NMR), H3PO4 31P NMR) and Me2Se
(
(
77Se NMR). IR spectra were run on a Bruker IFS 25 instrument.
GC/MS analyses (EI, 70 eV) were performed on a Hewlett-Packard
HP 5971A instrument. All steps of the experiment were carried
out in inert atmosphere (argon). Secondary phosphine selenides
1–4 were prepared by the oxidation of corresponding secondary
phosphines by elemental selenium in benzene [3a], the initial
diphenylphosphine was a commercial product, bis(2-aryl)- or
bis(2-hetaryl)ethylphosphines were obtained from red phosphorus
and alkene: styrene [3b], 1-(tert-butyl)-4-vinylbenzene) [3c] or 2-
vinylpyridine [1e].
3
3
7.45 (m, Ho, 2H, PhC@), 7.59 (dd, JHP = 23.0 Hz, JHH = 16.6 Hz, 1H,
@CHPh). 13C NMR (100.69 MHz, CDCl3): d 29.20 (CH2Ph), 33.30 (d,
1
1JCP = 47.5 Hz, CH2P), 116.73 (d, JCP = 70.5 Hz, @CP), 126.40 (Cp,
PhCH2), 128.10 (Co, PhC@), 128.50 (Co, PhCH2), 128.60 (Cm, PhCH2),
3
128.97 (Cm, PhC@), 130.20 (Cp, PhC@), 134.74 (d, JCP = 19.6 Hz, Ci,
3
2
PhC@), 140.68 (d, JCP = 15.4 Hz, Ci, PhCH2), 151.10 (d, JCP < 2 Hz,
@CPh). 31P NMR (161.98 MHz, CDCl3): d 33.15 (1JSeP = 714.2 Hz).
4.1. Synthesis and characteristics of alkenylphosphine selenides 6a–d
in the presence of AIBN: typical procedure (Table 1)
4.1.3. Bis[2-(4-tert-butylphenyl)ethyl](2-phenylvinyl)phosphine
selenide (6c)
Waxy product, yield 80%, Z:E = 75:25. Anal. Calc. for C32H41PSe:
C, 71.76; H, 7.72; P, 5.78; Se, 14.74. Found: C, 72.02; H, 7.99; P,
A mixture of phosphine selenide 1–4 and acetylene 5 (their mo-
lar ratio was 1:3) in the presence of 2 mass% AIBN was stirred un-
der an argon atmosphere at 65–70 °C. The reaction was monitored
using 31P NMR spectra that showed the disappearance of peaks of
the initial secondary phosphine selenide 1–4 at ꢀ2–5 (d) ppm and
the appearance of new peaks at ꢀ20–35 ppm corresponding to ter-
tiary alkenylphosphine selenides 6a–d. The excess phenylacety-
lene was then removed under vacuum, the residue was washed
twice with small amount of diethyl ether and dried in vacuum to
afford alkenylphosphine selenides 6a–d.
5.89; Se, 14.48%. IR (film, m
, cmÀ1): 1655 (C@C), 476 (P@Se). NMR
for Z-isomer: 1H NMR (400.13 MHz, CDCl3): d 1.29 (s, 18H, Me),
2.37 (m, 4H, CH2P), 2.85 (m, 4H, CH2C6H4), 6.01 (dd, 2JHP = 17.9 Hz,
3JHH = 13.4 Hz, 1H, @CHP), 6.91 (m, Ho, 4H, C6H4), 7.25-7.46 (m, 7H,
3
3
Hm, Hp, PhC@, Hm, C6H4), 7.28 (dd, JHP = 41.2 Hz, JHH = 13.4 Hz,
1H, @CHPh), 7.89 (m, Ho, 2H, PhC@). 13C NMR (100.69 MHz, CDCl3):
2
d
28.86 (d, JCP = 3.2 Hz, CH2C6H4), 31.25 (Me), 33.90 (d,
1JCP = 43.9 Hz, CH2P), 34.23 (CMe3), 121.33 (d, JCP = 63.1 Hz,
1
@CP), 125.3 (Cm, C6H4), 128.08 (Co, C6H4), 128.69 (Cm, PhC@),
3
129.50 (Cp, PhC@), 129.58 (Co, PhC@), 135.71 (d, JCP = 6.4 Hz, Ci,
3
2
4.1.1. (2-Phenylvinyl)(diphenyl)phosphine selenide (6a)
PhC@), 137.03 (d, JCP = 14.8 Hz, Ci, C6H4), 145.15 (d, JCP = 3.6 Hz,
@CPh), 149.15 (Cp, C6H4). 31P NMR (161.98 MHz, CDCl3): d 20.75.
77Se NMR (76.31 MHz, CDCl3): d -248.3 (1JSeP = 688.4 Hz). NMR
for E-isomer: 1H NMR (400.13 MHz, CDCl3): d 1.29 (s, 18H, Me),
2.38 (m, 4H, CH2P), 2.87 (m, 4H, CH2C6H4), 6.35 (dd, 2JHP = 21.8 Hz,
3JHH = 16.4 Hz, 1H, @CHP), 6.91 (m, Ho, 4H, C6H4), 7.25–7.46 (m, 9H,
Waxy product, yield 75%, Z:E = 97:3. Anal. Calc. for C20H17PSe:
C, 65.40; H, 4.67; P, 8.43; Se, 21.50. Found: C, 65.70; H, 4.38; P,
8.15; Se, 21.78%. IR (film, m
, cmÀ1): 1656 (C@C), 486 (P@Se). NMR
for Z-isomer: 1H NMR (400.13 MHz, CDCl3):
d 6.41 (dd,
3
2JHP = 18.1 Hz, JHH = 13.5 Hz, 1H, @CHP), 7.00 (m, Hm, Hp, 3H,
3
PhC@), 7.25 (m, Hm, 4H, PhP), 7.27 (m, Hp, 2H, PhP), 7.37 (dd,
Hm, C6H4, PhC@, Ho, Hm, Hp, PhC@), 7.60 (dd, JHP = 23.2 Hz,
3
3JHP = 43.8 Hz, JHH = 13.5 Hz, 1H, @CHPh), 7.46 (m, Ho, 2H, PhC@),
3JHH = 16.4 Hz, 1H, @CHPh). 13C NMR (100.69 MHz, CDCl3): d
28.55 (d, 2JCP = 2.0 Hz, CH2C6H4), 31.25 (Me), 34.10 (d,
7.86 (m, Ho, 4H, PhP). 13C NMR (100.69 MHz, CDCl3): d 122.05 (d,
3
1JCP = 74.1 Hz, @CP), 127.40 (Cm, PhC@), 128.40 (d, JCP = 12.5 Hz,
1
1JCP = 46.7 Hz, CH2P), 34.23 (CMe3), 117.01 (d, JCP = 67.5 Hz,
4
Cm, PhP), 128.81 (Cp, PhC@), 130.19 (d, JCP = 1.1 Hz, Co, PhC@),
@CP), 125.3 (Cm, C6H4), 128.30 (Co, C6H4), 128.69 (Co, PhC@),
4
1
3
131.32 (d, JCP = 3.0 Hz, Cp, PhP), 131.78 (Ci, JCP = 72.0 Hz, PhP),
128.90 (Cm, PhC@), 130.10 (Cp, PhC@), 134.75 (d, JCP = 18.8 Hz,
131.80 (d, 2JCP = 11.0 Hz, Co, PhP), 134.30 (d, 3JCP = 6.6 Hz, Ci, PhC@),
3
Ci, PhC@), 137.26 (d, JCP = 14.0 Hz, Ci, C6H4), 149.11 (Cp, C6H4),
2
145.85 (d, JCP = 2.2 Hz, @CPh). 31P NMR (161.98 MHz, CDCl3): d
2
150.25 (d, JCP = 6.0 Hz, @CPh). 31P NMR (161.98 MHz, CDCl3): d
20.19 (1JSeP = 719.2 Hz). NMR for E-isomer: 1H NMR
33.50. 77Se NMR (76.31 MHz, CDCl3): d -420.1 (1JSeP = 712.0 Hz).
2
3
(400.13 MHz, CDCl3): d 6.92 (dd, JHP = 20.1 Hz, JHH = 16.4 Hz, 1H,
@CHP), 7.35 (m, Hm, Hp, 3H, PhC@), 7.44 (m, Hm, Hp, 6H, PhP),
4.1.4. Bis[2-(2-pyridyl)ethyl](Z-2-phenylvinyl)phosphine selenide (6d)
Waxy product, yield 60%, Z:E = 95:5. Anal. Calc. for
C22H23N2PSe: C, 62.12; H, 5.45; N, 6.59; P, 7.28; Se, 18.56. Found:
3
3
7.52 (m, Ho, 2H, PhC@), 7.52 (dd, JHP = 33.9 Hz, JHH = 16.4 Hz,
1H, @CHPh), 7.80 (m, Ho, 4H, PhP). 13C NMR (100.69 MHz, CDCl3):
1
m
, cmÀ1): 1591
d 118.73 (d, JCP = 78.5 Hz, @CP), 128.08 (Co, PhC@), 128.30 (Cp,
C, 62.39; H, 5.72; P, 7.01; Se, 18.28%. IR (film,
(C@C), 468 (P@Se). NMR for Z-isomer: 1H NMR (400.13 MHz,
CDCl3): d 2.46 (m, 4H, CH2P), 3.02 (m, 4H, CH2Py), 6.03 (dd,
PhC@), 128.40 (Cm, PhP), 128.70 (Cm, PhC@), 130.0 (Cp, PhP),
3
131.80 (Co, PhP), 131.90 (Ci, PhP), 134.90 (d, JCP = 19.8 Hz, Ci,
2
PhC@), 148.94 (d, JCP = 6.6 Hz, @CPh). 31P NMR (161.98 MHz,
3
2JPH = 18.6 Hz, JHH 13.7 Hz, 1H, @CHP), 6.97 (m, 2H, H3, Py), 7.08
CDCl3): d 29.01 (1JSeP = 729.1 Hz).
(m, 2H, H5, Py), 7.25 (dd, 3JHP = 41.3 Hz, 3JHH = 13.7 Hz, 1H, @CHPh),
7.32 (m, 1H, Hp, PhC@), 7.38 (m, 2H, Hm, PhC@), 7.53 (m, 2H, H4,
Py), 7.83 (m, 2H, Ho, PhC@), 8.45 (m, 2H, H6, Py). 13C NMR
4.1.2. (2-Phenylvinyl)[bis(2-phenylethyl)]phosphine selenide (6b)
Waxy product, yield 70%, Z:E = 91:9. IR (film,
(C@C), 474 (P@Se). Anal. Calc. for C24H25PSe: C, 68.08; H, 5.95; P,
m
, cmÀ1): 1638
1
(100.69 MHz, CDCl3): d 30.57 (d, JCP = 45.2 Hz, CH2P), 31.56
1
(CH2Py), 121.40 (d, JCP = 60.0 Hz, @CP), 121.60 (C5, Py), 122.83

B.A. Trofimov et al. / Journal of Organometallic Chemistry 694 (2009) 677–682
681
(C3, Py), 128.40 (Cm, PhC@), 129.50 (Cp, PhC@), 129.69 (Co, PhC@),
1H, H4, furyl), 6.77 (dd, 3JHP = 39.4 Hz, 3JHH = 14.2 Hz, 1H, @CH-fur-
yl), 6.84 (dd, J3-4 = 3.4 Hz, J3–5 = 1.0 Hz, 1H, H3, furyl), 7.07–7.27
3
3
4
135.82 (d, JCP = 6.1 Hz, Ci, PhC@), 136.40 (C4, Py), 145.40 (d,
2JCP = 2.5 Hz, @CPh), 149.20 (C6, Py), 159.70 (C2, Py). 31P NMR
(161.98 MHz, CDCl3): d 22.3. 77Se NMR (76.31 MHz, CDCl3): d
À252.2 (1JSeP = 692.9 Hz).
(m, 10H, Ph), 7.51 (dd, J4–5 = 1.7 Hz, J3–5 = 1.0 Hz, 1H, H5, furyl).
3
4
13C NMR (100.69 MHz, CDCl3):
d 29.49 (CH2Ph), 34.13 (d,
1JCP = 45.6 Hz, CH2P), 112.59 (C4, furyl), 117.01 (C3, furyl), 117.60
1
(d, JCP = 62.3 Hz, @CP), 126.58 (Cp, Ph), 128.33 (Cm, Ph), 128.64
4.2. Synthesis and characteristics of alkenylphosphine selenides 6a, c,
e–f under UV-initiation: typical procedure (Table 2)
(Co, Ph), 130.09 (d, 2JCP = 7.6 Hz, @C-furyl), 140.74 (d, 3JCP = 15.3 Hz,
Ci, Ph), 144.63 (C5, furyl), 150.18 (d, JCP = 8.4 Hz, C2, furyl). 31P
3
NMR (161.98 MHz, CDCl3): d 24.70 (1JSeP = 690.1 Hz). NMR for E-
isomer: 1H NMR (400.13 MHz, CDCl3): d 2.30 (m, 4H, CH2P), 2.91
A solution of phosphine selenide 1–3 and acetylene 5, 7, 8 (their
molar ratio was 1:1) in dioxane was placed in a quartz ampoule
under an argon atmosphere and irradiated (200-W Hg arc lamp)
for the time indicated in Table 2. The solvent was then removed
under vacuum, the residue was purified as described above.
(m, 4H, CH2Ph), 6.23 (dd, 2JHP = 21.8 Hz, JHH = 16.4 Hz, 1H, @CHP),
3
3
3
6.43 (dd, J3–4 = 3.2 Hz, J4–5 = 1.7 Hz, 1H, H4, furyl), 6.54 (dd,
3J3–4 = 3.2 Hz, J3–5 = 1.0 Hz, 1H, H3, furyl), 7.07–7.27 (m, 10H, Ph),
4
3
3
7.41 (dd, JHP = 22.7 Hz, JHH = 16.4 Hz, 1H, @CHAfuryl), 7.42 (dd,
3J4–5 = 1.7 Hz, J3–5 = 1.0 Hz, 1H, H5, furyl). 13C NMR (100.69 MHz,
4
1
4.2.1. [2-(2-Naphthyl)vinyl](diphenyl)phosphine selenide (6e)
Waxy product, yield 53%, Z:E = 60:40. Anal. Calc. for C24H19PSe:
C, 69.07; H, 4.59; P, 7.42; Se, 18.92. Found: C, 68.79; H, 4.82; P,
CDCl3): d 29.14 (CH2Ph), 34.34 (d, JCP = 48.0 Hz, CH2P), 112.17
1
(C4, furyl), 113.79 (d, JCP = 69.5 Hz, @CP), 113.96 (C3, furyl),
126.36 (Cp, Ph), 128.24 (Cm, Ph), 128.56 (Co, Ph), 137.70 (d,
3
7.14; Se, 18.64%. IR (film,
m
, cmÀ1): 1650 (C@C), 477 (P@Se). NMR
2JCP = 7.6 Hz, @CAfuryl), 140.47 (d, JCP = 15.7 Hz, Ci, Ph), 144.26
for Z-isomer: 1H NMR (400.13 MHz, CDCl3):
d
6.50 (dd,
(C5, furyl), 151.22 (d, JCP = 22.0 Hz, C2, furyl). 31P NMR
3
3
3
2JHP = 18.1 Hz, JHH = 13.5 Hz, 1H, @CHP), 7.50 (dd, JHP = 43.1 Hz,
(161.98 MHz, CDCl3): d 33.72 (1JSeP = 714.2 Hz).
3JHH = 13.5 Hz, 1H, @CHNaphthyl), 7.18–7.52, 7.78–8.10 (m, 17H,
Ph, Naphthyl). 13C NMR (100.69 MHz, CDCl3):
d
122.60 (d,
4.3. Synthesis and characteristics of (2-phenylvinyl)[bis(2-
phenylethyl)]phosphine (9)
1JCP = 73.9 Hz, @CP), 126.36-133.12 (Ph, Naphthyl), 145.81 (d,
2JCP = 2.0 Hz, @CNaphthyl). 31P NMR (161.98 MHz, CDCl3):
d
20.33. 77Se NMR (76.31 MHz, CDCl3): d À261.2 (1JSeP = 717.1 Hz).
To a solution of phosphine selenide 6b (317 mg, 0.75 mmol) in
7.5 ml of toluene metal sodium (86 mg, 3.74 mmol) was added.
The reaction mixture was refluxed under an argon atmosphere
for 0.5 h, then cooled and filtered. After removal of toluene under
vacuum phosphine 9 (250 mg, 97%) was prepared as a waxy prod-
uct, Z:E = 80:20. Anal. Calc. for C24H25P: C, 83.69; H, 7.32; P, 8.99.
Found: C, 83.40; H, 7.07; P, 8.69%. NMR for Z-isomer: 1H NMR
(400.13 MHz, CDCl3): d 1.82 (m, 4H, CH2P), 2.71 (m, 4H, CH2Ph),
NMR for E-isomer: 1H NMR (400.13 MHz, CDCl3): d 7.02 (dd,
3
3
2JHP = 19.8 Hz, JHH = 16.6 Hz, 1H, @CHP), 7.67 (dd, JHP = 22.8 Hz,
3JHH = 16.6 Hz, 1H, @CHNaphthyl), 7.18–7.52, 7.78–8.10 (m, 17H,
Ph, Naphthyl). 13C NMR (100.69 MHz, CDCl3):
d 118.90 (d,
1JCP = 77.9 Hz, @CP), 126.36–133.12 (Ph, Naphthyl), 148.99 (d,
2JCP = 7.2 Hz, @CNaphthyl). 31P NMR (161.98 MHz, CDCl3):
29.18. 77Se NMR (76.31 MHz, CDCl3): d À310.3 (1JSeP = 727.0 Hz).
d
2
3
6.03 (dd, JHP = 3.1 Hz, JHH = 12.8 Hz, 1H, @CHP), 7.08–7.60 (m,
16H, @CHPh, Ph). 31P NMR (161.98 MHz, CDCl3): d À41.48. NMR
for E-isomer: 1H NMR (400.13 MHz, CDCl3): d 1.84 (m, 4H,
4.2.2. [2-(2-Naphthyl)vinyl][bis(2-phenylethyl)]phosphine selenide
(6f)
3
3
Waxy product, yield 74%, Z:E = 50:50. Anal. Calc. for C28H27PSe:
CH2P), 2.72 (m, 4H, CH2Ph), 6.53 (dd, JHP = 3.1 Hz, JHH = 17.2 Hz,
3
3
C, 71.03; H, 5.75; P, 6.54; Se, 16.68. Found: C, 70.79; H, 5.98; P,
1H, @CHP), 6.98 (dd, JHP = 13.3 Hz, JHH = 17.2 Hz, 1H, @CHPh),
7.08–7.60 (m, 15H, Ph). 31P NMR (161.98 MHz, CDCl3): d -26.40.
MS (EI), m/z: 344 (M+), 343, 315, 239, 237, 212, 149, 136, 133,
115, 105, 91, 77, 65, 51.
6.30; Se, 16.97%. IR (film, m
, cmÀ1): 1658 (C@C), 477 (P@Se). NMR
for Z-isomer: 1H NMR (400.13 MHz, CDCl3): d 2.25 (m, 4H,
CH2P), 2.76 (m, 4H, CH2Ph), 6.03 (dd, 2JHP = 18.1 Hz, 3JHH = 13.5 Hz,
3
1H, @CHP), 6.83 (m, 4H, Ho, PhCH2), 7.42 (dd, JHP = 41.1 Hz,
3JHH = 13.5 Hz, 1H, @CHNaphthyl), 7.07–7.91 (m, 12H, Ph, Naph-
thyl), 8.49 (s, 1H, H1, Naphthyl). 13C NMR (100.69 MHz, CDCl3): d
Acknowledgement
2
1
29.57 (d, JCP = 3.0 Hz, CH2Ph), 33.28 (d, JCP = 44.7 Hz, CH2P),
Financial support from the Russian Foundation for Basic Re-
search (Grant No. 07-03-00562) is gratefully acknowledged.
1
121.49 (d, JCP = 63.8 Hz, @CP), 126.03-129.63 (Ph, Naphthyl),
3
3
133.18 (d, JCP = 6.6 Hz, C2, Naphthyl), 140.21 (d, JCP = 15.4 Hz, Ci,
Ph), 145.56 (d, @CNaphthyl, JCP = 3.0 Hz, @CNaphthyl). 31P NMR
2
References
(161.98 MHz, CDCl3): d 20.91 (1JSeP = 688.4 Hz). NMR for E-isomer:
1H NMR (400.13 MHz, CDCl3): d 2.40 (m, 4H, CH2P), 2.99 (m, 4H,
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3
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