Alkyne-based, highly stereo- and regioselective synthesis of stereodefined functionalized vinyl tellurides

Article abstract of DOI:10.1021/jo001026b

(Z)-β-Aryltellurovinylphosphonates and (Z)-β-aryltellurovinyl sulfones were synthesized via the highly stereoselective anti-hydrotelluration of 1-alkynylphosphonates and 1-alkynyl sulfones. The configurations of these compounds were characterized via

Full text of DOI:10.1021/jo001026b

7
4
J . Org. Chem. 2001, 66, 74-80
Alk yn e-Ba sed , High ly Ster eo- a n d Regioselective Syn th esis of
Ster eod efin ed F u n ction a lized Vin yl Tellu r id es
Xian Huang,* Chun-Gen Liang, Qing Xu, and Qi-Wen He
Department of Chemistry, Zhejiang University, Xixi Campus, Hangzhou 310028,
People’s Republic of China, and Laboratory of Organometallic Chemistry,
Chinese Academy of Sciences, Shanghai 200032, People’s Republic China
huangx@mail.hz.zj.cn
Received J uly 8, 2000
(
Z)-â-Aryltellurovinylphosphonates and (Z)-â-aryltellurovinyl sulfones were synthesized via the
highly stereoselective anti-hydrotelluration of 1-alkynylphosphonates and 1-alkynyl sulfones. The
1
configurations of these compounds were characterized via H NMR spectra or NOESY experiments
and by X-ray diffraction analysis; (E)-â-aryltellurovinyl sulfones were obtained with the reaction
of sodium aryltellurate with (E)-2-iodovinyl sulfones to confirm the stereochemistry of the above
anti-hydrotelluration. When the tandem reaction of alkynes with diaryl ditellurides and sodium
arylsulfinates was carried out in AcOH/H O (4/1), the corresponding (E)-â-aryltellurovinyl sulfones
2
were obtained in one step in good yields. This reaction is highly regio- and stereoselective and
proceeds by using arylsulfinate as the sulfonyl radical precursor and diaryl ditellurides as free
radical acceptors. (E)-1-Iodo-2-aryltelluroalkenes can be obtained by the anti-addition of ArTeI with
terminal alkynes in THF. The stereochemistry of compound 17b was also determined by X-ray
diffraction analysis.
In tr od u ction
Stereoselective synthesis of substituted alkenes has
drawn a lot of attention in organic synthesis. Stereo- and
regioselecitve addition of organic reagents to alkynes is
one of the most efficient routes to stereodefined alkenes
(
Figure 1).
F igu r e 1.
Vinyl tellurides are important synthetic intermediates
because of their ready transformation to other organic
compounds with retention of configuration, e.g., trans-
application in carbon-carbon or carbon-heteroatom bond
formation reactions affording polyfunctionalized olefines.
Although the preparation of R-heteroatom-substituted
1
2
metalations to form their corresponding vinyllithium,
copper, zinc,4 magnesium,5 calcium,5 and sodium re-
3
1b,e,7
vinyl tellurides 1 and 2 have been extensively studied,
5
agents and their subsequent cross-coupling reaction to
there are only a few reports on the synthesis of 3- and
form stereodefined substituted alkenes.6 Recently the
synthesis of metal- or heteroatom-substituted vinyl tell-
urides has received intensive attention because of their
(3) (a) Comasseto, J . V.; Berriel, J . N. Synth. Commun. 1990, 20,
1681. (b) Tucci, F. C. Chieffi, A.; Comasseto, J . V. Tetrahedron Lett.
1
1
992, 33, 5721, (c) Marino, J . P.; Tucci, F. C.; Comasseto, J . V. Synlett
993, 761. (d) Chieffi, A.; Comasseto, J . V. Tetrahedron Lett. 1994,
*
To whom correspondence should be addressed. Fax: 86571
807077.
1) For reviews about vinylic tellurides, see: (a) Comasseto, J . V.;
35, 4063. (e) Araujo, M.; Comasseto, J . V. Synlett 1995, 1145. (f) Tucci,
F. C. Chieffi, A.; Comasseto, J . V.; Marino, J . P. J . Org. Chem. 1996,
61, 4975. (g) Araujo, M. A.; Barrientos-Astigarra, R. M.; Comasseto,
J . V. Tetrahedron Lett. 1999, 40, 5115.
(4) Terao, J .; Kambe, N.; Sonoda, N. Tetrahedron Lett. 1996, 37,
4741.
8
(
Ling, L. W.; Petragnani, N.; Stefani, H. A. Synthesis 1997, 373. (b)
Dabdoub, M. J .; Begnini, M. L.; Guerrero J r., P. G. Tetrahedron 1998,
4, 2371 (c) Dabdoub, M. J .; J ustino, A.; Guerrero J r., P. G. Organo-
5
metallics 1998, 17, 1901. (d) Dabdoub, M. J .; Baroni C. M. J . Org.
Chem. 2000, 65, 54-60. (e) Dabdoub, M. J .; Begnini, M. L.; Guerrero,
P. G., J r.; Baroni, C. M. J . Org. Chem. 2000, 65, 61-67.
(5) Kanda, T.; Sugino, T.; Kambe, N.; Sonoda, N. Phosphorus, Sulfur,
Silicon Relat. Elem. 1992, 67, 103.
(6) (a) Uemura, S.; Fukuzawa, S. I.; Patil, S. R. J . Organomet. Chem.
1983, 243, 9. (b) Chieffi, A. Comasseto, J . V. Tetrahedron Lett. 1994,
35, 4063. (c) Chieffi, A.; Comasseto, J . V. Synlett. 1995, 671. (d) Zeni,
G.; Comasseto, J . V. Tetrahedron Lett. 1999, 40, 4619. (e) Dabdoub,
M. J ., Dabdoub, V. B., Marino, J . P. Tetrahedron Lett. 2000, 41, 433.
(f) Dabdoub, M. J ., Dabdoub, V. B.; Marino, J . P. Tetrahedron Lett.
2000, 41, 437,
(
2) (a) Kauffman, T.; Allers, H. Chem. Ber. 1983, 116, 1001. (b) Hiiro,
T.; Mogami, T.; Kambe, N.; Fujiwara, S. I.; Sonoda, N. Angew. Chem.,
Int. Ed. Engl. 1987, 26, 1187. (c) Barros. S. M.; Dabdoub, M. J .;
Dabdoub, V. M. B.; Comasseto. J . V. Organometallics 1989, 8, 1661.
(
3
d) Barros, S. M.; Comasseto, J . V.; Berriel, J . Tetrahedron Lett. 1989,
0, 7353. (e) Dabdoub, M. J .; Dabdoub, V. B.; Comasseto, J . V.
Tetrahedron Lett. 1992, 33, 2261. (f) Ogawa, A.; Tsuboi, Y.; Obayashi,
R.; Yokoyama, K.; Ryu, I.; Sonoda, N. J . Org. Chem. 1994, 59, 1600.
(7) For the preparation of R-hetero (S, Se, Te, Zr, I, Br, Sn,
B)-substituted vinyl tellurides and their synthetic application, see: (a)
Ogawa, A., Ogawa, I.; Obayashi, R.; Umezu, K.; Doi, M., Hirao, T. J .
Org. Chem. 1999, 64, 86. (b) Braga, A. L.; Zeni, G.; Andrade, L H.;
Silveira, C. C. Synlett 1997, 595. (c) Braga, A.; Reckziegel, A.; Silveira,
C. C.; Comasseto, J . V. Synth. Commun. 1994, 24, 1165. (d) Dabdoub,
M. J .; Cassol, T. M.; Barbosa, S. L. Tetrahedron Lett. 1996, 37, 831.
(e) Stang, P. J .; Roberts, K. A.; Lynch, L. E. J . Org. Chem. 1984, 49,
1653. (f) Silveira, C. C.; Perin, G.; Braga. A. L. Tetrahedron Lett. 1995,
36, 7361. (g) Park, C. P.; Sung, J . W.; Oh, D. Y. Synlett. 1999, 1055.
(h) Huang, X.; Liang, C.-G. Synth. Commun. 2000, 30, 1903.
(g) Dabdoub, M. J .; Dabdoub, V. B. Tetrahedron 1995, 51, 9839. (h)
Dabdoub, M. J .; Begnini, M. L.; Cassol, T. M.; Guerrero J r., P. G.;
Silveira, C. C. Tetrahedron Lett. 1995, 36, 7623 (i) Mo, X.-S.; Huang,
Y.-Z. Tetrahedron Lett. 1995, 36, 3539. (j) Dabdoub, M. J .; Dabdoub,
V. B.; Pereira, M. A.; Zukerman-Schpector, J . J . Org Chem. 1996, 61,
9
503. (k) Dabdoub, M. J .; Dabdoub, V. B.; Guerrero J r., P. G.; Silveria,
C. C. Tetrahedron 1997, 53, 4199. (l) Huang, Y.-Z.; Mo, X.-S. Tetra-
hedron Lett. 1998, 39, 1945. (m) Dabdoub, M. J .; J acob, R. G.; Ferreira,
J . T. B.; Dabdoub, V. B.; Marques, F. Tetrahedron Lett. 1999, 40, 7159.
1
0.1021/jo001026b CCC: $20.00 © 2001 American Chemical Society
Published on Web 12/14/2000

Synthesis of Functionalized Vinyl Tellurides
J . Org. Chem., Vol. 66, No. 1, 2001 75
F igu r e 2.
Sch em e 1
aryltelluro-1-alkenyl sulfones (8) were obtained in good
yields (Scheme 2 and Table 1). No isomeric compounds
1
were obtained as determined by the H NMR spectra of
the crude products. The Z-configurations of these com-
pounds were characterized via the coupling constant of
vinyl protons (J ) 8.69 Hz) of compound 9a and the NOE
experiments for compounds 8b and 9b. The correlations
between the vinyl hydrogen and aryl proton in 8b or the
vinyl hydrogen and allylic hydrogen in 9b indicated that
the vinyl hydrogen is situated close to those groups (cis
relation) (Figure 3).
However, when the reaction mixture was stirred for a
longer time (overnight), 8a was easily converted to (E)-
2-phenylvinyl sulfone 10 in 76% yield via reductive
detelluration (eq 1).
4
-type of highly â-functionalized vinylic tellurides2f,8,9
(Figure 2).
As a part of our ongoing study aimed at the synthesis
7
h,9a-c
and application of bifunctionalized vinyl tellurides,
we report herein the stereo- and regioselective synthesis
of vinyltellurides containing sulfonyl, phosphonyl, and
iodo groups via the stereo- and regiodefined addition of
organic tellurides with alkynes.
Resu lts a n d Discu ssion
To further confirm the stereochemistry of the hydro-
telluration of 1-alkynyl sulfones 7, we developed a way
to reach E-2-aryltelluryl-1-alkenyl sulfones by the reac-
tion of E-2-iodo-1-alkenyl sulfones with sodium aryltel-
lurates in THF/EtOH at 0 °C. In all cases studied, only
the E-isomers (Scheme 3 and Table 2), which were
characterized by IR, MS, and H and C NMR spectros-
copy and comparison with the corresponding Z-isomers,
were obtained.
On the other hand, for compound E-13f, there was no
NOE correlation between the vinyl proton (6.73 ppm) and
the allylic hydrogen (3.55-3.58 ppm). NOE correlation
between the vinyl proton and aryl proton of the aryltel-
lurium group was observed. This indicated that vinyl
proton situated close to aryltellurium group (trans rela-
tion) (compare with compound Z-9b) (Figure 3).
An ti-Tellu r osu lfon a tion of 1-Alk yn es. It was re-
ported that arylselenovinyl sulfones can be prepared
High ly Ster eo- a n d Regioselective An ti-Hyd r o-
tellu r a tion of 1-Alk yn ylp h osp h on a tes a n d 1-Alk y-
n yl Su lfon es. Hydrotelluration of acetylenes is a widely
used method for the synthesis of vinyl tellurides. In the
case of addition to acetylenes bearing electron-withdraw-
ing groups such as acetylenic aldehydes, ketones, car-
boxylic acids, and esters, â-carbonylvinyl tellurides with
Z-configuration can be obtained.10 As our work was
initiated, there was no report on the hydrotelluration of
1
13
1
-alkynyl sulfones and 1-alkynylphosphonates. First, we
1
investigated the reaction of 1-alkynylphosphonate 5a (R
Ph) with PhTeNa (prepared by the reduction of
ditelluride with NaBH ) in THF/EtOH (1/1) at room
)
4
temperature (monitored by TLC). This reaction afforded
anti-hydrotelluration product, i.e., Z-2-phenyltellurovi-
nylphosphonate 6c, stereo- and regioselectively as de-
1
termined by the H NMR spectrum of the crude product.
Other substrates gave the same results (Scheme 1 and
Table 1).
conveniently from the selenosulfonation of alkynes with
11
2
PhSeSO Ar. We have developed here the stereo- and
The structures of these compounds were affirmatively
characterized via 1H NMR spectra or NOESY experi-
ments (Z-6a and Z-6e) and by X-ray diffraction analysis
of compound 6a to be in Z-configuration. In all cases, the
attack of sodium tellurate on alkynes occurred at the
â-position exclusively.
regioselective synthesis of E-2-aryltelluryl-1-alkenyl sul-
fones 12 by the tellurosulfonation reaction of alkynes
with ArTeTeAr and sodium arylsulfinates in AcOH/H
at 80 °C. The results of the reaction of alkynes (1.1 mmol)
with diaryl ditellurides (0.5 mmol) and ArSO Na (5
mmol) in AcOH/H O at 80 °C are shown in Table 3. With
R ) aryl, the reaction finished within 5 h, while with R
alkyl, the reaction was slower and finished within 24
h (Scheme 4). The reaction of trimethylsilylacetylene with
PhTeTePh and sodium arylsulfinate in AcOH/H O for 48
2
O
2
2
When the reaction of 1-alkynyl sulfones with ArTeNa
was carried out at room temperature for 20 min, the Z-2-
)
(
8) (a) Moura Campos, M.; Petragnani, N. Tetrahedron 1962, 18,
27. (b) Uemura, S.; Miyoshi, H.; Okano, M. Chem. Lett. 1979, 1357.
d) Stefani, H. A.; Petragnani, N.; Zukerman-Schpector, J .; Dornelles,
L.; Silva, D. O.; Braga, A. L. J . Organomet Chem. 1998, 562, 127.
9) (a) Huang, X.; Wang, Y.-P. Tetrahedron Lett. 1996, 37, 7417. (b)
2
5
(
(11) (a) Back, T. G.; Collins, S.; Kerr, R. S. J . Org. Chem. 1983, 48,
3077. (b) Back, T, G.; Collins, S.; Gokhale, U.; Law, K.-W. J . Org. Chem.
1983, 48, 4776. (c) Miura, T.; Kobayashi, M. J . Chem. Soc., Chem.
Commun. 1982, 438. (d) Back, T. G.; Krishna, M. V. J . Org. Chem.
1987, 52, 4265. (e) Back, T. G.; Krishna, M. V.; Muralidharan, K. R.
J . Org. Chem. 1989, 54, 4146. (f) Gancarz, R. A.; Kice, J . L. J . Org.
Chem. 1981, 46, 4899.
(
Huang, X.; Wang Y.-P. Synth. Commun. 1996, 26, 3087. (c) Zhao, C.-
Q.; Huang, X. Synth. Commun. 1997, 27, 237.
(10) (a) Detty, M. R.; Murray, B. J .; Smith, D. L.; Zumbulyadis, N.
J . Am. Chem. Soc. 1983, 105, 875. (b) Detty, M. R.; Murray, B. J . J .
Am. Chem. Soc. 1983, 105, 883.

7
6
J . Org. Chem., Vol. 66, No. 1, 2001
Huang et al.
Ta ble 1. Syn th esis of Z-2-a r yltellu r o-1-a lk en ylp h osp h on a tes 6a -f, Z-2-a r yltellu r o-1-a lk en yl su lfon es 8a ,b, or Dibr om id es
a ,b
9
entries
R1
E
Ar
reaction conditon
product: yield (%)
1
2
3
4
5
6
7
8
9
C6H5
C6H5
C6H5
C6H5
C5H11
C5H11
Ph
Ph
H
C6H13
PO(OEt)2
PO(OEt)2
PO(OEt)2
PO(OEt)2
PO(OEt)2
PO(OEt)2
4-CH3-C6H4SO2
4-CH3-C6H4SO2
4-CH3-C6H4SO2
4-CH3-C6H4SO2
4-CH3-C6H4
4-Cl-C6H4
C6H5
4-F-C6H4
4-CH3-C6H4
4-F-C6H4
Ph
4-F-C6H4
Ph
Ph
rt, overnight
rt, overnight
rt, overnight
rt, overnight
rt, overnight
rt, overnight
rt, 20 min
rt, 20 min
rt, 20 min
rt, 20 min
Z-6a : 59a
Z-6b: 63
a
a
Z-6c: 61
a
Z-6d : 67
a
Z-6e: 57
Z-6f: 59
Z-8a : 74
a
b
b
Z-8b: 75
c
Z-9a : 82
c
1
0
Z-9b: 71
a
Isolated by preparative TLC eluted with AcOEt/hexanes ) 1/5. b Isolated by chromatography eluted with AcOEt/hexanes ) 1/10.
c
Isolated by recrystallization with HCCl3/CH3OH.
Ta ble 2. Ster eoselective Syn th esis of
E-2-Ar yltellu r o-1-a lk en yl Su lfon e 12g a n d Dibr om id es
1
3a -f (m eth od A)
a
entry
R
Ar
product: yield (%)
1
1
1
1
1
1
1
1
2
3
4
5
6
7
C4H9
C4H9
C5H11
C5H11
C6H13
C6H13
C6H5
C6H5
4-FC6H4
C6H5
4-FC6H4
C6H5
4-FC6H4
C6H5
E-13a : 72c
c
E-13b: 71
c
E-13c: 64
c
E-13d : 63
c
E-13e: 57
E-13f: 62
E-12g: 63
c
F igu r e 3.
b
Sch em e 2
a
Reaction conditions: 0 °C, 20 min. b Isolated yields by chro-
c
matography on silica gel eluted with AcOEt/hexanes ) 1/10. The
yield of dibromotelluryl compounds by recrystallization from
HCCl3/CH3OH.
Ta ble 3. Syn th esis of E-2-a r yltellu r o-1-a lk en yl su lfon es
1
2g, 12h , a n d 12k or Dibr om id es 13 fr om
Tellu r osu lfon a tion of 1-Alk yn es (m eth od B)
reaction
entry
R
Ar
Ar′
time (h) product: yielda(%)
1
1
2
8
9
0
C4H9 C6H5
C5H11 C6H5
4-CH3-C6H4
4-CH3-C6H4
24
24
24
24
5
E-13a : 55
E-13c: 70
E-13d : 53
E-13e: 68
E-12g: 74
E-12h : 85
E-13i: 51
E-13j: 61
E-12k : 26
C5H11 4-F-C6H4 4-CH3-C6H4
C H 4-CH -C H
4
Sch em e 3
21 C H
6
13
6
5
3
6
2
2
2
2
2
2
3
4
5
6
C6H5 C6H5
C6H5 C6H5
C4H9 C6H5
C6H13 C6H5
Me3Si C6H5
4-CH3-C6H4
4-Cl-C6H4
C6H5
C6H5
4-CH3-C6H4
2
24
24
48
b
a
Isolated yield based on ArTeTeAr. b The yield of desilylated
product.
Sch em e 4
h produced the desilylated E-2-phenyltelluro-1-alkenyl
sulfone (12k ) (J ) 15.82 Hz)12 in 26% yield after a workup
with aqueous sodium bicarbonate followed by chroma-
tography on silica gel (see Scheme 5 and entry 26, Table
3
). The Z-isomer was not obtained. The configurations
1
of other compounds were determined by H NMR, IR, and
MS spectroscopy and comparison with the products which
were obtained by the reaction of E-2-iodo-1-alkenyl
sulfones with sodium aryltellurates. No significant
amounts of stereoisomers of the above products could be
isolated.
addition of a sulfonyl radical to the alkyne to form the
11a
2
-sulfonylvinyl radical intermediates 14 and 15, fur-
ther reaction of 14 with diaryl ditelluride produces
products 12 highly stereoselectively probably due to the
Recent reports have shown sulfonyl radical can be
generated from sodium arylsulfinate in aqueous acetic
acid.13 A plausible mechanism for the formation of E-2-
aryltelluro-1-alkenyl sulfones 12 is the regiospecific
1
bigger steric interaction of SO
proaching ArTeTeAr (Scheme 6).
2
Ar in 15 with the ap-
14
An ti-Ad d ition of Ar TeI w ith 1-Alk yn es. Recent
reports by our group and others have shown that the
(
12) Desilylation reaction of a vinylsilane with a similar structure
in HOAc was known; see: Ohnuma, T.; Heta, N.; Fujiwara, H.; Ban,
(13) Chuang, C. P.; Wang, S. F. Synth. Commun. 1995, 25, 3549,
Y. J . Org. Chem. 1982, 47, 4713.
and references therein.

Synthesis of Functionalized Vinyl Tellurides
J . Org. Chem., Vol. 66, No. 1, 2001 77
Sch em e 5
Ta ble 4. Syn th esis of (2-Iod o-1-a lk yl)vin yl Ar yl
Tellu r iu m Dibr om id es 17a -f
entry
Ar
R
product:a,b (yield%)
2
2
2
3
3
3
7
8
9
0
1
2
C6H5
4-Cl-C6H4
C6H5
4-Cl-C6H4
C6H5
4-Cl-C6H4
C4H9
C4H9
C5H11
C5H11
C6H13
C6H13
E-17a : 45
E-17b: 53
E-17c: 48
E-17d : 51
E-17e: 37
E-17f: 43
a
Reaction conditions: the reaction was carried out using
ArTeTeAr (0.5 mmol), I2 (0.55 mmol), and alkyne (1 mmol) in THF
at room temperature for 24 h. b Isolated yields by recrystallization
from HCCl3/CH3OH.
Sch em e 6
Con clu sion
Anti-hydrotelluration of 1-alkynyl sulfones or 1-alky-
nylphosphonates afforded Z-2-aryltelluro-1-alkenyl sul-
fone or phosphonates exclusively; E-2-Aryltelluro-1-
alkenyl sulfones were obtained by the reaction of
aryltellurol with E-2-iodo-1-alkenyl sulfones. When the
reaction of alkynes with diaryl ditelluride and sodium
2
arylsulfinate was carried in AcOH/H O (4:1), the corre-
sponding E-2-aryltelluro-1-alkenyl sulfones were ob-
tained in good yields stereo- and regioselectively. ArTeI
reacted with alkynes in THF to afford E-1-iodo-2-aryl-
telluroalkenes stereo- and regioselectively. Since vinyl
Sch em e 7
sulfones,17 vinylphosphonates, and vinyl iodides are
important intermediates in organic synthesis, we envis-
aged that these three classes of compounds are interme-
diates of synthetic importance with the combination of
the well-known chemical reactivity of the carbon-tel-
lurium bonds.
18
19
Sch em e 8
Exp er im en ta l Section
1
Gen er a l. H NMR spectra were recorded on a 400 or 500
MHz spectrometer and all 13C NMR spectra were recorded on
3
a 400 MHz spectrometer using CDCl as the solvent. Diaryl
ditellurides,1 1-alkynyl sulfones, 1-alkynylphosphonates,
0a
20
21
2
2
and E-2-iodovinylsulfonates were prepared by the methods
reported in the literature.
An ti-Hyd r otellu r a tion of 1-Alk yn ylp h osp h on a tes w ith
Ar TeNa . To a solution of diaryl ditelluride (0.5 mmol) in (1/
1
2
) (V/V) THF/EtOH (5 mL) under N was added sodium
addition reaction of alkynes with ArTeX
3
(X ) Cl, Br)
borohydride (1.2 mmol) in EtOH dropwise until the charac-
teristic dark-red color of the ditelluride faded. Then 1-alky-
nylphosphonate (1 mmol) in THF (2 mL) was added, and the
resulting solution was stirred overnight at room temperature,
quenched with saturated aqueous NH
CH Cl . The organic phase was dried over sodium sulfate and
concentrated under vacuum. The residue was purified by
preparative TLC on silica gel (eluent: AcOEt:hexanes ) 1:5)
to give compounds 6a -f.
occurred stereo- and regioselectively. We have found the
reaction of aryltellurim tribromides with alkynes gave
E- or Z-2-bromovinyl aryl tellurium dibromides, depend-
ing on the solvents used.9 Further studies involve their
4
Cl, and extracted with
a
2
2
application to the synthesis of polysubstituted alkenes
a,b
(
Scheme 7).9
It was also been reported that aryltelluryl iodides can
1
5
react as good electrophilic reagents with alkenes or
alkynylboronates.16 All these promoted us to examine the
reaction of aryltelluryl iodides with alkynes. It was found
that aryltelluryl iodides reacted stereo- and regioselec-
tively with alkynes in THF to afford E-1-iodo-2-aryltel-
(16) Gerard, J .; Bietlot, E.; Hevesi, L. Tetrahedon Lett. 1998, 39,
8
735.
17) Vinyl sulfones For reviews, See: (a) The Chemistry of Sulphones
(
and sulphoxides; Patai, S.; Rappoport, Z., Stirling, C. J . M., Eds.;
Wiley: Chichester, 1988. (b) Lucchi, O. D.; Pasquato, L. Tetrahedron
1
988, 44, 6755. (c) Block, E.; Aslam, M. Tetrahedron 1988, 44, 281. (e)
Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86, 903.
18) For a review on vinyl phosphonate, see: Minami, T.; Mo-
toyoshiya, J . Synthesis 1992, 333.
19) Dang, H. P.; Linstrumelle, G. Tetrahedron Lett. 1978, 191. (b)
King, A. O.; Okukado, N.; Negishi, E. J . Chem. Soc., Chem. Commun.
2
luro-1-alkenes 16, which can react with Br to give the
more stable dibromotellurides 17 with the retention of
the configuration (Scheme 8 and Table 4). The structure
of product 17b was clearly established by an X-ray
diffraction analysis. Reaction of aryltelluryl iodides with
(
(
1
977, 683.
alkynes in benzene and CH
2
Cl
2
was not clean.
(20) (a) Truce, W. E.; Wolf, G. C. J . Org. Chem. 1971, 36, 1727. (b)
Chen, Z. M.; Trudell, M. L. Synth. Commun. 1994, 24, 3149.
21) (a) Chattha, M. S.; Aguiar, A. M. J . Org. Chem. 1971, 36, 2719.
(
(
14) Kopchik, R. M.; Kampeier, J . A. J . Am. Chem. Soc. 1968, 90,
733.
15) Sung, J . W.; Park, C. P.; Gil, J . M.; Oh, D. Y. Synth. Commun.
998, 28, 2635.
(b) Hong, J . E.; Lee, C.-W.; Kwon, Y.; Oh, D. Y. Synth. Commun. 1996,
26, 1563.
(22) Iwata, N.; Morioka, T.; Kobayashi, T.; Asada, T.; kinoshita, H.;
Inomata, K. Bull. Chem. Soc. J pn. 1992, 65, 1379.
6
(
1

7
2
8
J . Org. Chem., Vol. 66, No. 1, 2001
Huang et al.
(
Z)-1-(Dieth oxyph osph on yl)-2-(4-m eth ylph en yltellu r yl)-
An ti-Hydr otellu r ation of 1-Alkyn yl Su lfon es with Ar Te-
Na . To a solution of diaryl ditelluride (0.25 mmol) dissolved
in (1/1) (V/V) THF/ethanol (2.5 mL) under N was added a
2
solution of sodium borohydride (0.6 mmol) in EtOH dropwise
until the characteristic dark-red color of the ditelluride faded,
and then 1-alkynyl sulfone (0.5 mmol) in THF was added. The
resulting solution was stirred at room temperature for 20 min,
-p h en yleth en e (6a ): yield 0.27 g (59%); mp 95-96 °C; ν
-
1
(KBr)/cm : 3060, 2985, 2810, 1650, 1560, 1490, 1450, 1400,
-
1
1
2
235, 840, 700, 610 cm ; δ
H
(400 MHz) 7.28-7.30 (d, J ) 7.9,
H), 6.98 (m, 5H), 6.40-6.72 (d, J ) 17.3, 1H), 4.16-4.23 (m,
1
3
4
H), 2.19 (s, 3H), 1.37-1.41 (m, 6H); C NMR δ 153.72 (d,
3
2
J
P-C ) 7.7 Hz), 142.94 (d, J P-C ) 24.6 Hz), 140.58, 137.83,
1
29.43, 127.74 (d, 4
J
P-C ) 1 Hz), 127.53, 127.37, 119.97 (d,
4
quenched with saturated aqueous NH Cl, and extracted with
1
2
J
P-C ) 189.9 Hz), 114.01, 62.21 (d, J P-C ) 5 Hz), 21.26, 16.56
AcOEt. The organic phase was dried over sodium sulfate.
Crude products (entries 7 and 8) were concentrated under
vacuum, and the residues were purified by preparative TLC
on silica gel (AcOEt/hexanes ) 1/10) to give compounds 8a ,b.
Crude products (entries 9 and 10) were treated with 1 equiv
3
+
(
2
9
d, J P-C ) 6.1 Hz); MS (EI) m/z: 460 (M , 38.22), 369 (5.45),
39 (42.74), 195 (68.29), 183 (36.13), 167 (100), 109 (46.26),
1 (49.99); (Found: C, 49.66; H, 4.98. Calcd for C19 PTe:
23 3
H O
C, 49.83; H 5.06%).
Z)-1-(Dieth oxyph osph on yl)-2-(4-ch lor oph en yltellu r yl)-
-p h en yleth en e (6b): yield 0.30 g (63%); mp 54-55 °C; ν
(
2
of Br in AcOEt and concentrated under vacuum. The residues
were purified by recrystallization with CH OH/HCCl to give
3 3
2
-
1
(KBr)/cm 3070, 2987, 1570, 1500, 1450, 1400, 1225, 1013,
products (Z)-9a and (Z)-9b.
8
6
35, 690, 610 cm-1; δ
.53 (d, J ) 17.1, 1H), 4.02-4.41 (m, 4H), 1.21-1.43 (m, 6H);
C NMR δ 153.46 (d, J P-C)7.6 Hz), 142.54 (d, J P-C )24.5
H
(400 MHz) 6.83-7.43 (m, 9H), 6.23-
(Z)-1-(4-Met h ylp h en ylsu lfon yl)-2-(p h en ylt ellu r yl)-2-
p h en yleth en e (8a ): yield 0.172 g (74%); mp 142-143 °C; ν
1
3
2
3
-1
(KBr)/cm 2940, 1601, 1529, 1434, 1320, 1083, 810, 655; δ
H
4
Hz), 141.83, 128.72, 127.84, 127.69 (d, J P-C ) 1.3 Hz), 127.54,
1
1
(500 MHz): 7.95-7.97 (d, J ) 8.2, 2H), 7.37-7.39 (m, 4H),
1
2
13
20.02 (d, J PC ) 189.2 Hz), 115.99, 62.31 (d, J P-C ) 5.2 Hz),
6.54 (d, J P-C ) 6.2 Hz); MS (EI) m/z: 480 (M , 20.83), 367
7.08-7.11 (m, 1H), 6.85-6.95 (m, 8H), 2.47 (s, 3H); C NMR
3
+
δ 147.94, 144.74, 140.80, 139.75, 138.09, 130.10, 130.03,
(
(
6.48), 239 (47.61), 195 (78.72), 167 (100), 109 (47.61), 81
33.63); (Found: C, 45.07; H, 4.13. Calcd for C18 PTe:
128.64, 128.26, 128.03, 127.87, 127.49, 127.43, 117.19, 21.78;
+
H
20ClO
3
MS (EI) m/z: 464 (M , 16.96), 207 (16.15), 193 (43.96), 155
C, 45.19; H 4.21%).
(45.62), 139 (26.50), 91(100), 77 (53.45), 65 (19.11); (Found:
(
Z)-1-(Dieth oxyp h osp h on yl)-2-(p h en yltellu r yl)-2-p h en -
18 2
C, 54.29; H, 3.86. Calcd for C21H O STe: C, 54.59; H, 3.93%).
-1
yleth en e (6c): yield 0.27 g (61%); mp 29-30 °C; ν (KBr)/cm
:
(Z)-1-(4-Met h ylp h en ylsu lfon yl)-2-(4-flu or op h en ylt el-
lu r yl)-2-p h en yleth en e (8b): yield 0.180 g (75%); mp 144-
3
100, 2985, 1560, 1480, 1450, 1400, 1230, 1020, 830, 690,
-1
-1
6
6
6
2
10 cm ; δ
H
(400 MHz) 7.40-7.42 (m, 2H), 6.89-7.08 (m, 8H),
145 °C; ν(KBr)/cm : 2940, 1576, 1486, 1394, 11314, 1234,
.38-6.42 (d, J ) 17.1, 1H), 4.16-4.23 (m, 4H), 1.38-1.41 (m,
1142, 1018, 810, 655; δ (500 MHz): 7.94-7.95 (d, J ) 8.2,
H
1
3
2
3
H); C NMR δ 153.56 (d, J P-C ) 7.7 Hz), 142.63 (d, J P-C
)
2H), 7.32-7.39 (m, 4H), 6.95-6.98 (m, 3H), 6.91 (s, 1H), 6.81-
6.83 (m, 2H), 6.58-6.62 (t, J ) 8.75, 2H), 2.47 (s, 3H); MS
4
4.5 Hz), 140.42, 128.38, 127.68, 127.62 (d, J P-C ) 1.1 Hz),
1
+
1
27.50, 127.28, 119.83 (d, J P-C ) 189.7 Hz), 117.91, 62.13 (d,
(EI) m/z: 482 (M , 14.55), 225 (11.45), 193 (45.25), 155 (46.98),
2
3
J
P-C ) 5.1 Hz), 16.46 (d, J PC ) 6.3 Hz); MS (EI) m/z: 446
139 (22.38), 91(100); (Found: C, 52.34; H, 3.50. Calcd for C
+
(
1
C
M , 40.94), 369 (12.24), 239 (44.68), 195 (69.72), 167 (100),
21
H
17FO
2
STe: C, 52.55; H 3.57%).
(Z)-2-(4-Meth ylph en ylsu lfon yl)vin ylph en yltellu r iu m di-
br om id es (9a ): yield 0.224 g (82%); mp161-162 °C; ν (KBr)/
09 (43.34), 77 (35.94); (Found: C, 48.77; H, 4.73. Calcd for
18
H
21
O
3
PTe: C, 48.70; H 4.77%).
-
1
(
Z)-1-(Dieth oxyph osph on yl)-2-(4-flu or oph en yltellu r yl)-
H
cm : 3002, 1594, 1436, 1295, 1257, 1140, 1078, 710; δ (400
2
(
δ
(
1
(
-p h en yleth en e (6d ): yield 0.31 g (67%); mp 39-40 °C; ν
MHz): 8.26-8.28 (m, 3H), 8.06-8.08 (d, J ) 8.32, 2H), 7.54-
7.56 (m, 3H), 7.43-7.45 (d, J ) 8.20, 2H), 6.95-6.97 (d, J )
8.69, 1H), 2.49 (s, 3H); δ 13C NMR 146.69, 134.64, 134.49,
134.14, 133.37, 131.81, 131.53, 130.48, 130.12, 129.13; MS (EI)
-1
KBr)/cm : 3080, 2987, 1580, 1480, 1230, 1030, 830, 695, 600;
(400 MHz) 7.35-7.38 (m 2H), 6.92-7.0 (m, 5H), 6.58-6.62
m, 2H), 6.37-6.41 (d, J ) 17.2, 1H), 4.17-4.21 (m, 4H), 1.38-
H
1
3
1
+
+
.41 (m, 6H); C NMR δ 162.74 (d, J F-C ) 247 Hz), 153.69
m/z: 467 (M - Br, 2.68), 388 (M - 2Br, 56.85), 298 (17.69),
2
3
3
d, J P-C ) 7.5 Hz), 142.73 (d, J F-C ) 7.6 Hz), 142.52 (d, J P-C
232 (24.60), 207 (43.64), 168 (29.80), 139 (41.76), 102 (35.29),
4
)
24.6 Hz), 127.63, 127.57 (d, J P-C ) 1.3 Hz), 127.41, 119.77
91 (65.35), 77 (100); (Found: C, 32.73; H, 2.52. Calcd for C15
Br STe: C, 33.01; H 2.59%).
(Z)-2-(4-Meth ylph en ylsu lfon yl)-1-h exylvin yl ph en yl tel-
lu r iu m d ibr om id e (9b): yield 0.224 g (71%); mp 127-128
°C; δ
14
H -
1
2
(
d, J P-C ) 189.4 Hz), 115.81 (d, J F-C ) 20.6 Hz), 112.49 (d,
2 2
O
4
2
3
J
F-C ) 3.8 Hz), 62.23 (d, J P-C ) 5.3 Hz), 16.49 (d, J P-C ) 6
+
Hz); MS (EI) m/z: 464 (M , 37.78), 369 (10.57), 239 (47.43),
1
(
95 (75.99), 183 (36.03), 167 (100), 109 (46.73) 91 (49.99);
Found: C, 46.56; H, 4.43. Calcd for C18 PTe: C, 46.80;
H 4.36%).
(
lu r yl)-1-h ep ten e (6e): yield 0.26 g (57%); oil; ν (film)/cm
030, 2950, 1570, 1500, 1465, 1400, 1235, 1040, 960, 800; δ
H
(400 MHz): 8.64-8.66 (d, J ) 7.23, 2H), 8.07-8.10 (d,
H
20FO
3
J ) 8.29, 2H), 7.55-7.61 (m, 3H), 7.41-7.43 (d, J ) 8.21, 2H),
6.44 (s, 1H), 2.54-2.58 (m, 2H), 2.48 (s, 3H), 1.40-1.43 (m,
1
3
Z)-1-(Diet h oxyp h osp h on a t o)-2-(4-m et h ylp h en ylt el-
2H), 1.07-1.16 (m, 6H), 0.75-0.79 (t, J ) 6.88, 3H); δ CNMR
153.31, 146.05, 137.45, 135.40, 131.99, 130.30, 130.10, 128.29,
126.96, 124.35, 35.91, 31.25, 28.54, 28.15, 22.32, 21.87, 13.95;
-
1
3
H
+
+
(
(
(
0
(
400 MHz) 7.78-7.80 (m, 2H), 7.05-7.07 (m, 2H), 6.21-6.26
d, J ) 16.74, 1H), 4.08-4.13 (m, 4H), 2.36 (s, 3H), 2.17-2.20
t, J ) 7.84, 2H), 1.31-1.36 (m, 8H), 1.08-1.10 (m, 2H), 0.96-
MS (EI) m/z: 551 (M - Br, 2.02), 472 (M - 2Br, 31.47), 207
(36.55), 109(100), 91(71.51), 77 (56.99); (Found: C, 39.80; H,
2 2
4.06. Calcd for C21H26Br O STe: C, 40.04; H, 4.16%).
Rea ction of (E)-2-Iod o-1-a lk en yl Su lfon es w ith Ar Te-
Na . To a solution of diaryl ditelluride (0.25 mmol) dissolved
.98 (m, 2H), 0.74-0.78 (t, J ) 7.19, 3H); MS (EI) m/z: 454
+
M , 28.33), 363 (9.65), 233 (100), 221(8.29), 205 (33.50), 177
50.13), 95 (87.94); (Found: C, 47.57; H, 6.43. Calcd for C18
(
H
29
-
2
in (1/1) (v/v) THF/ethanol (2.5 mL) under N was added sodium
PO
(
3
Te: C, 47.83; H 6.47%).
Z)-1-(Dieth oxyph osph on yl)-2-(4-flu or oph en yltellu r yl)-
borohydride (0.6 mmol) in EtOH dropwise until the charac-
teristic dark-red color of the ditelluride faded, and then (E)-
2-iodo-1-alkenyl sulfone (0.5 mmol) in THF was added at 0
°C. The resulting solution was stirred at room temperature
for 20 min, quenched with saturated aqueous NH Cl, and
4
extracted with AcOEt. The organic phase was dried over
-
1
1
2
7
1
1
0
1
-h ep ten e (6f): yield 0.26 g (59%); Oil; ν (film)/cm 3030,
950, 1570, 1500,1400, 1230, 1050, 960, 825; δ (400 MHz)
H
.87-7.91 (m, 2H), 6.93-6.98 (m, 3H), 6.24-6.28 (d, J ) 16.51,
H), 4.08-4.14 (m, 4H), 2.16-2.19 (t, J ) 7.08, 2H), 0.1.31-
.37 (m, 8H), 1.09-1.12 (m, 2H), 0.98-1.00 (m, 2H), 0.76-
.80 (t, J ) 7.19, 3H); C NMR δ 163.47 (d, J F-C ) 248 Hz),
55.31 (d, J P-C ) 6.1 Hz), 144.18 (d, J F-C ) 7.8 Hz), 116.60
sodium sulfate. Crude products 12a -f (entries 11-16) were
treated with 1 equiv of Br in AcOEt and concentrated under
2
1
3
1
2
3
vacuum. The residues were purified via recrystallization with
CH OH/HCCl to give (E)-13a -f. The crude product (entry 17)
2
1
(
d, J F-C ) 20.5 Hz), 115.85 (d, J P-C ) 192.4 Hz), 110.34 (d,
3
3
4
2
1
J
F-C ) 3.7 Hz), 61.94 (d, J P-C ) 5 Hz), 42.43 (d, J P-C ) 23
was concentrated under vacuum, and the residue was purified
by preparative TLC on silica gel (AcOEt:n-hexane ) 1:10) to
give compound (E)-12g.
4
3
Hz), 30.83, 29.62 (d, J P-C ) 1.2 Hz), 22.25, 16.45 (d, J P-C
)
+
6
.3 Hz), 13.90; MS (EI) m/z: 458 (M , 27.82), 363 (17.09), 233
75.13), 177 (44.59), 95 (100); (Found: C, 44.60; H, 5.71. Calcd
for C17 PTe: C, 44.78; H 5.75%).
(
(E)-2-(4-Meth ylph en ylsu lfon yl)-1-bu tylvin yl ph en yl tel-
lu r iu m d ibr om id e (13a ): yield 0.217 g (72%); mp 149-150
H
26FO
3

Synthesis of Functionalized Vinyl Tellurides
C; ν (KBr)/cm-1: 2926, 1595, 1438, 1319, 1142, 1082, 736; δ
J . Org. Chem., Vol. 66, No. 1, 2001 79
°
H
130.50, 130.12, 128.78, 127.52, 31.57, 31.30, 29.95, 28.88,
+
(500 MHz): 8.16-8.18 (m, 2H), 7.71-7.73 (d, J ) 8.26, 2H),
22.41, 21.72, 14.02; MS (EI) m/z: 551 (M - Br, 2.22), 472
+
7
2
1
3
1
1
4
.57-7.59 (m, 1H), 7.47-7.50 (m, 2H), 7.36-7.37 (d, J ) 8.0,
H), 6.77 (s, 1H), 3.56-3.59 (t, J ) 7.87, 2H), 2.46 (s, 3H),
.61-1.65 (m, 2H), 1.45-1.48 (m, 2H), 0.94-0.97 (t, J ) 7.37,
(M - 2Br, 33.05), 265 (16.65), 207 (36.55), 157 (36.77), 109
(100), 91 (71.51), 77 (56.99); (Found: C, 39.88; H, 4.11. Calcd
for C21
2 2
H26Br O STe: C, 40.04; H, 4.16%).
(E)-1-(4-Meth ylph en ylsu lfon yl)-2-ph en yltellu r yl-2-ph en -
yleth en e (12g): yield 0.146 g (63%); mp 129-130 °C; ν (KBr)/
H
cm : 3046, 1576, 1435, 1322, 1140, 1083, 769; δ (500 MHz):
7.77-7.79 (m, 2H), 7.42 (m, 1H), 7.30-7.32 (m, 4H), 7.26-
7.20 (m, 3H), 7.09-7.12 (m, 4H), 6.39 (s, 1H), 2.36 (s, 1H); δ
C NMR 144.90, 143.66, 140.83, 138.68, 137.26, 132.30,
1
3
H); δ C NMR 157.85, 145.49, 139.91, 137.10, 135.72, 132.46,
30.58, 130.20, 128.79, 127.60, 32.06, 31.38, 22.53, 21.79,
+
+
-1
3.78; MS (EI) m/z: 523 (M - Br, 3.89), 444 (M - 2Br,
9.31), 237 (28.62), 207 (54.21), 139 (41.63), 91 (84.77), 81
2 2
(100); (Found: C, 37.77; H, 3.60; Calcd for C19H22SO Br Te:
1
3
C, 37.92; H 3.68%).
(
E)-2-(4-Met h ylp h en ylsu lfon yl)-1-b u t ylvin yl 4-flu o-
130.29, 129.92, 129.34, 128.66, 127.83, 127.57, 127.41, 114.84,
21.59; MS (EI) m/z: 462 (M , 16.36), 309 (7.44), 207 (24.14),
155 (52.24), 105 (24.68), 91 (100), 77 (66.71); (Found: C, 54.12;
18 2
H, 3.87. Calcd for C21H O STe: C, 54.59; H, 3.93%).
An ti-Tellu r osu lfon a tes of 1-Alk yn es. A solution of alkyne
(1.1 mmol), sodium arylsulfinate (5 mmol), and diorgano
ditelluride (0.5 mmol) in 5 mL of 80% aqueous acetic acid was
heated at 80 °C for the time indicated in Table 3. The reaction
mixture was diluted with 20 mL of AcOEt, washed with
+
r op h en yl tellu r iu m d ibr om id e (13b): yield 0.22 g (71%);
mp 170-171 °C; ν (KBr)/cm : 2930, 1577, 1486, 1390, 1313,
234, 1142, 1081, 811, 777; δ
-
1
1
7
7
2
H
(500 MHz): 8.19-8.21 (m, 2H),
.71-7.73 (d, J ) 11.35, 2H), 7.37-7.38 (d, J ) 7.73, 2H),
.16-7.20 (m, 2H), 6.72 (s, 1H), 3.56-3.59 (t, J ) 7.52, 2H),
.47 (s, 3H), 1.58-1.66 (m, 2H), 1.44-1.48 (m, 2H), 0.94-0.97
1
3
1
(
t, J ) 7.14, 3H); δ C NMR 164.88 (d, J F-C ) 255.3 Hz),
3
1
1
2
(
(
58.07, 145.59, 139.81, 138.33 (d, J F-C ) 8.8 Hz), 136.94,
2
4
30.22, 127.58, 122.81 (d, J F-C ) 3.1 Hz), 117.98 (d, J F-C
)
2 4
saturated aqueous sodium bicarbonate, dried over Na SO , and
2 Hz), 32.02, 31.29, 22.51, 21.78, 13.75; MS (EI) m/z: 541
concentrated in a vacuum. Crude products (entreis 22, 23, and
26) were concentrated under vacuum, and the residues were
purified by preparative TLC on silica gel (AcOEt:hexanes )
1:10) to give compounds 12g, 12h , and 12k . Crude products
(entries 18-21, and 24 and 25) were treated with 1 equiv of
+
+
M
- Br, 8.88), 462 (M - 2Br, 48.20), 225 (39.20), 155
49.04), 139 (45.74), 95 (43,66), 91 (100), 81 (70.99); (Found:
FO STe: C, 36.82; H,
C, 36.70; H, 3.35. Calcd for C19
.41%).
E)-2-(4-Met h ylp h en ylsu lfon yl)-1-p en t ylvin yl p h en yl
tellu r iu m d ibr om id e (13c): yield 0.193 g (64%); mp 97-98
H
21Br
2
2
3
(
Br
2
in AcOEt and concentrated under vacuum. The residues
OH/HCCl3.
were purified by recrystallization with CH
3
-1
°
C; ν (KBr)/cm : 2926, 1595, 1438, 1319, 1143, 1081, 811, 736;
(500 MHz): 8.17-8.19 (m, 2H), 7.71-7.73 (d, J ) 8.27, 2H),
(E)-1-(4-Ch lor oph en ylsu lfon yl)-2-ph en yltellu r yl-2-ph en -
yleth en e (12h ): yield 0.412 g (85%); mp154-155 °C; ν (KBr)/
δ
7
2
1
3
1
2
2
8
H
-
1
.58-7.59 (m, 1H), 7.47-7.50 (m, 2H), 7.35-7.37 (d, J ) 8.17,
H), 6.78 (s, 1H), 3.55-3.58 (t, J ) 7.74, 2H), 2.46 (s, 3H),
.63-1.66 (m, 2H), 1.34-1.41 (m, 4H), 0.88-0.92 (t, J ) 6.94,
H
cm : 3020, 1576, 1326, 1142, 1083, 776, 605, 540; δ (500
MHz): 7.80-7.82 (m, 2H), 7.43-7.45 (m, 1H), 7.31-7.35 (m,
1
3
4H), 7.20-7.24 (m, 3H), 7.08-7.10 (m, 2H), 6.38 (s, 1H); δ
C
1
3
H); δ C NMR 157.86, 145.41, 139.93, 137.04, 135.67, 132.37,
NMR 146.57, 140.94, 140.17, 139.46, 137.13, 131.91, 130.45,
130.13, 129.09, 128.98, 128.93, 128.02, 127.45, 114.81; MS (EI)
m/z: 484 (M , 25.01), 309 (11.57), 277 (7.24), 213 (43.59), 205
30.49, 130.12, 128.79, 127.51, 31.51, 31.28, 29.64, 22.22,
1.73, 13.86; MS (EI) m/z: 523 (M+ - Br, 3.89), 444 (M
+
-
+
Br, 49.31), 237 (28.62), 207 (54.21), 139 (41.63), 91 (84.77),
1 (100); (Found: C, 38.81; H, 3.88. Calcd for C20
(32.02), 175 (36.40), 111 (59.97), 77 (100); (Found: C, 49.69;
H,3.08. Calcd for C20H15ClO STe: C, 49.79; H, 3.13%).
2
H
24Br
2
O
2
-
STe: C, 39.00; H,3.93%).
E)-2-(4-Met h ylp h en ylsu lfon yl)-1-p en t ylvin yl 4-flu o-
r op h en yl tellu r iu m d ibr om id e (13d ): yield 0.199 g (63%);
(E)-2-(P h en ylsu lfon yl)-1-bu tylvin yl p h en yl tellu r iu m
d ibr om id e (13i): yield 0.300 g (51%); mp 135-136 °C; ν (KBr)/
(
-
1
H
cm : 3057, 2930, 1436, 1390, 1147, 1081, 735, 659; δ (500
-
1
mp 158-159 °C; ν (KBr)/cm : 2930, 1578, 1486, 1393, 1313,
MHz): 8.19-8.21 (m, 2H), 7.87-7.88 (m, 2H), 7.69-7.72 (m,
1H), 7.59-7.62 (m, 3H), 7.49-7.52 (m, 2H), 6.79 (s, 1H), 3.60-
3.63 (m, 2H), 1.64-1.68 (m, 2H), 1.46-1.50 (m, 2H), 0.96-
1
7
7
)
4
234, 1141, 1081, 811, 653; δ (500 MHz): 8.19-8.22 (m, 2H),
H
.72-7.73 (d, J ) 8.02, 2H), 7.57-7.59 (d, J ) 8.02, 1H), 7.37-
.38 (m, 2H), 7.17-7.20 (m, 2H), 6.73 (s, 1H), 3.55-3.58 (t, J
1
3
0.99 (m, 3H); δ C NMR 158.33, 139.93, 139.51, 135.66,
7.67, 2H), 2.47 (s, 3H), 1.63-1.66 (m, 2H), 1.34-1.40 (m,
134.22, 132.43, 130.52, 129.53, 128.87, 127.45, 31.99, 31.39,
H), 0.89-0.92 (t, J ) 6.62, 3H); δ 13C NMR 164.92 (d, J F-C
1
22.46, 13.73; MS (EI) m/z: 509 (M - Br, 2.98), 430 (M
+
+
-
3
)
255.1 Hz), 158.13, 145.57, 139.93, 138.32 (d, J F-C ) 8.8 Hz),
2Br, 28.58), 223 (19.10), 207 (38.51), 143 (30.67), 77 (100);
2
1
3
1
9
37.05, 130.21, 127.61, 122.84, 117.98 (d, J F-C ) 22.1), 31.49,
(Found: C, 36.66; H, 3.32; Calcd for C18
H, 3.43%).
2 2
H20Br O STe: C, 36.78;
+
1.33, 29.69, 22.26, 21.75, 13.85; MS (EI) m/z: 553 (M - Br,
+
.14), 476 (M - 2Br, 17.72), 225 (27.04), 157 (31.10), 95(100),
(E)-2-(P h en ylsu lfon yl)-1-h exylvin yl p h en yl tellu r iu m
d ibr om id e (13j): yield 0.376 g (61%); mp 96-98 °C; ν (KBr)/
2 2
1 (59.61); (Found: C, 37,77; H, 3.60. Calcd for C20H23Br FO -
-
1
STe: C, 37.90; H, 3.66%).
E)-2-(4-Met h ylp h en ylsu lfon yl)-1-h exylvin yl 4-flu o-
r op h en yl tellu r iu m d ibr om id e (13e): yield 0.185 g (57%);
H
cm : 3032, 2925, 1446, 1326, 1147, 1081, 792, 635; δ (500
(
MHz): 8.17-8.18 (m, 2H), 7.84-7.86 (m, 2H), 7.66-7.69 (m,
1H), 7.56-7.59 (m, 3H), 7.47-7.50 (m, 2H), 6.78 (s, 1H), 3.56-
3.59 (m, 2H), 1.62-1.68 (m, 2H), 1.38-1.42 (m, 2H), 1.29-
1.31 (m, 4H) 0.89-0.91 (m, 3H); δ 13C NMR 158.52, 140.17,
139.70, 135.71, 134.27, 132.52, 130.65, 129.60, 128.75, 127.58,
-
1
mp 118-120 °C; ν (KBr)/cm : 2926, 2854, 1578, 1486, 1394,
314, 1234, 1141, 1081, 811, 654; δ (500 MHz): 8.19-8.22
m, 2H), 7.71-7.73 (m, 2H), 7.36-7.38 (m, 2H), 7.17-7.20 (m,
H), 6.73 (s, 1H), 3.55-3.58 (m, 2H), 2.47 (s, 3H), 1.61-1.65
m, 2H), 1.38-1.40 (m, 2H), 1.28-1.30 (m, 4H), 0.89-0.91 (m,
1
H
(
2
+
31.70, 31.39, 30.07, 28.99, 22.49, 14.07; MS (EI) m/z: 537 (M
+
(
- Br, 2.32), 458 (M - 2Br, 35.20), 207 (39.46), 143 (40.32),
109 (97.88), 77 (100); (Found: C, 38.85; H, 3.84. Calcd for
1
3
1
3
1
1
3
H); δ C NMR 164.89 (d, J F-C) 255.3 Hz), 158.21, 145.57,
3
39.93, 138.34 (d,
22.85 (d, J F-C)3.2 Hz), 117.98 (d, J F-C) 22.1 Hz), 31.55,
1.34, 29.99, 28.93, 22.46, 21.77, 14.05; MS (EI) m/z: 569 (M
J
F-C) 8.7 Hz), 137.02, 130.21, 127.60,
C
20
H
24Br
2
O
2
STe: C, 39.00; H, 3.93%).
(E )-1-(4-Me t h ylp h e n ylsu lfon yl)-2-(p h e n ylt e llu r yl)-
eth en e (12k ): yield 0.1 g (26%); Mp 124-126 °C; δ (400
4
2
+
H
+
-
Br, 2.60), 490 (M - 2Br, 41.09), 265 (16.94), 225 (40.52),
MHz): 8.57-8.61 (d, J ) 15.83, 1H), 7.76-7.78 (m, 2H), 7.69-
7.72 (m, 2H), 741-7.43 (m, 1H), 730-7.33 (m, 4H), 6.41-6.45
(d, J ) 15.82, 1H), 2.42 (s, 3H); δ 13C NMR 144.32, 140.09,
137.48, 134.77, 130.29, 130.01, 129.72, 127.76, 126.15, 110.83,
1
55 (45.73), 139 (38.03), 109 (100), 91 (74.35); (Found: C,
8.73; H, 3.81. Calcd for C21 FO STe: C, 38.93; H3.89%).
E)-2-(4-Meth ylph en ylsu lfon yl)-1-h exylvin yl ph en yl tel-
lu r iu m d ibr om id e (13f): yield 0.195 g (62%); mp96-97 °C;
3
H
25Br
2
2
(
+
21.69; MS (EI) m/z: 388 (M , 50.83), 207 (40.66), 91 (65.35),
-
1
ν (KBr)/cm : 2924, 1595, 1437, 1319, 1143, 1081, 811, 736,
77 (100); (Found: C, 46.42; H, 3.56; Calcd for C15
C, 46.68; H, 3.66%).
14 2
H O STe:
6
7
44, 539; δ
H
(500 MHz): 8.17-8.19 (m, 2H), 7.72-7.73 (m, 2H),
.57-7.59 (m, 1H), 7.48-7.50 (m, 2H), 7.35-7.37 (m, 2H), 6.78
An ti-Ad d ition of Ar TeI w ith 1-Alk yn es. A mixture of 1
mmol of ArTeI (prepared by the reaction of a diarylditelluride
(
s, 1H), 3.55-3.58 (m, 2H), 2.46 (s, 3H), 1.62-1.65 (m, 2H),
1
.38-1.40 (m, 2H), 1.28-1.31 (m, 4H), 0.89-0.91 (m, 3H); δ
C NMR 157.91, 145.40, 139.95, 137.08, 135.67, 132.38,
(0.5 mmol) with I
2
(0.55 mmol) in THF at 0 °C) and 1 mmol of
1
3
an alkyne was stirred at room temperature for 12 h followed

8
0
J . Org. Chem., Vol. 66, No. 1, 2001
Huang et al.
by the treatment with saturated Na
2
S
2
O
3
. After stirring for
7.54 (m, 2H), 7.36 (s, 1H), 3.09-3.12 (t, J ) 7.63, 2H), 1.73-
1.77 (m, 2H), 1.39-1.48 (m, 4H), 0.92-0.96 (t, J ) 7.16, 3H);
3
0 min, the mixture was extracted with hexanes, dried over
1
3
CaCl
2
, and concentrated in a vacuum. The residues were
δ
C NMR 144.62, 139.16, 137.05, 130.62, 127.08, 95.66,
+
purified by preparative TLC on silica gel eluted with hexanes
38.08, 31.10, 28.33, 22.41, 13.97; MS (EI) m/z: 543 (M - 79,
to give compounds 16, which reacted with Br
afford (E)-17a -f.
2
(1 equiv) to
11.90), 464 (31.12), 241(40.27), 95 (100); (Found: C, 25.17; H,
2.55. Calcd for C13
2
H16Br ClITe: C, 25.10; H 2.59%).
(
E)-(2-Iod o-1-bu tyl)vin yl p h en yl tellu r iu m d ibr om id e
(
E)-(2-Iod o-1-h exyl)vin yl p h en yl tellu r iu m d ibr om id e
-1
(
2
8
17a ): yield 0.258 g (45%); mp 146-147 °C; ν (film)/cm : 3067,
-1
(
2
8
)
(
1
2
(
17e): yield 0.222 g (37%); mp 72-73 °C; ν (film)/cm : 3056,
928, 1636, 1438, 1253, 1112, 994, 730, 680; δ
H
(400 MHz)
925, 2850, 1582, 1437, 994, 728, 678; δ
.32 (m, 2H), 7.54-7.61 (m, 3H), 7.37 (s, 1H), 3.09-3.13 (t, J
7.78, 2H), 1.74-1.78 (m, 2H), 1.46-1.50 (m, 2H), 1.34-1.36
H
(400 MHz) 8.30-
.29-8.32 (m, 2H), 7.54-7.61 (m, 3H), 7.37 (s, 1H), 3.10-3.14
(
t, J 7.92, 2H), 1.72-1.77 (m, 2H), 1.48-1.54 (m, 2H), 0.98-
13
1
1
4
.01 (t, J ) 7.3, 3H); δ C NMR 144.52, 135.74, 132.19, 130.51,
30.39, 129.40, 95.52, 38.00, 30.72, 22.28, 13.90; MS (EI) m/z:
13
m, 4H), 0.90-0.93 (t, J ) 6.72, 3H); δ C NMR 144.53,
35.73, 132.19, 130.51, 129.43, 95.53, 38.25, 31.51, 28.73,
8.64, 22.57, 14.12, MS (EI) m/z: 523 (M - 79, 2.36), 442
+
95 (M - 79, 4.32), 416 (17.03), 334 (10.95), 207 (53.19), 77
+
2
(100). (Found: C, 24.96; H, 2.55. Calcd for C12H15Br ITe: C,
12.09), 334 (7.27), 207 (40.43),109 (100); (Found: C, 27.85;
H, 3.14. Calcd for C14 ITe: C, 27.95; H 3.18%).
E)-(2-Iod o-1-h exyl)vin yl 4-ch lor op h en yl tellu r iu m d i-
2
5.13; H 2.64%).
E)-(2-Iod o-1-bu tyl)vin yl 4-ch lor op h en yl tellu r iu m d i-
br om id e (17b): yield 0.322 g (53%); mp. 123-124 °C; ν (film)/
H
19Br
2
(
(
br om id e (17f): yield 0.273 g (43%); mp. 80-81 °C; ν (film)/
-
1
cm : 3065, 2955, 1636, 1559, 1471, 1385, 1094, 1088, 1003,
-1
cm : 3057, 2925, 2950, 1571, 1560, 1472, 1385, 1091, 1002,
8
7
1
1
2
3
07, 702; δ (400 MHz) 8.25-8.27 (m, 2H), 7.52-7.54 (m, 2H),
H
8
7
1
3
3
04, 720; δ (400 MHz) 8.25-8.27 (m, 2H), 7.52-7.54 (m, 2H),
H
.35 (s, 1H), 3.09-3.13 (t, J ) 7.98, 2H), 1.71-1.75 (m, 2H),
.48-1.54 (m, 2H), 0.98-1.01 (t, J ) 7.3, 3H); δ 13C NMR
44.58, 139.12, 137.06, 130.59, 127.04, 95.68, 37.87, 30.68,
2.23, 13.89; MS (EI) m/z: 529 (M+ - 79, 4.69), 450 (26.66),
68 (17.00), 241 (87.09), 81 (100). (Found: C, 23.83; H, 2.28.
.36 (s, 1H), 3.09-3.12 (t, J ) 7.54, 2H), 1.72-1.76 (m, 2H),
.46-1.49 (m, 2H), 1.33-1.37 (m, 4H), 0.90-0.93 (t, J ) 6.89,
13
H); δ C NMR 144.65, 139.21, 137.05, 130.65, 127.08, 95.58,
+
8.15, 31.49, 28.71, 28.64, 22.56, 14.12; MS (EI) m/z: 557 (M
-
79, 4.83), 478 (22.96), 241 (55.30), 109 (100); (Found: C,
Calcd for C12
2
H14Br ClITe: C, 23.71; H 2.32%).
2
6.41; H, 2.81. Calcd for C14 ClITe: C, 26.44; H 2.85%).
H18Br
2
(
E)-(2-Iod o-1-p en tyl)vin yl p h en yl tellu r iu m d ibr om id e
-
1
(
2
17c): yield 0.282 g (48%); mp 93-94 °C; ν (film)/cm : 3054,
Ack n ow led gm en t. Project No. 29772007 supported
by the National Nature Science Foundation of China.
We also thank Dr. Shengming Ma for helpful discussion.
930, 2984, 1636, 1584, 1437, 1116, 994, 729, 679; δ (400
H
MHz) 8.30-8.32 (m, 2H), 7.54-7.61 (m, 3H), 7.37 (s, 1H),
3
4
1
.09-3.13 (t, J ) 7.86, 2H), 1.75-1.78 (m, 2H), 1.39-1.49 (m,
H), 0.92-0.96 (t, J ) 7.0, 3H); δ 13C NMR 144.47, 135.73,
32.15, 130.46, 129.37, 95.63, 38.16, 31.10, 28.03, 22.40, 14.00;
Su p p or tin g In for m a tion Ava ila ble: 1H NMR spectra of
+
MS (EI) m/z: 509 (M - 79, 7.36), 430 (16.44), 334 (4.85), 207
(
6
a -f, 8a ,b, 9a ,b, 12g, 12h , 12k , 13a -f, 13i, 13j, and 17a -f;
38.17), 95 (100). (Found: C, 26.88; H, 2.92. Calcd for C13
H
17
-
13
C NMR spectra of 6a -d , 6f, 8a , 9a ,b, 12g, 12h , 12k , 13a -
Br
2
ITe: C, 26.57; H 2.92%).
E)-(2-Iod o-1-p en tyl)vin yl 4-ch lor op h en yl tellu r iu m
1
1
f, 13i-j, and 17a -f; H- H NOESY spectra of 6c, 6e, 8b, 9b,
and 13f, and ORTEP figures of 6a and 17b. This material is
available free of charge via the Internet at http://pubs.acs.org.
(
d ibr om id e (17d ): yield 0.317 g (51%); mp 104-105 °C; ν
-
1
(film)/cm 3054, 2931, 2869, 1560, 1472, 1385, 1179, 1093,
1
004, 806, 721, 655; δ (400 MHz) 8.25-8.27 (m, 2H), 7.52-
H
J O001026B