A Facile and Stereoselective Synthesis of Unsymmetrical Diallylsulfides via Indium-Promoted One-Pot Reaction of Baylis-Hillman Acetates, Sodium Thiosulfate, and Allyl Bromide

Yunkui Liu; Xiangsheng Xu; Hui Zheng; Danqian Xu; Zhenyuan Xu; Yongmin Zhang

doi:10.1055/s-2006-932496

LETTER

A Facile and Stereoselective Synthesis of Unsymmetrical Diallylsulfides via Indium-Promoted One-Pot Reaction of Baylis-Hillman Acetates, Sodium Thiosulfate, and Allyl Bromide

Yunkui Liu^a, Xiangsheng Xu^a, Hui Zheng^a, Danqian Xu^b, Zhenyuan Xu*^a, Yongmin Zhang*^b,c
^a State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, P. R. of China
Fax: +86(571)88320609; e-Mail: chrc@zjut.edu.cn;
^b Department of Chemistry, Zhejiang University, Xi-xi Campus, Hangzhou 310028, P. R. of China
^c State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China

Abstract

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Abstract

A facile and stereoselective synthesis of unsymmetrical diallylsulfides was achieved in moderate to good yields via indium-promoted one-pot reaction of Baylis-Hillman acetates, sodium thiosulfate, and allyl bromide.

Key words

stereoselective - diallylsulfides - allyl bromide - Baylis-Hillman acetates - indium

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References

References and Notes

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16

General Procedure for the Preparation of Sodium ( Z )-Allyl Thiosulfates.
In a 25-mL flask were added Na₂SSO₃·5H₂O (0.25 g, 1 mmol), Baylis-Hillman acetate 1 (1 mmol), and anhyd MeOH (15 mL). The mixture was stirred at r.t. for 4-8 h. Then, to the resultant mixture was added silica gel powder (2.0 g). After evaporation of the solvent, the silica gel-absorbed crude product was loaded to chromatography column for further purification using MeOH-EtOAc (1:1) as eluent.

According to the literature, in the ¹H NMR spectrum of a trisubstituted alkene the β-vinylic proton, cis and trans to the ester group are known to resonate at δ = 7.5 ppm and δ = 6.5 ppm, respectively, when alkene is substituted by an aryl group; while the same proton cis and trans to an ester group appears at δ = 6.8 ppm and δ = 5.7 ppm, respectively, when substituted by an alkyl one. See:

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18

Selected spectroscopic data for compound 2:
Compound 2a: ¹H NMR (400 MHz, DMSO-d ₆): δ = 3.71 (s, 3 H, OCH ₃), 4.05 (s, 2 H, methylene-H), 7.38-7.46 (m, 3 H, ArH), 7.63 (s, 1 H, ArCH=), 7.67-7.72 (m, 2 H, ArH). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 31.49, 52.35, 127.33, 128.86, 129.56, 130.42, 134.24, 140.77, 167.28. IR (KBr): ν = 3082, 3026, 1714, 1625 cm^-1. MS (70 eV): m/z (%) = 207 [M⁺ - SO₃Na]. Anal. Calcd for C₁₁H₁₁NaO₅S₂: C, 42.57; H, 3.57. Found: C, 42.89; H, 3.65.

19 Li CJ. Chem. Rev. 2005, 105: 3095

20

General Procedure for the One-Pot Synthesis of Unsymmetrical Diallylsulfides.
After the sodium (Z)-allyl thiosulfate was readily prepared under an inert atmosphere according to the procedure given in ref. 15, allyl bromide (3 mmol) and In (1.5 mmol) were added to the sodium (Z)-allyl thiosulfate solution, the resulting mixture was stirred at r.t. for 30 min. Then the mixture was stirred at 55 °C for 8-12 h. Upon completion, the reaction mixture was cooled down to r.t. and extracted with Et₂O (2 × 30 mL), washed with brine (15 mL), and dried over MgSO₄. After evaporation of solvent, the residue was purified by chromatography using cyclohexane-EtOAc (6:1) as eluent.

21

Selected spectroscopic data for compounds 3:
Compound 3a: oil. ¹H NMR (400 MHz, CDCl₃): δ = 3.16 (d, 2 H, J = 6.8 Hz), 3.59 (s, 2 H), 3.86 (s, 3 H), 4.84-5.04 (m, 2 H), 5.77 (ddt, 1 H, J ₁ = 17.2 Hz, J ₂ = 10.0 Hz, J ₃ = 6.8 Hz), 7.26-7.50 (m, 5 H, ArH), 7.76 (s, 1 H, ArCH=). ¹³C NMR (100 MHz, CDCl₃): δ = 28.11, 36.14, 52.44, 117.33, 125.72, 127.88, 128.82, 129.11, 129.84, 134.34, 140.81, 168.24. IR (film): ν = 3081, 3060, 3026, 1716, 1633, 1597 cm^-1.
MS (70 eV): m/z (%) = 248 [M⁺]. Anal. Calcd for C₁₄H₁₆O₂S: C, 67.71; H, 6.49. Found: C, 67.50; H, 6.62.
Compound 3c: oil. ¹H NMR (400 MHz, CDCl₃): δ = 3.19 (d, 2 H, J = 6.8 Hz), 3.55 (s, 2 H), 3.86 (s, 3 H), 4.96-5.06 (m, 2 H), 5.80 (ddt, 1 H, J ₁ = 17.2 Hz, J ₂ = 10.0 Hz, J ₃ = 6.8 Hz), 7.39 (d, 2 H, J = 8.0 Hz, ArH), 7.46 (d, 2 H, J = 8.0 Hz, ArH), 7.69 (s, 1 H, ArCH=). ¹³C NMR (100 MHz, CDCl₃): δ = 27.82, 36.06, 52.35, 117.33, 125.51, 128.86, 129.70, 130.94, 133.29, 133.93, 139.39, 167.66. IR (film): ν = 3076, 3054, 3023, 1718, 1632, 1593 cm^-1. MS (70 eV): m/z (%) = 282 [M⁺], 284 [M⁺ + 2]. Anal. Calcd for C₁₄H₁₅ClO₂S: C, 59.46; H, 5.35. Found: C, 59.21; H, 5.43.
Compound 3e: oil. ¹H NMR (400 MHz, CDCl₃): δ = 3.21 (d, 2 H, J = 6.8 Hz), 3.62 (s, 2 H), 3.84 (s, 3 H), 3.85 (s, 3 H), 4.99-5.07 (m, 2 H), 5.84 (ddt, 1 H, J ₁ = 16.8 Hz, J ₂ = 10.0 Hz, J ₃ = 6.8 Hz), 6.94 (d, 2 H, J = 9.2 Hz, ArH), 7.50 (d, 2 H, J = 9.2 Hz, ArH), 7.71 (s, 1 H, ArCH=). ¹³C NMR (100 MHz, CDCl₃): δ = 28.17, 35.22, 52.16, 55.31, 113.70, 114.07, 117.15, 127.41, 128.80, 131.63, 134.12, 140.71, 160.26, 168.17. IR (film): ν = 3075, 3058, 3023, 1714, 1632, 1605 cm^-1. MS (70 eV): m/z (%) = 278 [M⁺]. Anal. Calcd for C₁₅H₁₈O₃S: C, 64.72; H, 6.52. Found: C, 64.96; H, 6.62.