有机化学 ›› 2022, Vol. 42 ›› Issue (11): 3721-3729.DOI: 10.6023/cjoc202206029 上一篇    下一篇

研究论文

碘化钾催化无保护8-氨基喹啉的选择性C(5)-芳基硫醚化和C(5),C(7)-双芳基硫醚化及吲哚C(2),C(3)-双芳基硫醚化反应

吴豪志, 罗田, 姜建文*(), 万结平*()   

  1. 江西师范大学化学化工学院 南昌 330022
  • 收稿日期:2022-06-18 修回日期:2022-07-13 发布日期:2022-08-10
  • 通讯作者: 姜建文, 万结平
  • 基金资助:
    国家自然科学基金(22161022)

KI-Catalyzed Selective C(5)-Sulfenylation and C(5),C(7)-Disulfenylation of Unprotected 8-Aminoquinolines and the Indole C(2),C(3)-Disulfenylation

Haozhi Wu, Tian Luo, Jianwen Jiang(), Jieping Wan()   

  1. College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, 330022
  • Received:2022-06-18 Revised:2022-07-13 Published:2022-08-10
  • Contact: Jianwen Jiang, Jieping Wan
  • Supported by:
    National Natural Science Foundation of China(22161022)

报道了采用2.5 mol%碘化钾为唯一催化剂, 无需任何过渡金属催条件下无保护8-氨基喹啉的碳-氢甲芳基硫醚化反应. 有趣的是, 通过简单调控反应时间和介质可以实现选择性的C(5)-芳基硫醚化和C(5),C(7)-双芳基硫醚化. 在对二甲苯中反应12 h时为C(5)-芳基硫醚化. 另一方面, 延长反应时间至24 h并更换反应介质为甲苯则选择性地发生C(5),C(7)-双芳基硫醚化. 此外, 双芳基硫醚化反应可以扩展到吲哚类底物, 实现含2,3-二芳基硫醚结构的吲哚合成.

关键词: 碳-氢键官能化, 自由基, 8-氨基喹啉, 选择性, 芳基硫醚化

The aromatic C—H sulfenylation reactions of unprotected 8-aminoquinolines have been realized by employing KI as the only catalyst at 2.5 mol% loading without using any transition metal reagent. Interestingly, the selective C(5)-sulfenylation and C(5),C(7)-disulfenylation have been successfully achieved by simply controlling the reaction time. Reaction time of 12 h in p-xylene enables the C(5)-sulfenylation. On the other hand, prolonging the reaction time to 24 h and switching the reaction medium to toluene lead to the selective C(5),C(7)-double sulfenylation. Moreover, the double sulfenylation has been extended to the indole substrate for the selective synthesis of 2,3-disulfenyl indoles.

Key words: C—H functionalization, free radical, 8-aminoquinoline, selectivity, sulfenylation