Snapshot of Oxidation of Thiolate by Diiodine: Stabilization of Intermediate by NH···S Hydrogen Bonds

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• 作者：Taka-aki OkamuraToshihisa Kaga ; Satoshi Yamashita ; Ryosuke Furuya ; Kiyotaka Onitsuka
• 刊名：Journal of Organic Chemistry
• 出版年：2017
• 出版时间：February 17, 2017
• 年：2017
• 卷：82
• 期：4
• 页码：2187-2192
• 全文大小：429K
• ISSN：1520-6904

文摘

Ordinary thiolate (RS^–) reacts with diiodine (I₂) to afford an intermediate sulfenyl iodide (RSI) by releasing I^–; RSI is readily converted to disulfide (RSSR) by a disproportionation reaction. In the case of thiolate Ar¹S^– containing very bulky acylamino groups forming NH···S hydrogen bonds, the crystal of the intermediate, [Ar¹S–I–I]⁻, was obtained under usual conditions, and the structure was determined by X-ray diffraction analysis. The results show that the intramolecular NH···S hydrogen bonds stabilized the intermediate [Ar¹S–I–I]⁻, consistent with theoretical calculations.