吲哚-3-硫醚类化合物的合成研究进展

doi:10.6023/cjoc202211012

摘要/Abstract

吲哚-3-硫醚类化合物是一类重要的的生物活性分子, 在医药以及农用化学品等领域具有广泛应用. 如何通过简单、高效的方法构建此类结构单元, 尤其是实现吲哚C-3原子上C—S键的选择性合成, 已成为近年来高生物活性分子设计开发的重要手段. 总结了通过吲哚3位C—H键直接选择性硫醚化制备吲哚-3-硫醚类化合物的方法, 根据硫元素的不同来源对此类反应的研究进展进行综述.

关键词: 硫醚化, C—S键, 交叉偶联

3‑Sulfenylated indoles have been widely used in pharmaceutical and agrochemical industry due to their inherent potential biological activity. How to synthesize bioactive molecules containing such structural units via simple and efficient method, especially to achieve the selective construction of C—S bond on indole C-3 atom, has become an important means for the design and development of highly bioactive molecules in recent years. The recent development in the regioselective synthesis of 3-sulfenylated indoles via the direct sulfenylation of indoles at the C-3 position on the basis of different types of sulfenylating reagents is summarized.

Key words: sulfenylation, C—S bond, cross-coupling

引用此文

童宇星, 王子维, 刘奔, 徐耀威, 高颂, 唐向兵, 张兴华. 吲哚-3-硫醚类化合物的合成研究进展[J]. 有机化学, 2023, 43(4): 1310-1324.

Yuxing Tong, Ziwei Wang, Ben Liu, Yaowei Xu, Song Gao, Xiangbing Tang, Xinghua Zhang. Recent Advances in Synthesis of 3-Sulfenylated Indoles[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1310-1324.

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图/表 13

图式1. 含吲哚-3-硫醚结构的生物活性分子

Scheme 1. Some biologically active 3-sulfanylindoles

图式2. 过渡金属催化吲哚-3-硫醚的合成

Scheme 2. Transition metal-catalyzed the synthesis of 3?sul- fenylated indoles

图式3. I2/Oxidant促进吲哚-3-硫醚化合物的制备

Scheme 3. Preparation of 3?sulfenylated indoles promoted by I2/Oxidant

图式4. 电催化吲哚-3-硫醚类化合物的合成

Scheme 4. Electrocatalytic synthesis of 3-sulfanylindoles

图式5. 可见光介导吲哚-3-硫醚的合成

Scheme 5. Synthesis of 3?sulfenylated indoles induced by visible-light

图式6. 碘催化亚磺酸盐与吲哚衍生物的交叉偶联

Scheme 6. Cross-coupling of sodium sulfinates with indoles catalyzed by iodine

图式7. TsOH/n-Bu4NI催化吲哚与芳基亚磺酸交叉偶联

Scheme 7. Cross-coupling of indoles with sulfinic acids catalyzed by TsOH/n-Bu4NI

图式8. 碘催化吲哚与芳(烷)基磺酰氯交叉偶联

Scheme 8. Cross-coupling of indoles with aryl/alkyl sulfonyl chlorides catalyzed by iodine

图式9. 碘催化磺酰肼与吲哚选择性硫醚化反应

Scheme 9. Iodine-catalyzed regioselective sulfenylation of indoles with sulfonyl hydrazides

图式10. 溴化镁催化吲哚与N-芳(烷)硫基邻苯二甲酰亚胺的硫醚化反应

Scheme 10. MgBr2-catalyzed sulfenylation of indoles with N- thioalkyl- and N-thioarylphthalimides

图式11. 三氯化铈催化吲哚-3-硫醚的合成

Scheme 11. CeCl3-catalyzed the synthesis of 3?sulfenylated indoles

图式12. 碘催化吲哚与Bunte盐的交叉偶联

Scheme 12. Cross-coupling of indoles with bunte salts catalyzed by iodine

图式13. 二氯化碘苯促进吲哚-3-硫醚的合成

Scheme 13. Synthesis of 3?sulfenylated indoles mediated by a hypervalent iodine(III) reagent

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