Transition-Metal-Free Method for the Synthesis of Benzo[b]thiophenes from o-Halovinylbenzenes and K2S via Direct SNAr-Type Reaction, Cyclization, and Dehydrogenation Process

Xiaoyun Zhang; Weilan Zeng; Yuan Yang; Hui Huang; Yun Liang

doi:10.1055/s-0033-1339289

Synlett, Inhaltsverzeichnis

Synlett 2013; 24(13): 1687-1692
DOI: 10.1055/s-0033-1339289

letter

Transition-Metal-Free Method for the Synthesis of Benzo[b]thiophenes from o-Halovinylbenzenes and K₂S via Direct S_NAr-Type Reaction, Cyclization, and Dehydrogenation Process

Xiaoyun Zhang

^aNational & Local Joint Engineering Laboratory for New Petrochemical Materials and Fine Utilization of Resources, Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, Changsha, Hunan 410081, P. R. of China Fax: +86(731)88872533 eMail: liangyun1972@126.com

,

Weilan Zeng

^aNational & Local Joint Engineering Laboratory for New Petrochemical Materials and Fine Utilization of Resources, Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, Changsha, Hunan 410081, P. R. of China Fax: +86(731)88872533 eMail: liangyun1972@126.com

,

Yuan Yang

^aNational & Local Joint Engineering Laboratory for New Petrochemical Materials and Fine Utilization of Resources, Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, Changsha, Hunan 410081, P. R. of China Fax: +86(731)88872533 eMail: liangyun1972@126.com

,

Hui Huang

^aNational & Local Joint Engineering Laboratory for New Petrochemical Materials and Fine Utilization of Resources, Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, Changsha, Hunan 410081, P. R. of China Fax: +86(731)88872533 eMail: liangyun1972@126.com

,

Yun Liang*

^aNational & Local Joint Engineering Laboratory for New Petrochemical Materials and Fine Utilization of Resources, Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, Changsha, Hunan 410081, P. R. of China Fax: +86(731)88872533 eMail: liangyun1972@126.com

^bBeijing National Laboratory for Molecular Sciences, Beijing 100871, P. R. of China

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Abstract

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Abstract

A new, highly efficient procedure for the synthesis of benzothiophenes from easily available o-halovinylbenzenes and potassium sulfide has been developed. The reaction tolerated a wide range of functionalities, and various 2-substituted benzo[b]thiophenes are provided in the high yields in the absence of a transition-metal catalyst.

Key words

transition-metal-free - benzo[b]thiophenes - o-halovinylbenzenes - direct S_NAr-type reaction - cyclization - dehydrogenation process

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Referenzen

References and Notes

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10 Benzo[b]thiophenes 2; General Procedure Under the protection of nitrogen, an oven-dried Schlenk tube was charged with K₂S (0.9 mmol, 3 equiv) and the 1-fluoro-2-styryl derivative (0.3 mmol). The tube was evacuated and backfilled with nitrogen before DMF or MeCN (2 mL) was added. The reaction mixture was stirred at 140 °C, and after 24 h was quenched with H₂O. The mixture extracted with EtOAc, and the combined organic layers were washed with H₂O and brine, dried over Na₂SO₄, concentrated in vacuo and purified by column chromatography to afford the product. Analytical Data for Compound 2a white solid; isolated yield 96% (60 mg; mp 172.2–173.0 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.82 (d, J = 8.0 Hz, 1 H), 7.77 (d, J = 7.5 Hz, 1 H), 7.72 (d, J = 8.5 Hz, 2 H), 7.54 (s, 1 H), 7.42 (t, J = 7.8 Hz, 2 H), 7.36–7.29 (m, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 144.2, 140.7, 139.5, 134.3, 128.9, 128.2, 126.5, 124.5, 124.3, 123.5, 122.2, 119.4.

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