Stereoselective Synthesis of (Z)-β-Chlorovinyl Sulfones by Addition of Sulfonyl Chlorides to Acetylenes

Xueyuan Liu; Xinhua Duan; Zhenliang Pan; Yao Han; Yongmin Liang

doi:10.1055/s-2005-869876

LETTER

Stereoselective Synthesis of (Z)-β-Chlorovinyl Sulfones by Addition of Sulfonyl Chlorides to Acetylenes

Xueyuan Liu^a, Xinhua Duan^a, Zhenliang Pan^a, Yao Han^a, Yongmin Liang*^a,b
^a State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. China
^b State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China
Fax: +86(931)8912582; e-Mail: liangym@lzu.edu.cn;

Abstract

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Abstract

The addition reaction of sulfonyl chlorides with acetylenes in the presence of a copper salt is described. The reaction proceeds in toluene in the presence of CuCl with Me₂S as the additive to afford only (Z)-β-chlorovinyl sulfones in moderate to excellent yields.

Key words

halovinyl sulfones - sulfonyl chlorides - acetylenes - CuCl/Me₂S

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References

1a Simpkins NS. Sulphones in Organic Synthesis Pergamon; Oxford: 1993.

1b Tanaka K. Kaji A. In The Chemistry of Sulfones and Sulphoxides Patai S. Rapoport Z. Stirling CJM. Wiley; Chichester: 1988. Chap. 15.

1c Carreno MC. Chem. Rev. 1995, 95: 1717

1d Yoshida K. Hayashi T. J. Am. Chem. Soc. 2003, 125: 2872

1e Simpkins NS. Tetrahedron 1990, 46: 6951

1f Ranu BC. Guchhait SK. Ghosh K. J. Org. Chem. 1998, 63: 5250

2 Fuchs PL. Braish TF. Chem. Rev. 1986, 86: 903

3a De Lucchi O. Pasquato L. Tetrahedron 1988, 44: 6755

3b Huang DF. Shen TY. Tetrahedron Lett. 1993, 34: 4477

3c Hlasta DJ. Ackerman JH. J. Org. Chem. 1994, 59: 6184

4 Reddy PE, and Reddy RMV. inventors; PCT Int. Appl. WO 9918068. ; Chem. Abstr. 1999, 130, 281870

5 Konopa JK, Konieczny MT, Horowska BJ, Kunikowski AJ, Asao T, Nishino H, and Yamada Y. inventors; Jpn. Patent JP 9003037. ; Chem. Abstr. 1997, 126, 185889

6a Amiel Y. J. Org. Chem. 1971, 36: 3691

6b Amiel Y. J. Org. Chem. 1971, 36: 3697

6c Amiel Y. Tetrahedron Lett. 1971, 12: 661

6d Amiel Y. J. Org. Chem. 1974, 39: 3867

7 Truce WE. Wolf GC. J. Org. Chem. 1971, 36: 1727

8 Huang X. Duan DH. Chem. Commun. 1999, 1741

9

General procedure: To a solution of alkyne (1.0 mmol) and sulfonyl chloride (1.5 mmol) in toluene (5 mL) was added CuCl (0.1 mmol) and Me₂S (1.0 mmol). The reaction mixture was heated under argon to 110 °C for the time indicated. The mixture was then quenched by the addition of H₂O and extracted with diethyl ether. The isolated organic phase was dried over Na₂SO₄, filtered, concentrated in vacuo, and purified by column chromatography on silica gel eluting with ethyl acetate-hexane. 3f: mp 138-140 °C; IR (film): 1577, 1314, 1146, 562 cm^-1; ¹H NMR (CDCl₃, 300 MHz): δ = 7.12 (s, 1 H), 7.45-7.48 (m, 2 H), 7.52-7.60 (m, 4 H), 7.64-7.69 (m, 1 H), 8.06 (d, 2 H); ¹³C NMR (CDCl₃, 75 MHz): δ = 145.0, 140.4, 133.8, 132.0 (2 C), 129.1 (2 C), 128.6 (2 C), 128.1 (2 C), 127.9 (2 C), 126.3; MS (EI): m/z 356 (M⁺, 12), 233 (9), 205 (6), 180 (17), 152 (100), 125 (33), 101 (27), 77 (55).

CuX·Me₂S (X = I, Br) complex is an excellent catalyst for some conjugate addition reactions, see:

10a Dambacher J. Bergdahl M. Chem. Commun. 2003, 144

10b EI-Batta A. Hage TR. Plotkin S. Bergdahl M. Org. Lett. 2004, 6: 107