A facile regio- and stereocontrolled synthesis of (E)-disubstituted vinyl sulfones via transformation of alkenylzirconocenes with sulfonyl chlorides

Article abstract of DOI:10.1055/s-1999-2616

Alkenylzirconium reagents, readily obtained by hydrozirconation of terminal alkynes, can smoothly react with sulfonyl chlorides to afford (E)- disubstituted vinyl sulfones in moderate to good yields. Some γ- functionalized vinyl sulfones can be also conve

Full text of DOI:10.1055/s-1999-2616

LETTER
317
A Facile Regio- and Stereocontrolled Synthesis of (E)-Disubstituted Vinyl
Sulfones via Transformation of Alkenylzirconocenes with Sulfonyl Chlorides
De-Hui Duan, Xian Huang*
Department of Chemistry , Zhejiang University(Campus Xixi), Hangzhou, Zhejiang , P. R. China, 310028
Fax 86 571 8807077; E-mail: huangx@public.hz.zj.cn
Received 24 December 1999
fones but also γ-functionalized vinyl sulfones can be con-
Abstract: Alkenylzirconium reagents, readily obtained by hy-
veniently prepared in moderate to good yields (Scheme
drozirconation of terminal alkynes, can smoothly react with sulfo-
and Table).
nyl chlorides to afford (E)-disubstituted vinyl sulfones in moderate
to good yields. Some g-functionalized vinyl sulfones can be also
conveniently synthesized.
Key words: vinyl sulfone, hydrozirconation, alkenylzirconocene,
sulfonyl chloride, g-functionalized vinyl sulfone
Vinyl sulfones have served as a class of compounds of
Scheme
proven value in organic synthesis due to the reactivity of-
fered by the sulfonyl functional group.1 Thus vinyl sul-
fones are excellent acceptors for Michael additions2 and
2π partners in cycloaddition reactions.3 In addition, alkyl-
ative desulfonylation has also provided a new strategy for
stereospecific alkene synthesis.4 Recently, γ-functional-
ized vinyl sulfones have been occasionally applied to re-
arrangement reactions and cyclization reactions,5 which
has considerably extended the utilities of vinyl sulfones in
organic synthesis.
The aforementioned methodology relies strongly upon re-
gio- and stereoselective construction of the precursor vi-
nyl sulfones, and numerous strategies have been
developed toward this goal. A broadly used strategy in-
volved the process of addition prior to elimination to alk-
enes. Typical examples could include iodosulfonylation /
dehydroiodination,6
sulfonomercuriation/demercuria-
tion,7selenosulfonylation/oxidation/elimination reaction.8
While these procedures can efficiently provide vinyl sul-
fones, the number of the linear steps involved by the strat-
egy is unfavorable to the overall yield, and the toxicity of
selenium and mercury is also unfriendly to the environ-
ment. Alternative convergent process involved the combi-
nation of a sulfone-stabilized carbanion with a carbonyl
compound. In this regard, Knoevenagel condensation9
and Horner-Wittig reaction10 achieved great successes
and the (E)-vinyl sulfone was the exclusive product, but
the preparation of the starting materials such as sulfonom-
ethylphosphonates could be both inconvenient and time-
consuming. In addition, protodesilylation of α-phenylsul-
fonyl allyl silanes also provided an indirect approach to
vinyl sulfones.11 To our knowledge, no well-established
method is used to prepare γ-functionalized vinyl sul-
fones.12 Herein, we hope to report a facile regio- and ste- Recently, it has become very popular that syn-addition of
reocontrolled synthesis of (E)-disubstituted vinyl sulfones Schwartz’s reagent onto a terminal alkyne followed by
by the conversion of alkenylzirconocenes with sulfonyl treatment with electrophiles provides a trans-functional-
chlorides. With the strategy, not only general vinyl sul- ized alkene with a high level of stereochemical purity.13
Synlett 1999, No. 3, 317–318 ISSN 0936-5214 © Thieme Stuttgart · New York

318
D.-H. Duan, X. Huang
LETTER
(4) Meagher, T. P.; Shechter, H. J. Org. Chem. 1998, 63, 4181.
Kim, S. H.; Jin, Z.; Ma, S.; Fuchs, P. L. Tetrahedron Lett.
1995, 36, 4013. Fabre, J-L.; Julia, M.; Verpeaux, J-N. Tetra-
hedron Lett. 1982, 23, 2469.
The protocol has been successfully applied to the prepara-
tions of organophosphorus,14 -selenium15 and -tellurium
compounds,16 and amines.17 Surprisingly this strategy has
not been adapted previously for the synthesis of sulfones.
In the communication, we report the result of the hy-
drozirconation of terminal alkynes and transformation to
vinyl sulfones with sulfonyl chlorides.18 Exclusive (E)-
disubstituted vinyl sulfone is obtained, and no (Z)-isomer
is formed. (E)-Olefin geometry is verified by a coupling
(5) Giovannini, R.; Marcantoni, E.; Petrini, M. Tetrahedron Lett.
1998, 39, 5827. Aionso, I.; Carretero. J. C.; Garrido, J. L.;
Magro, V.; Pedregal, C. J. Org. Chem. 1997, 62, 5682.
Giovannini, R.; Petrini, M. Chem. Commun. 1997, 1829.
(6) Liu, L.K.; Chi, Y.; Jen, K. Y. J. Org. Chem., 1980, 45, 406.
(7) Sas, W. J. Chem. Soc., Chem. Commun. 1984, 862.
(8) Back, T. G.; Collins, S. J. Org. Chem. 1981, 46, 3249.
(9) Happer, D. A. R.; Steenson, B.E. Synthesis 1980, 806.
(10) Posner, G.H.; Brunelle, D. J. J. Org. Chem. 1972, 37, 3547.
(11) Umstead-Daggett, J.; Brummond, K. M. Tetrahedron Lett.
1993, 34, 2867.
3
constant ( JHH=15Hz ) for the vicinal olefinic protons.
This result shows that the reaction proceeds with retention
of configuration at the carbon attached to zirconium atom.
Thus the hydrozirconation /sulfonylation process is total-
ly regio- and stereocontrolled.
(12) Culvenor, C. C. J.; Davies, W.; Savige, W. E. J. Chem. Soc.
1949, 2198.
Under the reaction conditions, propargyl methyl ether and
propargyltrimethylsilane also achieve the satisfactory re-
sults (Entry 6-8 of Table). However propargyl alcohol and
propargyl bromide are not compatible with the strongly
hydridic character of Cp2Zr(H)Cl. The former is preferen-
tially converted to the corresponding anion under the re-
action conditions. So 2.2 equiv. Schwartz’s reagent is
necessary to accomplish the hydrozirconation reaction of
the alcohol (Entry 9 and 10 of Table). The latter is proba-
bly reduced to propyne to escape and no hydrozirconation
reaction takes place (Entry 11 of Table).
(13) Wipf, P.; Jahn, H. Tetrahedron 1996, 52, 12853.
(14) Zablocka, M.; Lgau, A.; Cenac, N.; Donnadieu, B.; Dahan, F.;
Majoral, J. P.; Pietrusiewicz, M. K. J. Am. Chem. Soc. 1995,
117, 8083.
(15) Huang, X.; Zhu, L.-S. J. Chem. Soc., Perkin Trans. 1 1996,
767.
(16) Dabdoub, M. J.; Begnini, M. L .; Cassol, T. M. ; Guerrero,
P.G.; Silveira, C.C. Tetrahedron Lett. 1995, 36, 7623.
(17) Zheng, B.; Srebnik, M. J. Org. Chem. 1995, 60, 1912.
(18) Typical Procedure:
A solution of 112 mg (1.0 mmol ) of propargyltrimethylsilane
in 5ml of THF was treated with 309 mg (1.2 mmol ) of
Cp2Zr(H)Cl and stirred at r.t. for 30 min. After addition of 229
mg (1.2 mmol ) of p-toluenesulfonyl chloride, the reaction
mixture was stirred at 40 °C for 2h. It was diluted with light
petroleum and stirred for a further 5 min, then the supernatant
was filtered through a short plug of silica gel. After concentra-
tion of the filtrate in vacuo, the residue was purified by prepa-
rative TLC on silica gel [petroleum (30-60)/ethyl acetate 5:1]
to yield 172 mg (64%) of (E)-3-trimethylsilyl-1-tosyl-1-pro-
pene as a colorless oil: IR (CHCl3) 2970, 1625, 1320, 1250,
1145, 1080 cm-1 ; 1H NMR (CDCl3) δ 0.04 (s, 9H), 1.73 (d,
2H, J = 8 Hz), 2.43 (s, 3H), 6.05 (d, 1H, J = 15 Hz), 6.93
(d t, 1H, J = 15, 8 Hz), 7.28 (d, 2H, J = 8 Hz), 7.72 (d, 2H, J =
8 Hz ); MS (EI) m/z (relative intensity %) 268 (3) (M+), 251
(12), 161 (58), 149 (40), 130 (21), 129 (27), 91 (27), 73(100);
Anal. calcd. for C13H20O2SSi C%, 58.17; H%, 7.51. Found:
C%, 57.86; H%, 7.53.
In conclusion, the hydrozirconation / sulfonylation strate-
gy provides a direct route to (E)-disubstituted vinyl sul-
fones (including some previously difficult to prepare γ-
functionalized vinyl sulfones) from terminal alkynes. The
method has some advantages such as readily available
starting materials, mild reaction conditions, straightfor-
ward access to the exclusive (E)-configurated product and
little pollution of the environment.
Acknowledgement
Project 29772007 supported by National Natural Science Foundati-
on of China and this work also supported by the Laboratory of
Organometallic Chemistry, Shanghai Instituted of Organic Chemi-
stry Academia Sinica.
(19) Benati, L.; Capella, L.; Montevecchi, P. C.; Spagnolo, P. J.
Chem. Soc., Perkin Trans. 1 1995, 1035. Trost, B. M.;
Ghadiri, M. R. Bull. Soc. Chim. Fr. 1993, 130, 433. Hirata, T.;
Sasada, Y.; Ohtani, T.; Asada, T.; Kinoshita, H.; Senda, H.;
Inomata, K. Bull. Chem. Soc. Jpn. 1992, 65, 75. Mikolajczyk,
M.; Grzejszczak, S.; Midura, W.; Zatorski, A. Synthesis 1975,
278.
References and Notes
(1) Simpkins, N. S. Tetrahedron 1990, 46, 6951.
(2) Fuchs, P. L.; Braish, T. F. Chem. Rev. 1986, 86 , 903.
(3) Delucchi, O.; Pasquato, L. Tetrahedron 1988, 44, 6755.
Synlett 1999, No. 3, 317–318 ISSN 0936-5214 © Thieme Stuttgart · New York