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Synlett 2006(4): 0571-0574  
DOI: 10.1055/s-2006-932496
LETTER
© Georg Thieme Verlag Stuttgart · New York

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

Yunkui Liua, Xiangsheng Xua, Hui Zhenga, Danqian Xub, 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
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Publication History

Received 23 November 2005
Publication Date:
20 February 2006 (online)

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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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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.

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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.

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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.

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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.