Acid-Promoted Reaction of Sulfonyl Chlorides with Alkenes: New Approach to the Regioselective Synthesis of β-Hydroxyl Sulfone Derivatives

Chanjuan Xi; Chunbo Lai; Chao Chen; Ruji Wang

doi:10.1055/s-2004-829090

LETTER

Acid-Promoted Reaction of Sulfonyl Chlorides with Alkenes: New Approach to the Regioselective Synthesis of β-Hydroxyl Sulfone Derivatives

Chanjuan Xi*, Chunbo Lai, Chao Chen, Ruji Wang
Key Laboratory for Bioorganic Phosphorus Chemistry of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China
Fax: +86(10)62618239; e-Mail: cjxi@tsinghua.edu.cn;

Abstract

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Abstract

Reaction of sulfonyl chlorides with alkenes and water in the presence of catalytic amount of sulfonic acid provided β-hydroxyl sulfone derivatives in high yields.

Key words

acid-catalyzed - alkene - hydroxyl sulfonylation reaction - sulfone - sulfonyl chloride

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References

<A NAME="RU08404ST-1A">1a</A> Julia M. Paris JM. Tetrahedron Lett. 1973, 4833

<A NAME="RU08404ST-1B">1b</A> Kocienski PJ. Lythogoe B. Ruston SJ. J. Chem. Soc., Perkin Trans. 1 1978, 829

<A NAME="RU08404ST-1C">1c</A> Kocienski PJ. Lythogoe B. Waterhouse I. J. Chem. Soc., Perkin Trans. 1 1980, 1045

<A NAME="RU08404ST-1D">1d</A> Mandai T. Yanagi T. Araki K. Morisaki Y. Kawada M. Otera J. J. Am. Chem. Soc. 1984, 106: 3670

<A NAME="RU08404ST-1E">1e</A> Achmatowicz B. Baranowska E. Daniewski AR. Pankowshi J. Sansano JM. Tetrahedron 1990, 46: 3993

<A NAME="RU08404ST-2A">2a</A> Tavares DF. Vogt PF. Can. J. Chem. 1967, 45: 1519

<A NAME="RU08404ST-2B">2b</A> Harwood LM. Julia M. Thuillier GL. Tetrahedron 1980, 36: 2483

<A NAME="RU08404ST-2C">2c</A> Maiti AK. Bhattacharyya P. Indian J. Chem., Sect. B 1996, 35: 67

<A NAME="RU08404ST-2D">2d</A> Cho B. Kim D. Tetrahedron: Asymmetry 2001, 12: 2043

<A NAME="RU08404ST-2E">2e</A> Gotor V. Rebolledo F. Liz R. Tetrahedron: Asymmetry 2001, 12: 513

<A NAME="RU08404ST-2F">2f</A> Zhao G. Hu J. Qian Z. Yin W. Tetrahedron: Asymmetry 2002, 13: 2095

For representative examples of Cu(I)-catalyzed addition of sulfonyl chlorides to alkenes, see:

<A NAME="RU08404ST-3A">3a</A> Asscher M. Vofsi D. J. Chem. Soc. 1964, 4962

<A NAME="RU08404ST-3B">3b</A> Orochov A. Asscher M. Vofsi D. J. Chem. Soc. B 1969, 255

<A NAME="RU08404ST-3C">3c</A> Sinnreich J. Asscher M. J. Chem. Soc., Perkin Trans. 1 1972, 1543

<A NAME="RU08404ST-3D">3d</A> Orochov A. Asscher M. Vofsi D. J. Chem. Soc., Perkin Trans. 2 1973, 1000

<A NAME="RU08404ST-3E">3e</A> Da Silva Correa CMM. Waters A. J. Chem. Soc. C 1968, 1874

<A NAME="RU08404ST-3F">3f</A> Ameil Y. J. Org. Chem. 1974, 39: 3867

<A NAME="RU08404ST-3G">3g</A> Percec V. Barboiu B. Kim H.-J. J. Am. Chem. Soc. 1998, 120: 305

<A NAME="RU08404ST-4">4</A> For peroxide-induced addition of sulfonyl chlorides to alkenes, see: Kharash MS. Zavist AF. J. Am. Chem. Soc. 1951, 73: 964

For selected examples of Ru(II)-catalyzed addition of sulfonyl chlorides to alkenes, see:

<A NAME="RU08404ST-5A">5a</A> Kamigata N. Sawada H. Kobayashi M. Chem. Lett. 1979, 159

<A NAME="RU08404ST-5B">5b</A> Kamigata N. Sawada H. Kobayashi M. J. Org. Chem. 1983, 48: 3793

<A NAME="RU08404ST-5C">5c</A> Kamigata N. Ozaki J. Kobayashi M. J. Org. Chem. 1985, 50: 5045

<A NAME="RU08404ST-5D">5d</A> Kamigata N. Fukushima T. Terakawa Y. Yoshida M. Sawada H. J. Chem. Soc., Perkin Trans. 1 1991, 627

<A NAME="RU08404ST-5E">5e</A> Kameyama M. Kamigata N. Kobayashi M. Chem. Lett. 1986, 527

<A NAME="RU08404ST-5F">5f</A> Kameyama M. Kamigata N. Bull. Chem. Soc. Jpn. 1989, 62: 648

Crystallographic data of 1b: colorless plate, orthorhombic, Space group Pbca (No. 61), a = 10.199 (3), b = 16.367 (6), c = 17.701 (5) Å, α = 90.00°, β = 90.00°, γ = 90.00°, Z = 8, R ₁ = 0.1563, wR ₂ = 0.1519 (all data), GOF = 1.053.

<A NAME="RU08404ST-7">7</A> Biswas GK. Bhattacharyya P. Synth. Commun. 1991, 21: 569

<A NAME="RU08404ST-8">8</A> Bilaya EE. Obushak ND. Ganushchak NI. Russ. J. Org. Chem. 1999, 35: 632

<A NAME="RU08404ST-9">9</A> Young DJ. Stirling CJM. J. Chem. Soc., Perkin Trans. 2 1997, 425

Representative Procedure for the Hydroxyl Sulfonylation of Alkenes. Preparation of 1-Phenyl-2-( p -toluenesulfonyl)ethanol ( 1a).
p-Toluenesulfonyl chloride (286 mg, 1.5 mmol) and toluene-4-sulfonic acid (35 mg, 0.20 mmol) were dissolved in 5 mL THF. To the solution was added styrene (116 µL, 1.0 mmol) and H₂O (22 µL, 1.2 mmol) at r.t. The mixture was warmed up to 50 °C and stirred for 36 h. Then it was quenched with H₂O and the aqueous layers were extracted with Et₂O (20 mL) for 3 times, and the combined organic layers were dried over Na₂SO₄. The ether extract was evaporated and the crude product was purified by column chromatography on silica gel (EtOAc/petroleum ether = 1:4) to afford compound 1a [7] (207 mg) as white powder in 75%. ¹H NMR (CDCl_3, SiMe₄): δ = 2.46 (s, 3 H), 3.32 (d, J = 14.5 Hz, 1 H), 3.47 (dd, J = 10.0, 14.5 Hz, 1 H), 3.76 (br s, 1 H), 5.25 (d, J = 10.0 Hz, 1 H), 7.26-7.31 (m, 5 H), 7.38 (d, J = 7.8 Hz, 2 H), 7.84 (d, J = 7.8 Hz, 2 H). ¹³C NMR (CDCl₃, SiMe₄): δ = 21.7, 64.0, 68.5, 125.7, 128.0, 128.3, 128.8, 130.1, 136.2, 140.7, 145.3. ESI-MS: 283.1 [M + Li⁺], 299.1 [M + Na⁺].

1- p -Chlorophenyl-2-( p -toluenesulfonyl)ethanol ( 1b): [2c] white powder (224 mg, 72%). ¹H NMR (CDCl₃, SiMe₄): δ = 2.46 (s, 3 H), 3.28 (d, J = 14.5 Hz, 1 H), 3.43 (dd, J = 10.0, 14.5 Hz, 1 H), 3.88 (br s, 1 H), 5.23 (d, J = 9.5 Hz, 1 H), 7.21-7.28 (m, 4 H), 7.37 (d, J = 7.8 Hz, 2 H,), 7.37 (d, J = 8.0 Hz, 2 H). ¹³C NMR (CDCl₃, SiMe₄): δ = 21.7, 63.8, 67.9, 27.1, 128.0, 128.9, 130.1, 134.0, 136.1, 139.3, 145.4. ESI-MS: 333.1, 335.1 [M + Na⁺].

1-Tolyl-2-( p -toluenesulfonyl)ethanol ( 1c): [2c] white powder (206 mg, 70%). ¹H NMR (CDCl₃, SiMe₄): δ = 2.30 (s, 3 H), 2.46 (s, 3 H), 3.29 (dd, J = 1.8, 14.3 Hz, 1 H,), 3.47 (dd, J ₁ = 10.1 Hz, J ₂ = 14.3 Hz, 1 H), 3.69 (br s, 1 H), 5.20 (d, J = 9.84 Hz, 1 H), 7.12-7.18 (m, 4 H), 7.37 (d, J = 8.0 Hz, 2 H), 7.82 (d, J = 8.4 Hz, 2 H). ¹³C NMR (CDCl₃, SiMe₄): δ = 21.2, 21.8, 64.1, 68.4, 125.7, 128.1, 129.5, 130.2, 136.3, 137.9, 138.2. 145.3. ESI-MS: 297.1 [M + Li⁺], 313.1 [M + Na⁺].

2-Phenyl-1-( p -toluenesulfonyl)-propan-2-ol ( 1d): [8] white powder (238 mg, 82%). ¹H NMR (CDCl₃, SiMe₄): δ = 1.69 (s, 3 H), 2.37 (s, 3 H), 3.65 (AB, q, J = 14.8 Hz, 2 H), 4.64 (br s, 1 H), 7.14-7.28 (m, 5 H), 7.47 (d, J = 8.2 Hz, 2 H), 7.27 (d, J = 8.4 Hz, 2 H). ¹³C NMR (CDCl₃, SiMe₄): δ = 21.7, 30.9, 66.8, 73.3, 124.7, 127.2, 127.6, 128.3, 129.8, 137.4, 144.6. ESI-MS: 297.0 [M + Li⁺], 313.0 [M + Na⁺].

2-Methanesulfonyl-1-phenyl-ethanol ( 1e): [2a] white powder (104 mg, 51%). ¹H NMR (CDCl₃, SiMe₄): δ = 3.03 (s, 3 H), 3.14 (d, J = 14.8 Hz, 1 H,), 3.44 (dd, J = 10.0, 14.8 Hz, 1 H), 3.21 (br s, 1 H), 5.32 (d, J = 10.3 Hz, 1 H), 7.34-7.38 (m, 5 H). ¹³C NMR (CDCl₃, SiMe₄): δ = 43.0, 62.5, 69.4, 125.8, 128.7, 129.1, 141.2. ESI-MS: 206.9 [M + Li⁺], 222.9 [M + Na⁺].

1-(4-Chlorophenyl)-2-methanesulfonylethanol ( 1f): white powder (101 mg, 43%). ¹H NMR (CDCl₃, SiMe₄): δ = 3.05 (s, 3 H), 3.12 (d, J = 14.8 Hz, 1 H,), 3.41 (dd, J = 10.3, 14.8 Hz, 1 H), 3.26 (br s, 1 H), 5.32 (d, J = 10.0 Hz, 1 H), 7.30-7.35 (m, 4 H). ¹³C NMR (CDCl₃, SiMe₄): δ = 43.0, 62.3, 68.7, 127.2, 129.3, 134.5, 139.6. ESI-MS: 238.9, 240.9 [M + Na⁺]. HRMS: anal. calcd for C₉H₁₁ClO₃S: 234.0117, 236.0088; found: 234.0111, 236.0046.

1-Tolyl-2-(methanesulfonyl)ethanol ( 1g): white powder (130 mg, 61%). ¹H NMR (CDCl₃, SiMe₄): δ = 2.34 (s, 3 H), 3.02 (s, 3 H), 3.08-3.13 (m, 2 H), 3.43 (dd, J = 10.1, 14.9 Hz, 1 H), 5.26 (d, J = 10.3 Hz, 1 H), 7.18 (d, J = 8.2 Hz, 2 H), 7.25 (d, J = 7.9 Hz, 2 H). ¹³C NMR (CDCl₃, SiMe₄): δ = 21.2, 42.9, 62.5, 69.2, 125.7, 129.7, 138.3, 138.6. ESI-MS: 221.0 [M + Li⁺]. HRMS: anal. calcd for C₁₀H₁₄O₃S: 214.0664; found: 214.0665.

1-Methanesulfonyl-2-phenyl-propan-2ol ( 1h): [9] oily liquid (152 mg, 71%). ¹H NMR (CDCl₃, SiMe₄): δ = 1.73 (s, 3 H), 2.42 (s, 3 H), 3.52 (AB q, J = 14.8 Hz, 2 H), 4.36 (br s, 1 H), 7.42-7.49 (m, 5 H). ¹³C NMR (CDCl₃, SiMe₄): δ = 30.7, 43.2, 65.7, 72.6, 124.9, 127.9, 128.9, 144.65. ESI-MS: 220.9 [M + Li⁺].