Studies on hydrozirconation of 1-alkynyl sulfoxides or sulfones and the application for the synthesis of stereodefined vinyl sulfoxides or sulfones

Article abstract of DOI:10.1021/jo0111154

The hydrozirconation reaction of 1-alkynyl sulfoxides or sulfones with CP₂Zr(H)Cl in THF at room temperature predominantly gave Z-β-zirconated vinyl sulfoxides or sulfones with excellent regioselectivity. Compared with 1-alkynyl sulfoxides, the hydrozirconation reaction of 1-alkynyl sulfones exhibits great synthetic potential, leading to the efficient preparation of Z-β-halovinyl sulfones, Z-β-sulfonyl α,β-unsaturated ketones, and Z-β-alkynyl vinyl sulfones. Although the reaction mechanisms are still not clear, the neighboring group participation of the sulfinyl or sulfonyl group may be playing an important role in this unique hydrozirconation reaction.

Full text of DOI:10.1021/jo0111154

Stu d ies on Hyd r ozir con a tion of 1-Alk yn yl Su lfoxid es or Su lfon es
a n d th e Ap p lica tion for th e Syn th esis of Ster eod efin ed Vin yl
Su lfoxid es or Su lfon es
Xian Huang,*,†,‡ Dehui Duan,†,‡ and Weixin Zheng†
Department of Chemistry, Zhejiang University (Campus Xixi), Hangzhou 310028, Zhejiang, P. R. China,
and State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, P. R. China
huangx@mail.hz.zj.cn
Received November 30, 2001
The hydrozirconation reaction of 1-alkynyl sulfoxides or sulfones with Cp2Zr(H)Cl in THF at room
temperature predominantly gave Z-â-zirconated vinyl sulfoxides or sulfones with excellent
regioselectivity. Compared with 1-alkynyl sulfoxides, the hydrozirconation reaction of 1-alkynyl
sulfones exhibits great synthetic potential, leading to the efficient preparation of Z-â-halovinyl
sulfones, Z-â-sulfonyl R,â-unsaturated ketones, and Z-â-alkynyl vinyl sulfones. Although the reaction
mechanisms are still not clear, the neighboring group participation of the sulfinyl or sulfonyl group
may be playing an important role in this unique hydrozirconation reaction.
In tr od u ction
enic sulfones exhibited nice regioselectivity and yielded
the trans-addition product Z-2-zirconated-1-alkenyl sul-
fones. Thus, we envisioned that the hydrozirconation
reaction of 1-alkynyl sulfoxides or sulfones could provide
a highly efficient synthetic approach to stereodefined
vinyl sulfoxides or sulfones (eq 1).7 In this paper, we
1-Alkenylzirconium (IV) complexes can be readily
prepared by the cis-insertion of C,C-triple bonds into the
Zr-H bond of Schwartz’s reagent [Cp2Zr(H)Cl].1 It is
well-documented that these alkenylzirconocenes can
undergo many transformations with the retention of the
configurations of the C,C-double bonds.2 The hydro-
zirconation of a heteroatom-substituted alkyne provides
a convenient approach to an alkenylic intermediate with
two functionalities, which may be utilized for the stereo-
selective synthesis of polysubstituted alkenes. In these
reactions, the zirconium group occupies the position R
to these heteroatoms highly regioselectively and the
stereoselectivity exhibits cis-addition exclusively.3
report the hydrozirconation of 1-alkynyl sulfoxides and
sulfones and demonstrate its potential application to the
synthesis of vinyl sulfoxides or sulfones in detail.
Efficien t a n d h igh ly ster eoselective m eth od olo-
gies for th e syn th esis of vin yl su lfoxid es a n d su l-
fon es a r e of cu r r en t in ter est4,5 due to their importance
in organic synthesis.6 In our preliminary communication,7
the hydrozirconation reaction of aryl-substituted acetyl-
Resu lts a n d Discu ssion s
Hyd r ozir con a tion Rea ction of 1-Alk yn yl Su lfox-
id es. When phenylacetylenic sufoxide 1a was treated
with Cp2Zr(H)Cl in THF at room temperature followed
by protonolysis, E-vinyl sulfoxides 3a was obtained
exclusively. The E-olefin geometry was verified by the
coupling constant of the two olefinic protons (3J HH ) 15.2
Hz).8 When the in-situ formed alkenylzirconium inter-
mediate 2a was treated with NBS at room temperature,
Z-â-bromovinyl sufoxide 4a was formed exclusively. Its
configuration was determined by the comparison with the
authentic sample prepared from the trans-hydrobromi-
nation reaction of 1a 9 (Scheme 1).
* Corresponding author. Fax: 86-571-88807077.
† Zhejiang University (Campus Xixi).
‡ Chinese Academy of Sciences.
(1) (a) Hart, D. W.; Schwartz, J . J . Am. Chem. Soc. 1974, 96, 8115.
(b) Schwartz, J .; Labinger, J . A. Angew. Chem., Int. Ed. Engl. 1976,
15, 333.
(2) For a recent review on alkenylzirconocene, see: Wipf, P.; J ahn,
H. Tetrahedron 1996, 52, 12853.
(3) (a) Dabdo2.ub, M. J .; Baroni, A. C. M. J . Org. Chem. 2000, 65,
54. (b) Sung, J . W.; J ang, W. B.; Oh, D. Y. Tetrahedron Lett. 1996, 37,
7537. (c) Huang, X.; Wang, J .-H.; Yang, D.-Y. J . Chem. Soc., Perkin
Trans. 1 1999, 673.
(4) (a) Liu, L. K.; Chi, Y.; J en, K. Y. J . Org. Chem. 1980, 45, 406.
(b) Back, T. G.; Collins, S. J . Org. Chem. 1981, 46, 3249. (c) Happer,
D. A. R.; Steenson, B. E. Synthesis 1980, 806. (d) Posner, G. H.;
Brunelle, D. J . J . Org. Chem. 1972, 37, 3547.
(5) (a) Mikolajczyk, M.; Perlikowska, W.; Omelanczuk, J .; Cristau,
H. J .; Perraud-Darcy, A. J . Org. Chem. 1998, 63, 9716. (b) Kosugi, H.;
Kitaoka, M.; Tagami, K.; Takahashi, A.; Uda, H. J . Org. Chem. 1987,
52, 1078. (c) Posner, G. H.; Tang, P. W. J . Org. Chem. 1978, 43, 4131.
(6) (a) De Lucchi, O.; Pasquato, L. Tetrahedron 1988, 44, 6755. (b)
Simpkins, N. S. Tetrahedron 1990, 46, 6951. (c) Fuchs, P. L.; Braish,
T. F. Chem. Rev. 1986, 86, 903. (d) Carreno, M. C. Chem. Rev. 1995,
95, 1717.
(7) Huang, X.; Duan, D. H. J . Chem. Soc., Chem. Commun. 1999,
1741.
(8) Mikolajczyk, M.; Midura, W. H.; Grzejszczak, S.; Zatorski, A.;
Chefczynska, A. J . Org. Chem. 1978, 43, 473.
10.1021/jo0111154 CCC: $25.00 © 2003 American Chemical Society
Published on Web 02/11/2003
1958
J . Org. Chem. 2003, 68, 1958-1963

Studies on Hydrozirconation
SCHEME 1
SCHEME 4
SCHEME 2
SCHEME 5
SCHEME 3
On the basis of the structures of these products, it can
be concluded that the hydrozirconation reaction exhibits
a trans-addition stereoselectivity, affording Z-alkenyl-
zirconocene intermediate 2a , in which the zirconium
group occupies the 2-position highly regioselectively.
In addition, the hydrozirconation of alkyl-substituted
acetylenic sulfoxides 1b-1d followed by subsequent
protonolysis also produced E-vinyl sulfoxides 3b -3d
predominantly, with a trace amount of the opposite
stereoisomers. The E-configurations were established by
the comparison with the literature data5b (Scheme 2).
The subsequent treatment of alkyl-substituted acetyl-
enic sulfoxides 1c-e with Cp2Zr(H)Cl and NBS gave
inseparable mixtures of two Z (major) and E (minor)
stereoisomers 4b-d (Scheme 3) with good selectivity. The
was converted to Z-2-bromo-2-phenyl-1-(4′-tolylsulfonyl)-
ethene 9d with m-CPBA (Scheme 4).
H yd r ozir con a t ion R ea ct ion of 1-Alk yn yl Su l-
fon es. When phenylacetylenic sulfone 5a was treated
with 1.2 equiv of Cp2Zr(H)Cl in THF at room tempera-
ture, the reaction gave a clear yellow solution within
about 5 min, which shows the end of hydrozirconation.
After the mixture was divided into two equal parts via a
graduated syring, H2O and D2O were added to quench
the reaction, respectively. After the usual workup, pure
products were obtained and their structures were deter-
1
mined by H NMR spectra (Scheme 5).
1
Z-configuration of product 4c was verified by its H-1H
Again, we observed that deuterium atom occupies the
2-position in 8a [verified by its Ha chemical shift (6.86
ppm)] and locates at the same side of the carbon-carbon
double bond with the sulfonyl group [as determined by
the coupling constant of olefinic protons (15.4 Hz) in 7a ],12
indicating a trans-addition type reaction of 5a with
Schwartz’s reagent.
This reaction can be extended to other arylacetylenic
sulfones (Table 1). The substituents attached to sulfonyl
groups have little effect on the results (entries 2 and 3,
Table 1), while the aryl substituents attached to the
acetylenic bond affect the stereochemical outcome slightly.
In entries 2 and 4-7 of Table 1, small amounts of
Z-products were also formed.
2D NOESY spectrum.
Several points should be noted: (1) No R-bromovinyl
sufoxides were formed, indicating a high regioselectivity.
(2) By increasing the bulkiness of the substituents
attached to acetylenic bond, more trans-addition product
was obtained [compare 4d (15/1) with 4b (9.2/1)] (Scheme
3). (3) Low yields are ascribed to the instability of both
the substrates and products.10
Tr a n sfor m a tion of Vin yl Su lfoxid es to Vin yl Su l-
fon es.11 The synthesis of stereodefined vinyl sulfones can
be realized by the hydrozirconation/oxidization sequence
of 1-alkynyl sulfoxides. E-1-(4′-Tolylsulfinyl)hex-1-ene 3b
was stereoselectively oxidized to E-1-(4′-tolylsulfonyl)hex-
1-ene 7h with H2O2, while Z-â-bromovinyl sulfoxide 4a
(11) Farina, V.; Hauck, S. I. J . Org. Chem. 1991, 56, 4317.
(12) (a) Cardillo, G.; Savoia, D.; Umani-Ronchi, A. Synthesis 1975,
453. (b) Bentani, L.; Capella, L.; Montevecchi, P. C.; Spagnolo, P. J .
Chem. Soc., Perkin Trans. 1 1995, 1035.
(9) Ma, S. M.; Lu, X. Y.; Li, Z. G. J . Org. Chem. 1992, 57, 709.
(10) Russel, G. A.; Ochrymowycz, L. A. J . Org. Chem. 1970, 35, 2106.
J . Org. Chem, Vol. 68, No. 5, 2003 1959

Huang et al.
TABLE 1. Hyd r ozir con a tion of 1-Alk yn yl Su lfon es 5a
a n d Su bsequ en tly P r oton olysis w ith H2O or D2Oa
TABLE 2. Hyd r ozir con a tion of 1-Alk yn yl Su lfon es a n d
Su bsequ en tly Cou p lin g Rea ction s of Alk en ylzir con iu m
Com p lexes w ith 1-Alk yn yl Br om id es in th e P r esen ce of
Cu Cla
yield
entry
Ar
Ph
Ph
Ph
R
productsa
(%)b
Z/ Ec
1
2
3
4
Ph
10a
10b
10c
10d
65
70
62
68
88/12
100/0
100/0
95/5
n-Bu
CH3OCH2
Ph
yield
entry
Ar
Ar′
alkyne producta (%)b
E/Zc
p-Tol
1
2
3
4
5
6
7
8
9
Ph
Ph
Ph
Ph
5a
5b
5c
5d
5e
5f
7a
7b
7c
7d
7e
7f
72 >99
a
p-Tol
p-ClC6H4
Ph
69 >98/2
68 >99
The reaction was carried out at room temperature using 1.2
equiv of CuCl and 1.2 equiv of 1-alkynyl bromides for 3 h under a
nitrogen atmosphere. Isolated yields from 1-alkynyl sulfones.
b
p-ClC6H4
p-BrC6H4
p-MeC6H4
64 96/4
68 95/5
c Measured by 1H NMR spectra.
Ph
Ph
65 94/6
72 94.5/5.5
70 95/5
p-MeOC6H4 Ph
5g
5a
5d
7g
8a
8b
easily available by the known methods.14,15 Utilizing the
coupling reaction of ethenyl bifunctional group reagents
6 with 1-alkynyl bromides in the presence of CuCl at
room temperature,16 Z-polysubstituted-3-yn-1-enyl sul-
fones 10 can be prepared in 62-70% yields (Table 2). The
Z-configuration of product 10c was determined by its 1H-
1H 2D NOESY spectrum.
Ph
Ph
Ph
p-ClC6H4
65 95.5/4.5
a
Reaction conditions: (1) Cp2ZrH(Cl) (1.2 equiv), THF, rt, 5
b
min; (2) 10 equiv of H2O or D2O, THF, rt, 30 min. Isolated yields
from 1-alkynyl sulfones. c Determined by 1H NMR spectra.
SCHEME 6
Following the reported protocols, either a mixture of
two stereoisomers of â-sulfonyl R,â-unsaturated ketones17
or only E-isomer can be obtained.18 In our study, acylation
of the alkenyl zirconocenes 6 in the presence of copper(I)
bromide at room temperature19 could produce Z-â-
sulfonyl R,â-unsaturated ketones 11a and 11b smoothly
in 70% and 65% yields, respectively. Their configurations
were verified by 1H-1H 2D NOESY spectra and the X-ray
diffraction study of compound 11b.20
Un d er t h e ca t a lysis of P d (P P h 3)4, t h e cr oss-
cou p lin g r ea ction of a lk en ylzir con ocen e 6a with
allyl bromide provided a facile synthesis of Z-2-phenyl-
1-phenylsulfonyl-1,4-pentadiene 12, whose configuration
was verified by its 1H-1H 2D NOESY spectrum and
X-ray diffraction study.21
There are some regio- and stereochemical issues as-
sociated with the addition of Cp2Zr(H)Cl to the unsym-
metrical acetylenic sulfoxides or sulfones. A slight tem-
perature effect on the stereoselectivity of this reaction
(Z/E: -27 °C, >99: 1; 20 °C, 98: 2; 45 °C, 96: 4) was
observed. In addition, when different amounts of methyl
phenyl sulfone were added to the reaction mixture, a
change of the stereoselectivity (from >99/1 for 0.2 equiv
to 96/4 for 10 equiv) was observed, indicating that the
sulfonyl group may play an important role in this
hydrozirconation reaction, which could be related to the
ability of their neighboring group participation (Scheme
7).
Syn th etic Ap p lica tion s of th e Hyd r ozir con a tion
Rea ction of 1-Alk yn yl Su lfon es (Sch em e 6). The
alkenylzirconium intermediates can react with different
electrophiles with the retention of configuration.2 When
Z-â-sulfonyl alkenylzirconocenes 6 were treated with
halogenation reagents such as NCS, NBS, or iodide at
room temperature, Z-â-halovinyl sulfones 9 were formed
exclusively in 56-65% yields. The configuration of 9b was
determined by the comparison with the product from the
trans-hydrobromination reaction of 5a .9
(14) Hohmann, M.; Krause, N. Chem. Ber. 1995, 128, 851.
(15) Truce, W. E.; Wolf, G. C. J . Org. Chem. 1971, 36, 1727.
(16) Hara, R.; Liu, Y.; Sun, W.-H.; Takahashi, T. Tetrahedron Lett.
1997, 38, 4103.
(17) Haynes, R. K.; Vonwiller, S. C.; Stokes, J . P.; Merlino, L. M.
Aust. J . Chem. 1988, 41, 881.
(18) Najera, C.; Baldo, B.; Yus, M. J . Chem. Soc., Perkin Trans. 1
1988, 1029.
Alk-3-yn-1-enyl sulfones are one of most versatile
organic synthetic intermediates,13 which are usually not
(13) (a) Yoshimatsu, M.; Hayashi, M.; Tanabe, G.; Muraoka, O.
Tetrahedron Lett. 1996, 37, 4161. (b) Yoshimatsu, M.; Hasegawa, J .
Tetrahedron Lett. 1996, 37, 7381.
(19) Wipf, P.; Xu, W. Synlett 1992, 718.
(20) CCDC no. 188257.
(21) CCDC no. 188258.
1960 J . Org. Chem., Vol. 68, No. 5, 2003

Studies on Hydrozirconation
6.8 Hz, 1H), 7.30 (d, J ) 8.2 Hz, 2H), 7.49 (d, J ) 8.2 Hz, 2H).
MS (m/z): 223 (M+ + 1, 100).
SCHEME 7
E-1-(4′-Tolylsu lfin yl)h ep t-1-en e (3c).5b Yield: 47%, pale
yellow oil. IR (neat): 2956, 1492, 1457, 1044 cm-1 1H NMR
.
(400 MHz, CDCl3) δ: 0.88 (t, J ) 7.4 Hz, 3H), 1.27-1.30 (m,
4H), 1.41-1.47 (m, 2H), 2.18-2.24 (m, 2H), 2.40 (s, 3H), 6.21
(d t, J ) 15.2 Hz, 1.4 Hz, 1H), 6.59 (d t, J ) 15.2 Hz, 6.8 Hz,
1H), 7.30 (d, J ) 8.3 Hz, 2H), 7.49 (d, J ) 8.1 Hz, 2H). MS
(m/z): 237 (M+ + 1, 100).
E-1-(4′-Tolylsu lfin yl)oct -1-en e (3d ).5b Yield: 39%, pale
yellow oil. IR (neat): 1733, 1595, 1457 cm-1 1H NMR (400
.
MHz, CDCl3) δ: 0.87 (t, J ) 7.0 Hz, 3H), 1.23-1.33 (m, 6H),
1.41-1.47 (m, 2H), 2.19-2.24 (m, 2H), 2.40 (s, 3H), 6.21 (d t,
J ) 15.2 Hz, 1.4 Hz, 1H), 6.59 (d t, J ) 15.2 Hz, 6.8 Hz, 1H),
7.30 (d, J ) 8.4 Hz, 2H), 7.49 (d, J ) 8.4 Hz, 2H). MS (m/z):
251 (M+ + 1, 11), 131 (100).
Con clu sion
The treatments of 1-alkynyl sulfoxides or sulfones with
Cp2Zr(H)Cl afforded Z-â-zirconated vinyl sulfoxides or
sulfones predominantly. Compared with 1-alkynyl sulf-
oxides, the hydrozirconation reaction of 1-alkynyl sul-
fones has more synthetic potential. So it was explored
for further synthetic transformation to Z-â-halovinyl
sulfones, Z-â-sulfonyl-R,â-unsaturated ketones, and Z-â-
alkynyl-substituted vinyl sulfones, providing a comple-
mentary synthetic approach to stereodefined Z-poly-
substituted vinyl sufones.
Gen er a l P r oced u r e for th e P r ep a r a tion of Z-â-Br om o-
vin yl Su lfoxid es 4. To the yellowish green solution
2
(prepared as described above) was added 2.5 equiv of NBS and
the mixture was stirred overnight. After usual workup, the
residue was purified by preparative TLC on silica gel (light
petroleum ether/ethyl acetate 4/1 or 10/1) to yield 4.
Z-2-Br om o-2-ph en yl-1-(4′-tolylsu lfin yl)eth en e (4a). Yield:
23%. IR (KBr): 2997, 1490, 1045 cm-1 1H NMR (300 MHz,
.
CDCl3) δ: 2.32 (s, 3H), 6.98 (s, 1H,), 7.24-7.29 (m, 5H), 7.46-
7.49 (m, 2H), 7.61 (d, J ) 8.1 Hz). MS (m/z): 323 [M+ + 1
(81Br), 2], 321 [M+ + 1 (79Br), 2], 193 (100). HRMS (EI): calcd
-
for C15H13BrOS (M+ O) 304.0121, found 303.9919.
Z-2-Br om o-1-p h en ylsu lfin ylh ex-1-en e (4b). Yield: 40%,
pale yellow oil. IR (neat): 2924, 1594, 1085, 813 cm-1. 1H NMR
(400 MHz, CDCl3) δ: 0.87 (t, J ) 7.4 Hz, 3H), 1.25-1.31 (m,
2H), 1.51-1.57 (m, 2H), 2.53 (t, J ) 7.1 Hz, 2H), 6.58 (s, 1H),
Exp er im en ta l Section
Melting points were uncorrected. 1H NMR spectra were
recorded in CDCl3 with TMS as internal standard. MS and
HRMS spectra were performed with electron impact ionization
(EI). THF was distilled from sodium-benzophenone ketyl
immediately before use. Sodium sulfinate,23 iodophenylacet-
ylene,24 1-bromoalkynes,25 Cp2Zr(H)Cl,26 1-alkynyl sulfoxides
1a -1e,5b phenylacetylenic sulfones 5a -5c,27 and acetylenic
sulfones 5d -5g15 were prepared by the literature methods.
Gen er a l P r oced u r e for th e P r ep a r a tion of E-â-Mon o-
su bstitu ted Vin yl Su lfoxid es 3 by th e Hyd r olysis of
Alk en ylzir con ocen es 2. To a suspension of Cp2Zr(H)Cl (309
mg, 1.2 mmol) in THF (5 mL) in a Schlech reaction tube was
added 1-alkynyl sulfoxide 1 (1.0 mmol) under nitrogen. The
mixture was stirred for 5 min at room temperature to obtain
a clear yellowish green solution of Z-alkenylzirconocene 2, to
which was added H2O (0.2 mL), and the mixture was stirred
for 30 min to obtain a nearly white turbid solution. After being
diluted with 5 mL of light petroleum ether and stirred for
further 5 min, the supernatant layer was filtered through a
short plug of silica gel. After evaporation, the residue was
purified by preparative TLC on silica gel (light petroleum
ether/ethyl acetate 10/1) to yield E-vinyl sulfoxide 3.
7.49-7.53 (m, 3H), 7.70-7.72 (m, 2H). MS (m/z): 289 [M+
+
1 (81Br), 36], 287 [M+ + 1 (79Br), 36], 209 (100). HRMS (EI):
-
calcd for C12H15BrOS (M+ O) 270.0278, found 270.0075.
Z-2-Br om o-1-(4′-tolylsu lfin yl)h ept-1-en e (4c). Yield: 43%,
pale yellow oil. IR (neat): 2929, 1732, 1045, 805 cm-1. 1H NMR
(400 MHz, CDCl3) δ: 0.86 (t, J ) 7.2 Hz, 3H), 1.23-1.29 (m,
4H), 1.55-4.59 (m, 2H), 2.41 (s, 3H), 2.52 (t, J ) 7.0 Hz, 2H),
6.58 (s, 1H), 7.32 (d, J ) 8.2 Hz, 2H), 7.61 (d, J ) 8.2 Hz, 2H).
MS (m/z): 317 [M+ + 1 (81Br), 100], 315 [M+ + 1 (79Br), 100].
HRMS (EI): calcd for C14H19BrOS (M+ - O) 298.0591, found
298.0393.
Z-2-Br om o-1-(4′-tolylsu lfin yl)oct-1-en e (4d ). Yield: 42%,
pale yellow oil. IR (neat): 2927, 2856, 1595, 1047 cm-1 1H
.
NMR (400 MHz, CDCl3) δ: 0.85 (t, J ) 7.0 Hz, 3H), 1.24 (m,
6H), 1.54-1.58 (m, 2H), 2.41 (s, 3H), 2.51 (t, J ) 7.5 Hz, 2H),
6.57 (s, 1H), 7.32 (d, J ) 8.2 Hz, 2H), 7.60 (d, J ) 8.2 Hz, 2H).
MS (m/z): 331 [M+ + 1 (81Br), 43], 329 [M+ + 1 (79Br), 43].
HRMS (EI): calcd for C15H21BrOS (M+ - O) 312.0747, found
312.0538.
Gen er a l P r oced u r e for th e P r ep a r a tion of E-â-Mon o-
su bstitu ted Vin yl Su lfon es 7 by th e P r oton olysis of
Alk en ylzir con ocen es 6. To a suspension of Cp2Zr(H)Cl (155
mg, 0.6 mmol) in THF (4 mL) under nitrogen was added an
acetylenic sulfone 5. The mixture was stirred for 5 min at room
temperature to obtain a clear yellow solution of alkenyl-
zirconocene 6. To this yellow solution was added H2O (0.2 mL)
and the mixture was stirred for 30 min to obtain a nearly white
turbid solution. After usual workup, the residue was purified
by preparative TLC on silica gel (light petroleum/ethyl acetate
15/1) to yield 7.
E-2-P h en yl-1-(p h en ylsu lfon yl)eth en e (7a ). Yield: 72%,
colorless solid. Mp: 74.5-75.5 °C (cyclohexane) [lit.12a mp:
76°C (C6H6)]. IR (KBr): 1620, 1450, 1320, 1140 cm-1. 1H NMR
(300 MHz, CDCl3) δ: 6.86 (d, J ) 15.4 Hz, 1H), 7.39-7.58 (m,
8H), 7.69 (d, J ) 15.4 Hz, 1H), 7.94-7.97 (m, 2H). MS (m/z):
244 (M+, 18), 91 (100).
E-2-P h en yl-1-(4′-tolylsu lfon yl)eth en e (7b). Yield: 69%,
colorless solid. Mp: 120-121 °C (cyclohexane) (lit.6a mp: 120-
121 °C). IR (KBr): 1640, 1310, 1140 cm-1. 1H NMR (300 MHz,
CDCl3) δ: 2.36 (s, 3H), 6.80 (d, J ) 15.4 Hz, 1H), 7.26-7.42
E-2-P h en yl-1-(4′-tolylsu lfin yl)eth en e (3a ). Yield: 23%,
colorless crystal. Mp: 81-82 °C (petroleum ether) (lit.8 mp:
82 °C). IR (KBr): 2998, 1492, 1044 cm-1. H NMR (300 MHz,
1
CDCl3) δ: 2.34 (s, 3H), 6.75 (d, J ) 15.0 Hz, 1H), 7.19-7.39
(m, 8H), 7.51 (d, J ) 8.1 Hz, 2H). MS (m/z): 243 (M+ + 1, 1),
194 (100).
E-1-(4′-Tolylsu lfin yl)h ex-1-en e (3b).5b Yield: 45%, pale
yellow oil. IR (neat): 2929, 1558, 1457, 1041, 755 cm-1 1H
.
NMR (400 MHz, CDCl3) δ: 0.89 (t, J ) 7.2 Hz, 3H), 1.32-
1.36 (m, 2H), 1.42-1.46 (m, 2H), 2.19-2.25 (m, 2H), 2.41 (s,
3H), 6.21 (d t, J ) 15.2 Hz, 1.4 Hz, 1H), 6.59 (d t, J ) 15.2 Hz,
(22) (a) Ma, S. M.; Negishi, E. I. J . Org. Chem. 1997, 62, 784. (b)
Ma, S.; Wei, Q.; Wang, H. Org. Lett. 2000, 2, 3893.
(23) Whitmore, F. C.; Hamilton, F. H. Organic Syntheses; Wiley:
New York, 1941; Collect. Vol. 1, p 492.
(24) Rao, M. L. N.; Periasamy, M. Synth. Commun. 1995, 25, 2295.
(25) Cacchi, S.; Caglioti, L.; Zappelli, P.J . Org. Chem. 1973, 38, 3653.
(26) Buchwald, S. L.; Lamaire, S. J .; Nielsen, R. B.; Watson, B. T.;
King, S. M. Tetrahedron Lett. 1987, 28, 3895.
(27) Suzuki, H.; Abe, H. Tetrahedron Lett. 1996, 37, 3717.
J . Org. Chem, Vol. 68, No. 5, 2003 1961

Huang et al.
(m, 7H), 7.69 (d, J ) 15.4 Hz, 1H), 7.77 (d, J ) 8.2 Hz, 2H).
MS (m/z): 258 (M+, 36), 91 (100).
purified by preparative TLC on silica gel (petroleum ether/
ethyl acetate 10/1 as eluent) to yield 9.
E-1-(4′-Ch lor op h en ylsu lfon yl)-2-p h en ylet h en e (7c).
Z-2-Ch lor o-2-p h en yl-1-(p h en ylsu lfon yl)et h en e (9a ).
Yield: 60%, colorless solid. Mp: 83-84 °C (methanol) (lit.32b
mp: 84 °C). IR (KBr): 1595, 1320, 1305, 1235, 1175, 1145
Yield: 68%, colorless solid. Mp: 82-84 °C (cyclohexane) (lit.6d
mp:78-78.5 °C). IR (KBr): 1630, 1600, 1320, 1150 cm-1 1H
.
1
NMR (400 MHz, CDCl3) δ: 6.83 (d, J ) 15.4 Hz, 1H), 7.40-
7.54 (m, 7H), 7.70 (d, J ) 15.4 Hz, 1H), 7.89 (d, J ) 7.8 Hz,
2H). MS (m/z): 280 [M+ (37Cl), 5], 278 [M+ (35Cl), 15], 91 (100).
E-2-(4′-Ch lor op h en yl)-1-(p h en ylsu lfon yl)eth en e (7d ).
Yield: 64%, colorless solid. Mp: 129-130 °C (cyclohexane)
cm-1. H NMR (300 MHz, CDCl3) δ: 7.15 (s, 1H), 7.41-7.67
(m, 8H), 8.05-8.09 (m, 2H). MS (m/z): 280 [M+ (37Cl), 8], 278
[M+ (35Cl), 22], 77 (100).
Z-2-Br om o-2-p h en yl-1-(p h en ylsu lfon yl)et h en e (9b ).
Yield: 63%, pale yellow solid. Mp: 89.5-90.5 °C (methanol)
(lit.32a mp: 88 °C). IR (KBr): 1605, 1460, 1325, 1150 cm-1. 1H
NMR (400 MHz, CDCl3) δ: 7.33 (s, 1H), 7.38-7.43 (m, 3H),
7.55-7.66 (m, 5H), 8.06-8.08 (m, 2H). MS (m/z): 324 [M+
(81Br), 8], 322 [M+, (79Br), 8], 77 (100).
(lit.28 mp:130 °C). IR (KBr): 1617, 1486, 1321, 1309, 1149 cm-1
.
1H NMR (400 MHz, CDCl3) δ: 6.85 (d, J ) 15.4 Hz, 1H), 7.40
(d, J ) 8.6 Hz, 2H), 7.46 (d, J ) 8.6 Hz, 2H), 7.55-7.66 (m,
4H), 7.96 (m, 2H). MS (m/ z): 280 [M+ (37Cl), 10], 278 [M+
(35Cl), 24], 136(100).
Z-2-Iod o-2-p h en yl-1-(p h en ylsu lfon yl)eth en e (9c). Yield:
56%, pale yellow solid. Mp: 113-115 °C (methanol). IR
E-2-(4′-Br om op h en yl)-1-(p h en ylsu lfon yl)eth en e (7e).
Yield: 68%, colorless solid. Mp: 150-152 °C (cyclohexane)
(lit.29 mp: none reported). IR (KBr): 1620, 1583, 1485, 1447,
(KBr): 1460, 1320, 1150, 1090 cm-1 1H NMR (300 MHz,
.
CDCl3) δ: 7.27 (s, 1H), 7.31-7.71 (m, 8H), 8.06-8.09 (m, 2H).
MS (m/z): 371(M+ + 1, 13), 77 (100). Anal. Calcd for C14H11
IO2S: C 45.42, H 2.99. Found: C 45.18, H 2.87.
-
1
1308, 1154 cm-1. H NMR (400 MHz, CDCl3) δ: 6.86 (d, J )
15.4 Hz, 1H), 7.35 (d, J ) 8.3 Hz, 2H), 7.42-7.66 (m, 6H), 7.95
(m, 2H). MS (m/z): 324 [M+ (81Br), 37], 322 [M+ (79Br), 36],
182 (100).
Z-2-Br om o-2-p h en yl-1-(4′-t olylsu lfon yl)et h en e (9d ).
Yield: 65%, colorless solid. Mp: 109-110 °C (methanol) (lit.32a
mp: 108 °C). IR (KBr): 1610, 1580, 1450, 1330, 1160 cm-1
.
E-2-(4′-Tolyl)-1-(p h en ylsu lfon yl)eth en e (7f). Yield: 65%,
colorless solid. Mp: 139-140 °C (cyclohexane) (lit.30 mp: 138-
139 °C). IR (KBr): 1606, 1308, 1147 cm-1. 1H NMR (400 MHz,
CDCl3) δ: 2.37 (s, 3H), 6.81 (d, J ) 15.4 Hz, 1H), 7.20 (d, J )
8.0 Hz, 2H), 7.38 (d, J ) 8.0 Hz, 2H), 7.53-7.62 (m, 3H), 7.66
(d, J ) 15.4 Hz, 1H), 7.95 (d, J ) 7.3 Hz, 2H). MS (m/z): 258
(M+, 25), 116 (100).
1H NMR (400 MHz, CDCl3) δ: 2.46 (s, 3H), 7.31 (s, 1H), 7.36-
7.44 (m, 5H), 7.55 (m, 2H), 7.95 (d, J ) 8.3 Hz, 2H). MS (m/z):
338 [M+ (81Br), 8], 336 [M+ (79Br), 8], 91 (100).
Z-2-Iod o-2-p h en yl-1-(4′-tolylsu lfon yl)eth en e (9e). Yield:
60%, slight brown solid. Mp: 98-100 °C (methanol). IR
1
(KBr): 1610, 1330, 1150, 750, 660 cm-1. H NMR (300 MHz,
CDCl3) δ: 2.39 (s, 3H), 7.17-7.41 (m, 8H), 7.88 (d, J ) 8.3
E-2-(4′-Meth oxylph en yl)-1-(ph en ylsu lfon yl)eth en e (7g).
Yield: 72%, colorless solid. Mp: 120-121 °C (cyclohexane)
[lit.31 mp: 123-124 °C (MeOH)]. IR (KBr): 1604, 1512, 1310,
Hz, 2H). MS (m/z): 385 (M+ + 1, 17), 91 (100). Anal. Calcd for
C
15H13IO2S: C 46.89, H 3.41. Found: C 46.88, H 3.39.
1
1264, 1143 cm-1. H NMR (400 MHz, CDCl3) δ: 3.83 (s, 3H),
Gen er a l P r oced u r e for th e P r ep a r a tion of Z-Alk -3-yn -
6.71(d, J ) 15.3 Hz, 1H), 6.90 (d, J ) 8.7 Hz, 2H), 7.44 (d, J
) 8.7 Hz, 2H), 7.52-7.61 (m, 3H), 7.64 J ) 15.3 Hz, 1H), 7.95
(d, J ) 7.5 Hz, 2H). MS (m/z): 274 (M+, 23), 132 (100).
Gen er a l P r oced u r e for th e P r ep a r a tion of E-2-Deu -
ter iovin yl Su lfon es 8 by th e Deu ter iolysis of Alk en yl-
zir con ocen es 6. To this yellow solution of 6 (prepared as
described above) was added 0.2 mL of D2O, and the mixture
was stirred for 30 min to obtain a nearly white turbid solution.
After usual workup, the residue was purified by preparative
TLC on silica gel (light petroleum ether/ethyl acetate ) 15/ 1)
to yield a pure product 8.
1-en yl Su lfon es 10. To the yellow solution of 6 (prepared as
described above) were added CuCl (59 mg, 0.6 mmol) and
phenylacetylenic bromide (109 mg, 0.6 mmol). The mixture
was stirred for 3 h at room temperature. After workup as
described above, the residue was purified by preparative TLC
on silica gel (petroleum ether/ethyl acetate 12/1 as eluent) to
yield 10.
Z-2, 4-Diph en yl-1-(ph en ylsu lfon yl)bu t-1-en -3-yn e (10a).
Yield: 65%, colorless solid. Mp: 136-137°C (cyclohexane). IR
(KBr): 2215, 1655, 1570, 1465, 1325, 1160, 1095 cm-1. 1H NMR
(400 MHz, CDCl3) δ: 7.13 (s, 1H), 7.40-7.72 (m, 13H), 8.08
(d, J ) 7.3 Hz, 2H). MS (m/z): 344 (M+, 11), 178 (100). Anal.
Calcd for C22H16O2S: C 76.72, H 4.68. Found: C 76.88, H 4.63.
Z-2-P h en yl-1-(ph en ylsu lfon yl)oct-1-en -3-yn e (10b). Yield:
70%, colorless solid. Mp: 66-68 °C (cyclohexane). IR (KBr):
E-2-Deu ter o-2-p h en yl-1-(p h en ylsu lfon yl)eth en e (8a ).
Yield: 70%, colorless solid. Mp: 73.5-75 °C (cyclohexane)
(lit.12b mp: none reported). IR (KBr): 1620, 1450, 1320, 1140
1
cm-1. H NMR (400 MHz, CDCl3) δ: 6.86 (s, 1H), 7.38-7.63
(m, 8H), 7.95-7.97 (m, 2H). MS (m/z): 245 (M+, 7), 92 (100).
Anal. Calcd for C14H11DO2S: C 68.55, H 5.34. Found: C 68.50,
H 5.35.
1
3130, 2218, 1650, 1570, 1330, 1320, 1160 cm-1. H NMR (300
MHz, CDCl3) δ: 0.95 (t, J ) 7.0 Hz, 3H), 1.43-1.67 (m, 4H),
2.52 (t, J ) 7.2 Hz, 2H), 7.07 (s, 1H), 7.37-7.64 (m, 8H), 8.03-
8.06 (m, 2H). MS (m/z): 325 (M+ + 1, 33), 115 (100). Anal.
Calcd for C20H20O2S: C 74.04, H 6.21. Found: C 74.16, H 6.20.
Z-5-Meth oxy-2-p h en yl-1-(p h en ylsu lfon yl)p en t-1-en -3-
yn e (10c). Yield: 62%, colorless solid. Mp: 67-69 °C (cyclo-
hexane). IR (KBr): 3030, 2215, 1650, 1590, 1465, 1330, 1165,
E-2-Deu t er o-2-(4′-ch lor op h en yl)-1-(p h en ylsu lfon yl)-
eth en e (8b). Yield: 65%, colorless solid. Mp: 128-129 °C
(cyclohexane). IR (KBr): 1618, 1321, 1149 cm-1. 1H NMR (400
MHz, CDCl3) δ: 6.84 (s, 1H), 7.37 (d, J ) 8.5 Hz, 2H), 7.43 (d,
J ) 8.5 Hz, 2H), 7.55-7.64 (m, 3H), 7.94-7.96 (m, 2H). MS
(m/z): 281 [M+ (37Cl), 10], 279 [M+ (35Cl), 24], 136 (100). Anal.
Calcd for C14H10DClO2S: C 60.01, H 4.32. Found: C 60.07, H
4.30.
Gen er a l P r oced u r e for t h e P r ep a r a t ion of Zâ-Ha lo-
vin yl Su lfon es 9. To the yellow solution of 6 (prepared as
described above) was added 1.25 mmol of NCS or NBS or 0.75
mmol of I2 and the mixture was then stirred for 2 h at room
temperature. After workup as described above, the residue was
1090 cm-1 1H NMR (400 MHz, CDCl3) δ: 3.49 (s, 3H), 4.42
.
(s, 2H). 7.09 (s, 1H), 7.38-7.64 (m, 8H), 8.04-8.06 (m, 2H).
MS (m/z): 313 (M+ + 1, 17), 85 (100). Anal. Calcd for
C
18H16O3S: C 69.21, H 5.16. Found: C 69.44, H 5.36.
Z-2,4-Dip h en yl-1-(4′-tosyl)bu t-1-en -3-yn e (10d ). Yield:
68%, colorless solid. Mp: 117-118 °C (cyclohexane). IR
(KBr): 2230, 1615, 1570, 1460, 1360, 1330, 1315, 1160, 1095
cm-1. 1H NMR (400 MHz, CDCl3) δ: 2.41 (s, 3H), 7.11 (s, 1H),
7.28-7.44 (m, 8H), 7.62-7.71 (m, 4H), 7.96 (d, J ) 8.3 Hz,
2H). MS (m/z): 358 (M+, 9), 192 (100). Anal. Calcd for
(28) J ang, W. B.; J eon, H. J .; Oh, D. Y. Synth. Commun. 1998, 28,
1253.
C
23H18O2S: C 77.07, H 5.06. Found: C 77.30, H 5.16.
(29) Srinivasan, C.; Granesan, P. K.; Arumugam, N. Indan J . Chem
1983, 22B, 649.
(30) Matano, Y.; Yoshimune, M. Azuma, N.; Suzuki, H. J . Chem.
Soc., Perkin Trans. 1 1996, 1971.
Gen er a l P r oced u r e for t h e P r ep a r a t ion of Z-â-Su l-
fon yl-r,â-u n sa tu r a ted Keton es 11. To the yellow solution
(31) Enders, D.; Papadopoulos, K.; Herdtweck, E. Tetrahedron 1993,
49, 1821.
(32) (a) Amiel, Y. J . Org. Chem. 1974, 39, 3867. (b) Amiel, Y. J . Org.
Chem. 1971, 36, 3691. (c) Amiel, Y. J . Org. Chem. 1971, 36, 3697.
1962 J . Org. Chem., Vol. 68, No. 5, 2003

Studies on Hydrozirconation
of 6 (prepared as described above) were added CuBr (86 mg,
0.6 mmol) and acyl chloride (64 mg, 0.6 mmol). The mixture
was stirred for 3 h at room temperature. After workup as
described above, the residue was purified by preparative TLC
on silica gel (petroleum ether/ethyl acetate 8/1 as eluent) to
yield 11.
acetate 10/1 as eluent to yield a colorless solid. Mp: 69-70
°C (cyclohexane). IR (KBr): 3045, 1610, 1485, 1310, 1155 cm-1
.
1H NMR (300 MHz, CDCl3) δ: 3.79-3.82 (m, 2H), 4.91-4.99
(m, 2H), 5.56-5.72 (m, 1H), 6.50 (s, 1H), 7.29-7.56 (m, 8H),
7.89-7.94 (m, 2H). MS (m/z): 285 (M+ + 1, 4), 284 (M+, 8),
142 (100). Anal. Calcd for
Found: C 71.75, H 5.67.
C17H16O2S: C 71.80, H 5.67.
Z-3-P h en yl-4-p h en ylsu lfon ylbu t-3-en -2-on e (11a ). Yield:
70%, colorless solid. Mp: 115-116 °C (cyclohexane/ethyl
acetate 10/1). IR (KBr): 1738, 1615, 1588, 1455, 1340, 1315,
Ack n ow led gm en t. This work was supported by
Project 29772007 of the National Natural Science
Foundation of China and the State Key Laboratory of
Organometallic Chemistry, Shanghai Institute of Or-
ganic Chemistry, Chinese Academy of Sciences. The
authors wish to thank Prof. Shengming Ma for his
assistance.
1
1170, 1150 cm-1. H NMR (300 MHz, CDCl3) δ: 2.54 (s, 3H),
6.44 (s, 1H), 7.34-7.62 (m, 8H), 7.95-7.98 (m, 2H). MS (m/z):
287 (M+ + 1, 44), 102 (100). Anal. Calcd for C16H14O3S: C
67.11, H 4.93. Found: C 67.44, H 4.96.
Z-1,2-Dip h en yl-3-p h en ylsu lfon ylp r op -2-en -1-on e (11b).
Yield: 65%, colorless solid. Mp: 141-143 °C (cyclohexane/ethyl
acetate 10/1). IR (KBr): 3085, 3062, 1690, 1610, 1460, 1340,
1320, 1240, 1222, 1160 cm-1 1H NMR (400 MHz, CDCl3) δ:
.
6.80 (s, 1H), 7.35-7.58 (m, 11H), 7.93-7.98 (m, 4H). MS (m/
z): 349 (M+ + 1, 20), 105 (100). Anal. Calcd for C21H16O3S: C
72.39, H 4.63. Found: C 72.44, H 4.66.
Th e P r oced u r e for P r ep a r a tion of E-2-P h en yl-1-p h en -
ylsu lfon yl-1,4-p en t a d ien e 12. To a yellow solution of 6
(prepared as described above) were added Pd(PPh3)4 (0.025
mmol, 29 mg) and allyl bromide (73 mg, 0.6 mmol). The
mixture was stirred for 12 h at 40 °C. After workup as
described above, pure product 12 (73 mg, 51%) was obtained
by preparative TLC on silica gel with petroleum ether/ethyl
Su p p or tin g In for m a tion Ava ila ble: Experimental de-
tails for the preparation of the starting materials, the proce-
dure of trans-hydrohalogenation of compound 1a and 5a , and
the oxidation of vinyl sulfoxides; 1H NMR spectra copies of
compounds 3a -3d , 4a -4d , 7a -7h , 8a -8b, 9a -9e,10a -10d ,
11a -11b, 12; ORTEP drawing of compounds 11b and 12. This
material is available free of charge via the Internet at
http://pubs.acs.org.
J O0111154
J . Org. Chem, Vol. 68, No. 5, 2003 1963