A stereoselective synthetic route to (Z)-1-arylthio vinylstannanes

Article abstract of DOI:10.1039/a809042d

Acetylenic stannanes react with Cp₂Zr(H)Cl (Cp=η⁵-C₅H₅) to give organozirconium(IV) complexes, which are trapped with arylsulfenyl chloride to afford (Z)-l-arylthio vinylstannanes.

Full text of DOI:10.1039/a809042d

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290 J. CHEM. RESEARCH (S), 1999
J. Chem. Research (S),
1999, 290^291y
A Stereoselective Synthetic Route to
(Z)-1-Arylthio Vinylstannanesy
Xian Huang* and Ping Zhongz
Department of Chemistry, Zhejiang University, at Xixi Campus, Hangzhou, 310028, P.R. China
Acetylenic stannanes react with Cp2ZrꢀH†Cl ꢀCp ˆ Z5-C5H5† to give organozirconium(IV) complexes, which are
trapped with arylsulfenyl chloride to afford (Z)-l-arylthio vinylstannanes.
3
Vinyl sul¢des1
and vinylstannanes4 have been used as
Table 1 Synthesis of compounds 3a^ga
synthetic intermediates to construct some ole¢ns.
(E)-1-Phenylthiovinylstannanes can be prepared by the
reaction of 1-phenylthio-1-alkynes with tributyltin hydride,5
but the Z-stereoisomers have not been reported. Herein,
we report a convenient approach to (Z)-1-phenylthiovinyl-
stannanes from acetylenic stannanes.
Product
R
R0
Ar
Yield(%)
3a
3b
3c
3d
3e
3f
Ph
MeOCH2
Bu
Bu
Bu
Bu
Bu
Bu
Bu
Et
Ph
Ph
Ph
4-MeC6H4
4-MeC6H4
4-ClC6H4
Ph
80
76
70
74
69
76
68
Ph
MeOCH2
MePh
OCH2
Recently, it has become popular to transform
alkenylzirconium(IV) complexes to other functional groups
with a high level of stereochemical purity.6 Vinylzirconium
complexes react with phenyltellurenyl iodide or arylselenenyl
bromides readily to a¡ord (E)-vinylic tellurides7 or (E)-vinylic
selenides.8 Considering the high electrophility of arylsulfenyl
chlorides, we tried to react them with the vinylzirconium
complexes 29 produced by hydrozirconation of acetylenic
stannanes 1. Experimental results show that Cp2ZrꢀH†Cl10
adds to acetylenic stannananes11 in THF at room temperature
stereospeci¢cally with high regioselectivity to yield the vinylic
3g
a The products were identified by MS, 1H NMR and IR
spectroscopy.
The 1,1-difunctional compounds 3 have recently emerged
as valuable reagents for organic synthesis. For example,
palladium-catalyzed coupling reaction of 3a with
diphenyliodonium chloride a¡ords (E)-1-phenyl-1-phenylthio-
styrene (5) in 78% yield. Vinylsul¢de 5 is readily hydrolyzed
in the presence of TiCl4 to a¡ord 1-phenylacetophenone
(6) in 96% yield.4 This synthetic route, in which 3a is equiv-
alent to the synthon PhCH2C ˆ O, also provides a new
method to obtain the ketone 6 (Scheme 3).
Zr complex 2 which react with arylsulfenyl chlorides12
IV
rapidly at 0 8C to afford vinylstannanes 3. Yields are good
to excellent (Scheme 1 and Table 1).
R
H
SnR'3
R
H
SnR'3
SAr
Cp2Zr(H)Cl
Ph
SnBu3
+ Ph2I+Cl–
Ph
Ph
Ph
TiCl4/H2O
Ph
ArSCl
Pd(PPh3)4/Cul
RC CSnR'3
ZrCp2Cl
H
SPh
H
SPh
O
1
2
3
3a
5
6
Scheme 1 R ˆ Ph, Bu, MeOCH2; R0 ˆ Et, Bu; Ar ˆ Ph,
Scheme 2
4-MeC6H4, 4-ClC6H4
Experimental
1-Phenylthio vinylstannanes can be transformed into vinylic
sul¢des. As the reaction occurs steroselectively,13 it can be
used to con¢rm the con¢guration of arylthio vinylstannanes
3. For example, the con¢guration of vinylstannane 3b could
be con¢rmed from compound 4 which was obtained by treat-
ment of 3b with n-butyllithium in THF followed by
hydrolysis; the reaction occurs stereoselectively (Scheme 2).13
Particularly diagnostic for the stereochemistry of 4 is the
coupling constant between the vicinal protons Ha and Hb
which show a typical value of JHH of 16 Hz which is consist-
ent with an E-con¢guration. Therefore, we can con¢rm that
the arylthio vinylstannanes 3 have Z con¢guration.
1H NMR spectra were recorded on a AZ-300 spectrometer with
TMS as internal standard. Mass spectra were obtained on Finigan 8230
mass spectrometer. IR spectra were determined on PE-683 instrument
as neat ¢lms. All reactions were carried out in pre-dried glassware
(140 8C, 4 h) and cooled under a stream of dry nitrogen. All solvents
were dried, deoxygenated and redistilled before use.
General Procedure for the Synthesis of 3a^g.öA mixture of
Cp2ZrꢀH†Cl (1mmol) and 1 (1mmol) in THF (5 ml) was stirred
at room temperature for 40 min. The resulting solution was cooled
to 0 8C and ArSCl (1 mmol) was injected and the mixture was
stirred at 0±10 8C for 40 min. The solvent was then removed by
rotary evaporation under reduced pressure. The residue was
extracted with light petroleum (3 Â 6 ml) and ®ltered through a
short plug of silica gel. After evaporation of the ®ltrate, the residue
was puri®ed by preparative TLC on silica gel eluting with light
petroleum.
MeOCH2
H
SnBu3
SPh
MeOCH2
Ha
Hb
1. –78 ˚C, BunLi, THF
2. H2O
3a: oil. IR (¢lm): n=cm 1 3160,1590, 1585, 1485, 1095, 810; dHꢀCDCl3†
‡
7.50^7.10 (m, 10 H), 6.75 (s, 1H), 1.40^0.70 (m, 27 H); MS: m/z 502 (M ,
SPh
26.00), 470 (20.12), 359 (23.25), 251 (100), 216 (74.09), 184 (54.99), 108
(29.33%); Calc. for C26H38SSn: C, 62.29; H, 7.64. Found: C, 62.44,
H, 7.67%.
3b
4
1
3b: oil. IR (¢lm): n=cm 3095, 1590, 1470, 1020, 735; dHꢀCDCl3†
Scheme 2
7.43^7.10 (m, 5 H), 6.44 (t, J 6.0 Hz, 1H), 3.70 (d, J 6.0 Hz, 2 H), 3.22
‡
(s, 3 H), 1.35^0.70 (m, 27 H); MS: m/z 469 (M , 5.15), 255 (12.48),
177 (22.01), 147 (100), 103 (18.69), 45 (17.35%); Calc. for
* To receive any correspondence.
C22H38OSSn: C, 56.31; H, 8.16. Found: C, 56.45, H, 8.19%.
1
y This is a Short Paper as de¢ned in the Instructions for Authors,
Section 5.0 [see J. Chem. Research (S), 1999, Issue 1]; there is
therefore no corresponding material in J. Chem. Research (M).
z Permanent address: Department of Chemistry, Yichun Normal
Institute, Yichun, 336000, P.R. China.
3c: oil. IR (¢lm): n=cm 3090, 1595, 1485, 1025, 870; dHꢀCDCl3†
7.40^7.16 (m, 5 H), 6.25 (t, J 6.0 Hz, 1H), 2.45^2.32 (m, 2 H); 1.65^0.68
‡
(m, 34 H); MS: m/z 482 (M , 3.11), 291 (76.64), 190 (81.31), 147 (64.96),
103 (46.35), 81 (100%). Calc. for C24H42SSn: C, 59.89; H, 8.79. Found:
C, 60.01, H, 8.82%.

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J. CHEM. RESEARCH (S), 1999 291
1
3d: oil. IR (¢lm): n=cm 3150, 1605, 1485, 1020, 825 dHꢀCDCl3†
Project 29772007 was supported by the National Nature
Science Foundation of China and this work also supported
by The Laboratory of Organometallic Chemistry, Chinese
Academy of Science.
‡
7.45^7.00 (m, 10 H), 2.28 (s, 3 H), 1.60^0.70 (m, 27 H); MS: m/z 515 (M ,
6.52), 459 (100), 246 (49.47), 226 (36.01), 123 (32.06), 91 (28.62%); Calc.
for C27H40SSn: C, 62.93; H, 7.82. Found: C, 62.98, H, 7.80%.
1
3e: oil. IR (¢lm): n=cm 3140, 1600, 1420, 285 dHꢀCDCl3† 7.30^6.9 0
(m, 4 H), 6.40 (t, J 6.0 Hz, 1H), 3.80 (d, J 6.0 Hz, 2 H), 3.20 (s, 3 H),
‡
2.28 (s, 3 H), 1.55^0.70 (m, 27 H); MS: m/z 483 (M , 3.35), 289 (30.17),
283 (59.85), 161 (100), 117 (13.26), 45 (11.03%); Calc. for
C
23H40OSSn: C, 57.16; H, 8.34. Found: C, 57.33, H, 8.38%.
Received, 19th November 1998; Accepted, 20th January 1999
Paper E/8/09042D
1
3f: oil. IR (¢lm): n=cm 3150, 1605, 1485, 1015, 820 dHꢀCDCl3†
‡
7.45^7.05 (m, 9 H), 7.00 (s, 1H), 1.60^0.65 (m, 27 H); MS: m/z 534 ,
1.30), 479 (31.39), 386 (33.65), 262 (41.26), 244 (100), 210 (53.8), 57
(39.33%). Calc. for C23H37ClSSn: C, 58.29; H, 6.96. Found: C, 58.26,
H, 6.96%.
1
References
3g: oil. IR (¢lm): n=cm 3080, 1590, 1480, 1385, 1190, 1020, 740
dHꢀCDCl3† 7.40^7.10 (m, 4 H), 6.40 (t, J 6.0 Hz, 1H), 4.10 (d, J 6.0 Hz,
1
B. M. Trost and A. C. Lavoie, J. Am. Chem. Soc., 1983, 105,
5075.
‡
2 H), 3.18 (s, 3 H), 1.30 (s, 3 H), 1.30^0.65 (m, 15 H); MS: m/z 385 (M ,
3.76), 321 (25.18), 291 (19.57), 255 (100), 177 (35.86), 147 (47.77), 45
(29.49%). Calc. for C16H26OSSn: C, 49.90; H, 6.804. Found: C, 49.97,
H, 6.76%.
2
3
4
A. Alexakis and J. F. Normant, Synthesis, 1985, 72.
T.-Y. Luh and Z. J. Ni, Synthesis, 1990, 89.
J. K. Stille and J. H. Simpson, J. Am. Chem. Soc., 1987, 109,
2138.
P. A. Magriotis, J. T. Brown and M. E. Scott, Tetrahedron
Lett., 1991, 32, 5047.
P. Wipf and H. Jahn, Tetrahedron, 1996, 52, 12853.
J. W. Sung, C. W. Lee and D. Y. Oh, Tetrahedron Lett., 1995,
36, 1503.
X. Huang and L. S. Zhu, J. Chem. Soc., Perkin Trans. 1, 1996,
767.
Synthesis of (E)-Vinylsul¢de (4).öBuLi (1ml, 1 M hexane solution)
was added to a THF (5.0 ml) solution of 3b (1.0 mmol) at 78 8C.
After stirring for 30 min, the mixture was hydrolyzed with satu-
rated aq. NH4Cl and extracted with CH2Cl2 ꢀ2 Â 10 ml). The
organic extract was dried with MgSO4, ®ltered and concentrated in
vacuo. The residue was puri¢ed by column chromatography over
silica gel, eluting with petroleum to give (E)-vinylsul¢de 4 (yield:
90%).
5
6
7
8
9
1
4. oil. IR (¢lm): n=cm 3080, 1595, 1488, 950; dHꢀCDCl3† 7.0 0^7.50
B. H. Lipshutz, R. Keil and J. C. Barton, Tetrahedron Lett.,
1992, 33, 5861.
(m, 5 H), 6.30 (d, 1H, J 16 Hz), 5.70 (dd, J 16, 6 Hz, 1 H), 3.82 (d,
2 H, J 6 Hz), 3.20 (s, 3 H).
10 S. L. Buchwald, S. J. Lamaire, R. B. Nielsen, B. T. Watson and
S. M. King, Tetrahedron Lett., 1987, 28, 3895 and references
cited therein.
11 M. W. Logue and T. Teng, J. Org. Chem., 1982, 47, 2549.
12 D. N. Harpp, B. T. Friedlander and R. A. Smith, Synthesis,
1979, 181.
13 B. T. Grobel and D. Seebach, Chem. Ber., 1977, 110, 867.
14 T. Mukaiyama, K. Kamio, S. Kobayashi and H. Takei, Bull.
Chem. Soc., 1972, 45, 3723.
15 F. M. Beringer, M. Drexler, E. M. Gindler and C. C.
Lumpkin, J. Am. Chem. Soc., 1953, 75, 2705.
16 J. Nakayama, S. Takeue and M. Hoshino, Tetrahedron Lett.,
1984, 25, 2679.
Synthesis of (E)-1-Phenyl-1-phenylthioethene (5).öVinyltributyl-
stannane 3a (0.5 mmol) and diphenyliodonium chloride15 (0.5 mmol)
were dissolved in DMF (5 ml) under nitrogen at room temperature.
PdꢀPPh3† (0.05 mmol) and Cu (0.4 mmol) were then added and
4
the mixture stirred at room temperature and monitored by TLC
for the disappearance of the starting organostannane. The reaction
mixture was diluted with CH2Cl2 (15 ml), ¢ltered and stirred with
20% aqueous KF (10 ml) for 30 min before being dried and con-
centrated. The residue was puri¢ed by column chromatography on
silica gel, eluting with petroleum to give 5 (yield: 78%).
1
5. mp 76^77 8C (lit.,16 77±78 8C) IR (KBr): n=cm 3080, 1625,
1580, 1480, 1075, 1020, 730; dHꢀCDCl3† 7.45±7.06 (m, 16 H).