Highly selective phosphinotelluration of terminal alkynes using a (Ph 2P)2-(PhTe)2 mixed system upon visible light irradiation: Straightforward access to 1-phosphino-2-telluro-alkenes

Article abstract of DOI:10.1021/om9008982

Simultaneous and regioselective introduction of both phosphino and telluro groups into carbon-carbon triple bonds has been attained successfully by using a novel mixed system of diphosphine and ditelluride under visible light irradiation conditions. Upon irradiation with a xenon lamp (500 W) through the filter (hv > 400 nm), terminal alkynes undergo highly selective phosphinotelluration in the presence of tetraphenyldiphosphine and diphenyl ditelluride, affording l-(diphenylphosphino)-2-(phenyltelluro)alkenes, regioselectively, in moderate to good yields. The regioselectivity of this phosphinotelluration of terminal alkynes is discussed by comparison with those of the thiophosphination using a (Ph₂P)₂-(PhS)₂ binary system and the selenophosphination using a (Ph₂P) ₂-(PhSe)₂ binary system.

Full text of DOI:10.1021/om9008982

312 Organometallics 2010, 29, 312–316
DOI: 10.1021/om9008982
Highly Selective Phosphinotelluration of Terminal Alkynes Using a
(Ph2P)2-(PhTe)2 Mixed System upon Visible Light Irradiation:
Straightforward Access to 1-Phosphino-2-telluro-alkenes
Shin-ichi Kawaguchi, Takashi Ohe, Takamune Shirai, Akihiro Nomoto, Motohiro Sonoda,
and Akiya Ogawa*
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University,
1-1 Gakuen-cho, Nakaku, Sakai, Osaka 599-8531, Japan
Received October 13, 2009
Simultaneous and regioselective introduction of both phosphino and telluro groups into carbon-carbon
triple bonds has been attained successfully by using a novel mixed system of diphosphine and ditelluride
under visible light irradiation conditions. Upon irradiation with a xenon lamp (500 W) through the filter
(hν>400 nm), terminal alkynes undergo highly selective phosphinotelluration in the presence of tetra-
phenyldiphosphine and diphenyl ditelluride, affording 1-(diphenylphosphino)-2-(phenyltelluro)alkenes,
regioselectively, in moderate to good yields. The regioselectivity of this phosphinotelluration of terminal
alkynes is discussed by comparison with those of the thiophosphination using a (Ph2P)2-(PhS)2 binary
system and the selenophosphination using a (Ph2P)2-(PhSe)2 binary system.
Introduction
mixed systems of interelement compounds under photoirradia-
tion conditions. In the case of the addition to alkynes, for
example, we already reported highly selective thioselenation,
thiotelluration, selenotelluration, thiophosphination, and seleno-
phosphination using (PhS)2-(PhSe)2,3 (PhS)2-(PhTe)2,4
Simultaneous introduction of two different heteroatom
groups into carbon-carbon unsaturated bonds is a powerful
tool to give multifunctionalized organic compounds directly.
For this purpose, radical addition reactions of interelement
compounds into unsaturated bonds via homolytic cleavage of
heteroatom-heteroatom linkages are promising, because the
combination of interelement compounds makes it possible to
synthesize a wide variety of multifunctionalized heteroatom
compounds.1,2 Along this line, we have recently developed
simultaneous and selective introduction of two different hetero-
atom groups to carbon-carbon unsaturated bonds using novel
6
(PhSe)2-(PhTe)2,4b (PhS)2-(Ph2P)2,5 and (PhSe)2-(Ph2P)2
mixed systems, respectively, as shown in Scheme 1.
These interelement compounds (Y-Y, Z-Z) undergo homo-
lytic cleavage upon photoirradiation, generating the correspond-
ing heteroatom-centered radicals (Y•, Z•), respectively.7-10
(5) (a) Shirai, T.; Kawaguchi, S-i.; Nomoto, A.; Ogawa, A. Tetra-
hedron Lett. 2008, 49, 4043. (b) Wada, T.; Kondoh, A.; Yorimitsu, H.;
Oshima, K. Org. Lett. 2008, 10, 1155.
*Corresponding author. Tel & Fax: þ81-72-254-9290. E-mail: ogawa@
chem.osakafu-u.ac.jp.
(6) Kawaguchi, S-i.; Shirai, T.; Ohe, T.; Nomoto, A.; Sonoda, M.;
Ogawa, A. J. Org. Chem. 2009, 74, 1751.
(1) For radical addition reactions via simultaneous introduction of
two different heteroatom moieties into unsaturated bonds, see for
example: (a) Toru, T.; Seko, T.; Maekawa, E.; Ueno, Y. J. Chem.
Soc., Perkin Trans. 1 1989, 1927. (b) Back, T. G.; Brunner, K.; Krishna,
M. V.; Lai, E. K. Y.; Muralidharan, K. R. In Heteroatom Chemistry; Block,
E., Ed.; VCH Publishers, Inc.: New York, 1990; Chapter 4. (c) Back, T. G.
Phosphorous Sulfur, Silicon, Relat. Elem. 1992, 67, 203.
(2) For the metal-catalyzed addition reactions via simultaneous
introduction of two different heteroatom moieties into unsaturated
bonds, see: Beletskaya, I. P.; Moberg, C. Chem. Rev. 2006, 106, 2320.
(3) (a) Ogawa, A.; Hirao, T. Rev. Heteroat. Chem. 1998, 18, 1.
(b) Ogawa, A.; Tanaka, H.; Yokoyama, H.; Obayashi, R.; Yokoyama, K.;
Sonoda, N. J. Org. Chem. 1992, 57, 111. (c) Ogawa, A.; Obayashi, R.; Ine,
H.; Tsuboi, Y.; Sonoda, N.; Hirao, T. J. Org. Chem. 1998, 63, 881.
(d) Ogawa, A.; Obayashi, R.; Sonoda, N.; Hirao, T. Tetrahedron Lett.
1998, 39, 1577. (e) Tsuchii, K.; Tsuboi, Y.; Kawaguchi, S-i.; Takahashi, J.;
Sonoda, N.; Nomoto, A.; Ogawa, A. J. Org. Chem. 2007, 72, 415.
(f) Mitamura, T.; Imanishi, Y.; Nomoto, A.; Sonoda, M.; Ogawa, A. Bull.
Chem. Soc. Jpn. 2007, 80, 2443.
(7) For the radical addition of organic disulfides to alkynes, see, for
example: (a) Heiba, E. I.; Dessau, R. M. J. Org. Chem. 1967, 32, 3837.
(b) Takaguchi, Y.; Katayose, Y.; Yanagimoto, Y.; Motoyoshiya, J.; Aoyama,
H.; Wakahara, T.; Maeda, Y.; Akasaka, T. Chem. Lett. 2003, 32, 1124.
(8) For the radical addition of organic diselenides to alkynes, see, for
example: (a) Back, T. G.; Krishna, M. V. J. Org. Chem. 1988, 53, 2533.
(b) Ogawa, A.; Yokoyama, K.; Yokoyama, H.; Sekiguchi, M.; Kambe, N.;
Sonoda, N. Tetrahedron Lett. 1990, 31, 5931. (c) Ogawa, A.; Yokoyama, H.;
Yokoyama, K.; Masawaki, T.; Kambe, N.; Sonoda, N. J. Org. Chem. 1991,
56, 5721. (d) Ogawa, A.; Takami, N.; Sekiguchi, M.; Yokoyama, H.;
Kuniyasu, H.; Ryu, I.; Sonoda, N. Chem. Lett. 1991, 20, 2241. (e) Ogawa,
A.; Doi, M.; Ogawa, I.; Hirao, T. Angew. Chem., Int. Ed. 1999, 38, 2027.
(f) Tsuchii, K.; Doi, M.; Hirao, T.; Ogawa, A. Angew. Chem., Int. Ed. 2003,
42, 3490. (g) Tsuchii, K.; Doi, M.; Ogawa, I.; Einaga, Y.; Ogawa, A. Bull.
Chem. Soc. Jpn. 2005, 78, 1534.
(9) For the radical addition of organic ditellurides to alkynes, see, for
example: (a) Ogawa, A.; Yokoyama, K.; Yokoyama, H.; Obayashi, R.;
Kambe, N.; Sonoda, N. J. Chem. Soc., Chem. Commun. 1991, 1748.
(b) Ogawa, A.; Yokoyama, K.; Obayashi, R.; Han, L.-B.; Kambe, N.; Sonoda,
N. Tetrahedron 1993, 49, 1177.
(10) For the radical addition of organic diphosphines to alkynes, see:
(a) Tzschach, V. A.; Baensch, S. J. Prakt. Chem. 1971, 313, 254. (b) Sato,
A.; Yorimitsu, H.; Oshima, K. Angew. Chem., Int. Ed. 2005, 44, 1694.
(c) Kawaguchi, S-i.; Nagata, S.; Shirai, T.; Tsuchii, K.; Nomoto, A.; Ogawa,
A. Tetrahedron Lett. 2006, 47, 3919.
(4) (a) Ogawa, A.; Obayashi, R.; Doi, M.; Sonoda, N.; Hirao, T.
J. Org. Chem. 1998, 63, 4277. (b) Ogawa, A.; Ogawa, I.; Obayashi, R.;
Umezu, K.; Doi, M.; Hirao, T. J. Org. Chem. 1999, 64, 86. (c) Mitamura, T.;
Tsuboi, Y.; Iwata, K.; Tsuchii, K.; Nomoto, A.; Sonoda, M.; Ogawa, A.
Tetrahedron Lett. 2007, 48, 5953. (d) Mitamura, T.; Iwata, K.; Ogawa, A.
Org. Lett. 2009, 11, 3422.
r
pubs.acs.org/Organometallics
Published on Web 12/16/2009
2009 American Chemical Society

Article
Scheme 1. Simultaneous Introduction of Two Different
Organometallics, Vol. 29, No. 2, 2010 313
Heteroatom Groups Including PhS, PhSe, PhTe, or Ph2P to
Alkynes upon Photoirradiation
Figure 1. ORTEP drawing of 5a depicted with thermal ellip-
soids at 50% probability. The hydrogens have been omitted for
clarity, and the CF3 group is disordered. Selected bond distances
˚
(A) and bond angles (deg): C(9)-C(10), 1.317(6); C(1)-C(10),
1.474(7); P(1)-C(9), 1.794(4); Te(1)-C(10), 2.125(4); Te(1)-
C(29), 2.083(7); C(10)-Te(1)-C(29), 96.5(2); Te(1)-C(10)-
C(9), 122.1(3); C(1)-C(10)-C(9), 125.1(4); P(1)-C(9)-C(10),
125.6(3).
Scheme 2. Simultaneous Introduction of Two Different
Heteroatom Groups Using Heteroatom Mixed Systems
thio or seleno group was introduced into the terminal
position of alkynes, and the phosphino group was intro-
duced into the inner one, regioselectively.5,6 Surprisingly,
X-ray analysis of 5a indicated different regioselectivity: a
phosphino group and telluro group were introduced into the
terminal and inner positions, respectively, with excellent
regioselectivity (Figure 1). Then the subsequent oxidation
under air for 24 h led to the corresponding phosphinyltelluro-
styrene derivative (5a) in 73% yield.
Then these radicals react with carbon-carbon triple bonds,
giving the corresponding adducts (Scheme 2).
The selectivity of these reactions is controlled by the
relative reactivities of interelement compounds: If Y• is more
reactive toward alkynes compared with Z•, alkynes undergo
selective addition of Y•, generating the corresponding vinyl
radical. Then, when Z-Z has higher carbon-radical-captur-
ing ability compared with Y-Y, the formed vinyl radicals
are captured selectively with Z-Z, affording the desired
multifunctionalized vinyl compounds successfully. In this
paper, we wish to report a novel simultaneous introduction
of both phosphino and telluro groups into alkynes upon
photoirradiation using a (Ph2P)2-(PhTe)2 mixed system.
In these dichalcogenide-diphosphine mixed systems, both
chalcogeno and phosphino radicals are generated in situ
(Scheme 2). Therefore, both chalcogeno and phosphino
radicals may attack the terminal position of alkynes. In fact,
however, either heteroatom-centered radical selectively at-
tacks the alkynes. On the basis of these regioselectivities in
the thiophosphination, selenophosphination, and phosphino-
telluration, the relative reactivity toward alkynes can be
estimated as follows: PhS• > PhSe• > Ph2P•> PhTe•.
Next, we examined this phosphinotelluration of phenyla-
cetylene under several reaction conditions (Table 1). With-
out photoirradiation, the desired phosphinotelluration did
not proceed at room temperature for a long time (entry 1).
Even upon heating at 60 °C, the phosphinotelluration did
not take place (entry 2). When irradiation through a filter
with a xenon lamp (hν>400 nm) was conducted at room
temperature for 10 h, the phosphinotelluration product (4b)
was obtained in good yield (entry 3). In the case of benzene11
Results and Discussion
When a mixture of 1-ethynyl-4-(trifluoromethyl)benzene
(1a, 0.5 mmol), tetraphenyldiphosphine (2, 0.5 mmol), and
diphenyl ditelluride (3, 0.5 mmol) in CDCl3 (0.6 mL,
degassed) was irradiated through a filter with a xenon lamp
(hν > 400 nm) at room temperature for 10 h, the desired
product (4a) bearing both phosphino and telluro groups was
obtained successfully in 96% yield (eq 1). In the cases of the
thiophosphination and selenophosphination of alkynes, a
(11) Chloroform or benzene was used as a solvent because tetraphenyl-
diphosphine has lower solubility in other common organic solvents.10c

314 Organometallics, Vol. 29, No. 2, 2010
Kawaguchi et al.
Table 1. Phosphinotelluration of Phenylacetylene under Several
Conditions
Scheme 3. Possible Pathway for Phosphinotelluration of
Alkynes
conditions (irradiation,
temp, time, solvent)
entry
yielda
1
2
3
4
dark, rt, 90 h, CDCl3
trace
trace
50%
trace
dark, heat (60 °C), 10 h, CDCl3
hν (>400 nm), rt, 10 h, CDCl3
hν (>400 nm), rt, 15 h, C6D6
aDetermined by 1H NMR.
Table 2. Photoinduced Phosphinotelluration of Alkynes Using
(Ph2P)2-(PhTe)2 Mixed System
irradiation induces selective cleavage of the ditelluride, gene-
rating PhTe•, which attacks the diphosphine to form Ph2P•
and PhTePPh2.
The phosphinotelluration of several alkynes was exam-
ined, and the results are shown in Table 2. A variety of
aromatic alkynes successfully underwent regioselective phos-
phinotelluration in moderate to high yields (entries 1-7). In
the case of a conjugate enyne, the phosphinotelluration
proceeded in moderate yield (entry 8). The phosphinotellura-
tion of aliphatic alkyne also proceeded regioselectively, al-
though prolonged photoirradiation was required (entry 9).
All of the obtained phosphinotelluroethenes 4a-i could be
transferred to the corresponding phosphine oxides 5a-i.
A possible pathway for the present phosphinotelluration is
shown in Scheme 3. As described already, the initiation for
this phosphinotelluration can be explained by the visible-
light-irradiated selective homolysis of ditelluride generating
PhTe•. The formed PhTe• attacks (Ph2P)2 to form the
phosphino radical (Ph2P•) and PhTePPh2, because the re-
activity of PhTe• toward carbon-carbon triple bonds is
relatively low. The formed Ph2P• attacks the terminal carbon
of alkynes, generating vinyl radical intermediate, which can
be captured with (PhTe)2 to give the phosphinotelluration
products 4, since (PhTe)2 has a higher ability for capturing
carbon radical compared with (Ph2P)2.
Conclusion
We have developed novel phosphinotelluration of term-
inal alkynes by the combination of (Ph2P)2 and (PhTe)2
under photoirradiation conditions. This system has achieved
simultaneous and regioselective introduction of both phos-
phino and telluro groups into carbon-carbon triple bonds.
We are currently investigating the application of this system
to the other compounds bearing heteroatom-heteroatom
linkages.
aDetermined by 1H and 31P NMR. bIsolated yield of E-isomer by
silica gel column chromatography. cIsolated yield of E/Z mixture. E/Z
stereoisomer ratio determined by 1H and 31P NMR.
as solvent, the addition did not proceed (entry 4). Since the
absorption maximum (λmax) of diphosphine and ditellu-
ride is 260 nm12 and 406 nm,9 respectively, visible-light
Experimental Section
General Comments. Alkynes, tetraphenyldiphosphine (2), and
diphenyl ditelluride (3) were obtained as commercial supplies.
Alkynes were purified by distillation before use. Other materials
(12) Troy, D.; Turpin, R.; Voigt, D. Bull. Soc. Chim. Fr. 1979, 241.

Article
Organometallics, Vol. 29, No. 2, 2010 315
were used without further purification. As the light source,
USHIO optical ModuleX (SX-UI500XQ) was used. H NMR
141.0, 150.3 (d, JC-P = 52.4 Hz), 160.0; 31P NMR (200 MHz,
CDCl3) δ 17.6; HRMS (EI) calcd for C27H23O2PTe 540.0498,
found 540.0500.
[Z-isomer] yellow oil; IR (NaCl) 3052, 2928, 1541, 1435, 1177,
1119, 735, 692 cm-1; 1H NMR (CDCl3, 500 MHz) δ 3.66 (s, 3H),
6.53 (d, J = 8.7 Hz, 2H), 6.91 (d, J = 6.9, 2H), 6.94 (d, JH-P =
12.8 Hz, 1H), 7.02 (d, J = 8.7 Hz, 2H), 7.05-7.08 (m, 1H), 7.38
(d, J = 7.8 Hz, 2H), 7.47-7.50 (m, 4H), 7.52-7.56 (m, 2H),
7.69-7.82 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 55.3, 112.8,
118.6, 122.8 (d, JC-P = 95.5 Hz), 128.3 (d, JC-P = 5.7 Hz),
128.4, 128.6 (d, J = 11.5 Hz), 129.4 (d, JC-P = 7.8 Hz), 131.2
(d, J = 10.5 Hz), 131.8, 133.1 (d, JC-P = 104.6 Hz), 135.7 (d,
1
spectra were recorded on a JEOL JNM-ECP-500 (500 MHz) FT
NMR system or JEOL JNM-400 (400 MHz) FT NMR system in
CDCl3 with Me4Si as an internal standard. 13C NMR spectra
were taken on a JEOL JNM-ECP-500 (125 MHz) FT NMR
system or JEOL JNM-300SXA (75 MHz) FT NMR system in
CDCl3. 31P NMR spectra were taken on a JEOL JNM- ECP-500
(200 MHz) FT NMR system in CDCl3 with 85% H3PO4
solution as an external standard. The 125Te NMR spectrum
was taken on a JEOL JNM- ECP-500 (158 MHz) FT NMR
system in CDCl3. The chemical shift refers to (PhTe)2 (δ =
420 ppm at 25 °C) in CDCl3 as an external standard. IR spectra
were determined on a Perkin-Elmer model 1600 spectrometer.
Melting points were determined on a Yanagimoto micro melting
point apparatus. HRMS were obtained on a JEOL JMS-
DX303 in the analytical section of Osaka University. Elemental
analyses were also performed there.
JC-P = 19.1 Hz), 140.2 (d, JC-P = 6.7 Hz), 152.2 (d, JC-P
=
1.9 Hz), 159.2; 31P NMR (200 MHz, CDCl3) δ 25.8; HRMS (EI)
calcd for C27H23O2PTe 540.0498, found 540.0493.
2-(Diphenylphosphinyl)-1-(4-methylphenyl)-1-(phenyltelluro)-
ethene (5d). [E-isomer] yellow oil; IR (NaCl) 3055, 2921, 2852,
1
2360, 1606, 1436, 1182, 1120, 794, 692, 524 cm-1; H NMR
General Procedure for Photoinduced Phosphinotelluration of
Alkynes with (Ph2P)2-(PhTe)2 Mixed System. (Ph2P)2 (188 mg,
0.5 mmol), (PhTe)2 (205 mg, 0.5 mmol), and alkyne (0.5 mmol)
were placed in CDCl3 (0.5 mL) in a sealed Pyrex glass NMR tube
under a nitrogen atmosphere. The mixture was stirred for 30 s,
and then the mixture was irradiated with a xenon lamp (500 W)
though the filter (hν>400 nm) at room temperature for 10-
85 h. The reaction mixture was left under air for 24 h. Purifica-
tion of the crude product was performed by preparative TLC.
The E and Z mixture (5c-5i) was obtained with purification by
preparative TLC to remove the starting materials and small
amounts of byproduct. To separate the E- and Z-isomers of
5c-5i, purification was performed by preparative TLC once
more: for example 5c, eluent AcOEt/hexane = 9:11, Rf = 0.15 for
E-isomer, Rf = 0.32 for Z-isomer; 5d, eluent AcOEt/hexane =
3:7, Rf = 0.10 for E-isomer, Rf = 0.15 for Z-isomer; 5e, eluent
AcOEt/hexane = 3:7, Rf = 0.10 for E-isomer, Rf = 0.23 for
Z-isomer.
(CDCl3, 500 MHz) δ 2.10 (s, 3H), 6.30 (d, JH-P = 18.1 Hz, 1H),
6.76 (d, J = 8.0 Hz, 2H), 7.09-7.16 (m, 6H), 7.19-7.24 (m, 4H),
7.71-7.76 (m, 5H), 7.84 (d, J = 6.8 Hz, 2H); 13C NMR (75
MHz, CDCl3) δ 21.0, 118.5, 123.0 (d, JC-P = 106.5 Hz), 127.4,
127.8, 128.0, 128.3, 128.4 (d, JC-P = 22.3 Hz), 128.6 (d, JC-P
=
11.6 Hz), 131.2 (d, JC-P = 9.9 Hz), 131.8, 133.1 (d, JC-P
=
104.1 Hz), 137.6, 140.3, 152.6; 31P NMR (200 MHz, CDCl3) δ
17.8; HRMS (EI) calcd for C27H23O2PTe 524.0549, found
524.0553.
[Z-isomer] yellow oil; IR (NaCl) 3053, 2962, 2854, 2358, 1546,
1434, 1176, 1018, 792, 692, 565 cm-1;1H NMR (CDCl3, 500 MHz)
δ 2.16 (s, 3H), 6.80 (d, JH-P = 8.0 Hz, 2H), 6.88-6.90 (m, 5H),
7.07 (t, J = 7.3 Hz, 1H), 7.38 (d, J = 7.3 Hz, 2H), 7.48-7.55 (m,
6H), 7.78-7.82 (m, 4H); 13C NMR (75 MHz, CDCl3) δ 21.0,
118.4, 123.0 (d, JC-P = 106.6 Hz), 127.4, 127.8, 128.0, 128.3, 128.6
(d, JC-P = 11.6 Hz), 131.2 (d, JC-P = 9.9 Hz), 131.8 (d, JC-P
=
2.5 Hz), 133.1 (d, JC-P = 104.9 Hz), 137.5, 140.26, 140.33 (d,
JC-P = 13.2 Hz), 152.6; 31P NMR (200 MHz, CDCl3) δ 25.7;
HRMS (EI) calcd for C27H23O2PTe 524.0549, found 524.0541.
2-(Diphenylphosphinyl)-1-(4-pentylphenyl)-1-(phenyltelluro)-
ethene (5e): [E-isomer] yellow oil; IR (NaCl) 3053, 2928, 2856,
2172, 1437, 1303, 1184, 1117, 1101, 997, 736, 718, 692 cm-1; 1H
NMR (400 MHz, CDCl3) δ 0.90 (t, J = 7.2 Hz, 3H), 1.18-1.51
(m, 6H), 2.41 (t, J = 7.7 Hz, 2H), 6.40 (d, JH-P = 17.6 Hz, 1H),
6.82 (d, J = 8.0 Hz, 2H), 7.14-7.52 (m, 15H), 7.91 (d, J =
8.0 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 14.0, 22.4, 30.8, 31.3,
Spectral and Analytical Data. (E)-2-(Diphenylphosphinyl)-
1-(phenyltelluro)-1-(4-trifluoromethylphenyl)ethene (E-5a): dark
yellow solid; mp 64-66 °C; IR (NaCl) 3051, 1558, 1541, 1436,
1
1325, 1164, 1116, 746, 720, 694, 524 cm-1; H NMR (CDCl3,
500 MHz) δ 6.57 (d, JH-P = 17.8 Hz, 1H), 7.21-7.35 (m, 12H),
7.40-7.44 (m, 5H), 7.87 (d, J = 6.7 Hz, 2H); 13C NMR
(125 MHz, CDCl3) δ 115.4, 124.5, 126.9 (q, JC-F = 285.4 Hz),
128.1, 128.7, 129.6, 130.1, 130.4 (d, JC-P = 90.0 Hz), 130.5
(q, JC-F = 32.7 Hz), 130.7, 131.0, 131.2, 133.5 (d, JC-P = 105.5 Hz),
141.0 (d, JC-P = 1.9 Hz), 147.7 (d, JC-P = 4.0 Hz); 31P NMR
(200 MHz, CDCl3) δ 17.5; HRMS (EI) calcd for C27H20F3OPTe
578.0266, found 578.0260.
35.5, 116.2, 126.0 (d, JC-P = 92.1 Hz), 127.8, 127.9 (d, JC-P
=
12.3 Hz), 128.7 (d, JC-P = 21.5 Hz), 129.3, 130.0, 130.6, 130.8
(d, JC-P = 9.9 Hz), 134.1 (d, JC-P = 104.5 Hz), 137.1 (d,
JC-P = 8.2 Hz), 141.1, 143.7, 151.1; 31P NMR (200 MHz,
CDCl3) δ 17.6, HRMS (EI) calcd for C31H31OPTe 580.1175,
found 580.1176.
[Z-isomer] yellow oil; IR (NaCl) 3053, 2954, 2926, 2855, 2172,
1435, 1177, 1119, 1102, 997, 731, 692 cm-1; 1H NMR (CDCl3,
400 MHz) δ 0.88 (t, J = 7.2 Hz, 3H), 1.12-1.47 (m, 6H), 2.40 (t,
J = 7.6 Hz, 2H), 6.78 (d, J = 8.1 Hz, 2H), 6.85-6.89 (m, 2H),
6.90 (d, JH-P = 22.9 Hz, 1H), 6.93-6.97 (m, 2H), 7.37 (d, J =
8.0 Hz, 2H), 7.46-7.55 (m, 6H), 7.76-7.84 (m, 4H); 13C NMR
(75 MHz, CDCl3) δ 14.0, 22.5, 31.02, 31.05, 35.3, 118.6, 122.6 (d,
(E)-2-(Diphenylphosphinyl)-1-phenyl-1-(phenyltelluro)ethene (E-5b):
dark yellow solid; mp 109-111 °C; IR (NaCl) 3051, 1558, 1541,
1
1436, 1184, 1114, 736, 719, 692, 520 cm-1; H NMR (CDCl3,
500 MHz) δ 6.45 (d, JH-P = 17.9 Hz, 1H), 7.01-7.04 (m, 3H),
7.19-7.22 (m, 4H), 7.28-7.34 (m, 7H), 7.40-7.44 (m, 4H),
7.90-7.93 (m, 2H); 13C NMR (125 MHz, CDCl3) δ 116.0, 126.1,
127.7, 127.9, 128.0 (d, JC-P = 11.5 Hz), 128.6, 129.1 (d, JC-P
90.0 Hz), 130.0, 130.7 (d, JC-P = 10.5 Hz), 130.9, 134.1 (d, JC-P
104.6 Hz), 139.8 (d, JC-P = 8.6 Hz), 141.1, 150.5 (d, JC-P
=
=
=
4.8 Hz); 31P NMR (200 MHz, CDCl3) δ 17.4; 125Te NMR
(158 MHz, CDCl3) δ 870; HRMS (EI) calcd for C26H21OPTe
510.0392, found 510.0394. Anal. Calcd for C26H21OPTe: C,
61.47; H, 4.17. Found: C, 61.51; H, 4.18.
JC-P = 105.3 Hz), 127.4, 127.8, 128.0, 128.2, 128.6 (d, JC-P =
11.5 Hz), 131.2 (d, JC-P = 9.9 Hz), 131.8 (d, JC-P = 3.3 Hz),
133.1 (d, JC-P = 108.6 Hz), 140.3, 140.4 (d, JC-P = 20.6 Hz),
142.6, 152.7; 31P NMR (200 MHz, CDCl3) δ 25.7.
2-(Diphenylphosphinyl)-1-(4-methoxyphenyl)-1-(phenyltelluro)-
ethene (5c): [E-isomer] yellow oil; IR (NaCl) 3054, 2924, 1541,
1435, 1175, 1119, 735, 693 cm-1; 1H NMR (CDCl3, 500 MHz)
δ 3.61 (s, 3H), 6.32 (d, J = 17.8 Hz, 1H), 6.48 (d, JH-P = 8.7 Hz,
2H), 7.11-7.14 (m, 4H), 7.18-7.24 (m, 6H), 7.31-7.37 (m, 5H),
7.83 (d, J = 7.8 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 55.2,
113.2, 116.2, 125.7 (d, JC-P = 91.9 Hz), 128.0 (d, JC-P = 11.7 Hz),
2-(Diphenylphosphinyl)-1-(4-fluorophenyl)-1-(phenyltelluro)-
ethene (5f). [E-isomer] yellow oil; IR (NaCl) 3055, 2358, 2175,
1598, 1498, 1434, 1222, 1184, 1118, 1026, 792, 694, 559 cm-1; 1H
NMR (CDCl3, 500 MHz) δ 6.50 (d, JH-P = 18.3 Hz, 1H), 6.70
(t, JH-F,H-H = 8.8 Hz, 2 H), 7.22-7.26 (m, 3H), 7.29-7.33 (m,
4H), 7.40-7.45 (m, 6H), 7.81-7.84 (m, 2H), 7.88 (d, J = 7.1 Hz,
2H); 13C NMR (75 MHz, CDCl3) δ 114.6 (d, JC-F = 21.5 Hz),
127.4 (d, JC-P = 91.7 Hz), 128.1 (d, JC-P = 12.4 Hz), 128.5
(d, JC-F = 13.2 Hz), 129.5, 130.1, 130.6 (d, JC-P = 9.9 Hz),
128.5 (d, JC-P = 13.6 Hz), 129.3, 129.7, 130.0, 130.6 (d, JC-P =
9.2 Hz), 130.8 (d, JC-P = 2.5 Hz), 132.8 (d, JC-P = 105.5 Hz),

316 Organometallics, Vol. 29, No. 2, 2010
Kawaguchi et al.
131.0 (d, JC-P = 2.5 Hz), 132.0 (d, JC-P = 14.9 Hz), 133.9 (d,
1.04-1.07 (m, 2H), 1.67-1.69 (m, 2H), 1.78-1.79 (m, 2H),
5.47 (s, 1H), 6.69 (d, J = 28.4 Hz, 1H), 7.10 (d, J = 7.8 Hz, 2H),
7.20-7.23 (m, 1H), 7.37-7.41 (m, 4H), 7.44-7.47 (m, 2H),
7.64-7.71 (m, 6H); 13C NMR (75 MHz, CDCl3) δ 21.4, 21.6,
24.7, 29.4, 118.4, 119.5 (d, JC-P = 105.5 Hz), 126.6, 127.9, 128.3,
128.5 (d, JC-P = 12.4 Hz), 131.1 (d, JC-P = 10.0 Hz), 131.6 (d,
J
C-P = 104.9 Hz), 135.9 (dd, JC-P = 8.3 Hz, JC-F = 3.3 Hz),
141.0, 149.2, 162.6 (d, JC-F = 248.6 Hz); 31P NMR (200 MHz,
CDCl3) δ 17.9; HRMS (EI) calcd for C26H20FOPTe 528.0298,
found 528.0290.
[Z-isomer] yellow oil; IR (NaCl) 3056, 2925, 2850, 1596, 1436,
1174, 1120, 729, 694, 559 cm-1; 1H NMR (CDCl3, 500 MHz) δ
6.66 (t, JH-F,H-H = 8.7 Hz, 2H), 6.88-6.94 (m, 3H), 6.98-7.00
(m, 2H), 7.09 (t, J = 7.4 Hz, 1H), 7.39 (d, J = 7.8 Hz, 2H),
JC-P = 2.5 Hz), 133.1 (d, JC-P = 103.6 Hz), 141.1 (d, JC-P
=
18.5 Hz), 141.3, 156.3; 31P NMR (200 MHz, CDCl3) δ 25.9;
HRMS (EI) calcd for C26H25OPTe 514.0705, found 514.0699.
Anal. Calcd for (C26H25OPTe)50(CHCl3)1: C, 59.99; H, 4.84.
Found: C, 59.97; H, 4.74.
7.45-7.50 (m, 4H), 7.53-7.56 (m, 2H), 7.77-7.81 (m, 4H); 31
P
NMR (200 MHz, CDCl3) δ 25.8; HRMS (EI) calcd for
C26H20FOPTe 528.0298, found 528.0302.
1-(Diphenylphosphinyl)-2-(phenyltelluro)oct-1-ene (5i): [E-
isomer] brown oil; IR (NaCl) 3052, 2950, 2925, 2852, 1558,
1-(4-Bromophenyl)-2-(diphenylphosphinyl)-1-(phenyltelluro)-
ethene (5g). [E-isomer] yellow oil; IR (NaCl) 3053, 2920, 2343,
1500, 1436, 1180, 1118, 798, 692, 524 cm-1; 1H NMR (CDCl3,
500 MHz) δ 6.49 (d, JH-P = 18.0 Hz, 1H), 7.22-7.27 (m, 5H),
7.31-7.35 (m, 4H), 7.49-7.51 (m, 3H), 7.79-7.84 (m, 4H),
7.87-7.89 (m, 3H); 13C NMR (75 MHz, CDCl3) δ 122.8,
127.6 (d, JC-P = 99.0 Hz), 128.1 (d, JC-P = 11.6 Hz), 128.7
(d, JC-P = 14.0 Hz), 129.5, 129.6, 130.1, 130.65, 130.71 (d,
1
1436, 1189, 726, 692, 497 cm-1; H NMR (500 MHz, CDCl3)
δ 0.73 (t, J = 7.3 Hz, 3H), 1.00-1.12 (m, 6H), 1.32-1.38 (m,
2H), 2.78-2.82 (m, 2H), 6.12 (d, J = 23.3 Hz, 1H), 7.19-7.23
(m, 2H), 7.28-7.34 (m, 5H), 7.35-7.38 (m, 2H), 7.46-7.50 (m,
4H), 7.77-7.78 (m, 2H); 13C NMR (125 MHz, CDCl3) δ 140.0
22.4, 28.6, 30.6, 31.4, 38.8 (d, JC-P = 7.6 Hz), 113.8, 124.6 (d,
J
C-P = 92.1 Hz), 128.4 (d, JC-P = 12.4 Hz), 129.1, 129.8, 130.7
J
C-P = 12.4 Hz), 131.1 (d, JC-P = 2.5 Hz), 133.7 (d, JC-P
=
(d, JC-P = 9.5 Hz), 131.3, 134.6 (d, JC-P = 103.6 Hz), 141.1,
155.0 (d, JC-P = 3.8 Hz); 31P NMR (200 MHz, CDCl3) δ 19.7;
HRMS (FAB) calcd for C26H29OPTe 518.1018, found 518.1020.
Anal. Calcd for C26H29OPTe: C, 71.52; H, 6.69. Found: C,
71.76; H, 6.80.
[Z-isomer] brown oil; IR (NaCl) 3054, 2951, 2925, 2852, 1558,
1436, 1190, 726, 692, 500 cm-1; 1H NMR (500 MHz, CDCl3) δ
0.72 (t, J = 7.3 Hz, 3H), 0.90-0.97 (m, 4H), 1.04-1.11 (m, 2H),
1.26-1.33 (m, 2H), 2.20 (t, J = 7.3 Hz, 2H), 6.69 (d, J = 27.0
Hz, 1H), 7.17 (d, J = 7.8 Hz, 2H), 7.28-7.31 (m, 1H), 7.38-7.48
(m, 6H), 7.65-7.69 (m, 4H), 7.84 (d, J = 8.3 Hz, 2H); 13C NMR
107.6 Hz), 138.8 (d, JC-P = 9.1 Hz), 140.4, 141.0; 31P NMR
(200 MHz, CDCl3) δ 18.0; HRMS (FAB) calcd for [M þ Hþ]
C26H21BrOPTe 588.9576, found 588.9569.
[Z-isomer] yellow oil; IR (NaCl) 3053, 2962, 2360, 1546, 1475,
1434, 1174, 1120, 1068, 798, 692, 526 cm-1; 1H NMR (CDCl3,
500 MHz) δ 6.87 (d, J = 8.3 Hz, 2H), 6.91-6.94 (m, 2H),
7.08-7.12 (m, 4H), 7.39 (d, J = 6.9 Hz, 2H), 7.48-7.50 (m, 4H),
7.54-7.57 (m, 2H), 7.76-7.80 (m, 4H); 31P NMR (200 MHz,
CDCl3) δ 26.0.
1-(1-Cyclohexenyl)-2-(diphenylphosphinyl)-1-(phenyltelluro)-
ethene (5h): [E-isomer] yellow oil; IR (NaCl) 3445, 2168, 1645,
(125 MHz, CDCl3) δ 14.0, 22.4, 28.3, 30.1, 31.4, 43.0 (d, JC-P
17.2 Hz), 116.2, 118.5 (d, JC-P = 110.3 Hz), 128.6 (d, JC-P
10.5 Hz), 128.9, 130.9 (d, JC-P = 10.5 Hz), 131.1 (d, JC-P
=
=
=
1603, 1501, 1437, 1290, 1252, 1177, 1115, 1026, 718, 694 cm-1
;
1H NMR (300 MHz, CDCl3) δ 0.91-1.09 (m, 4H), 1.62-1.99
(m, 4H), 6.03 (s, 1H), 6.66 (d, JH-P = 19.6 Hz, 1H), 7.22-7.68
(m, 12H), 7.78-7.91 (m, 3H); 13C NMR (75 MHz, CDCl3)
δ 20.8, 21.5, 25.0, 28.7, 114.7, 119.8, 125.6 (d, JC-P = 96.5 Hz),
9.5 Hz), 131.7, 133.3 (d, JC-P = 103.6 Hz), 142.0, 153.9;
31P NMR (200 MHz, CDCl3) δ 26.8.
128.2 (d, JC-P = 12.4 Hz), 129.0, 129.6, 130.9 (d, JC-P
=
Acknowledgment. This work is supported by a Grant-
in-Aid for Scientific Research on Scientific Research
(B, 19350095), from the Ministry of Education, Culture,
Sports, Science and Technology, Japan, and supported by
a Grant-in-Aid for JSPS Fellows (No. 21-10516) from the
Japan Society for the Promotion of Science.
9.2 Hz), 131.0 (d, JC-P = 3.1 Hz), 134.8 (d, JC-P = 103.8 Hz),
138.0 (d, JC-P = 8.6 Hz), 141.0, 154.3; 31P NMR (200 MHz,
CDCl3) δ 17.6; HRMS (EI) calcd for C26H25OPTe 514.0705,
found 514.0701.
[Z-isomer]13 pale yellow solid; mp 154-156 °C; IR (NaCl)
3412, 1645, 1603, 1504, 1435, 1250, 1173, 1115, 1026, 718, 694
cm-1 1H NMR (500 MHz, CDCl3) δ 0.92-0.96 (m, 2H),
;
Supporting Information Available: X-ray structure details for
5a (CIF). This material is available free of charge via the Internet
at http://pubs.acs.org.
(13) Braga, A. L.; Vargas, F.; Zeni, G.; Silveira, C. C.; de Andrade,
L. H. Tetrahedron Lett. 2002, 43, 4399.