二氟卡宾参与下从邻乙烯基苯胺出发构建3-取代吲哚酮类化合物

doi:10.6023/cjoc202210031

有机化学 ›› 2023, Vol. 43 ›› Issue (3): 1146-1156.DOI: 10.6023/cjoc202210031 上一篇下一篇

所属专题：有机氟化学虚拟合辑；中国女科学家专辑

研究论文

二氟卡宾参与下从邻乙烯基苯胺出发构建3-取代吲哚酮类化合物

黄华^a, 李鑫^a, 苏建科^a, 宋秋玲^a^,^b^,^c^,^*()

a 华侨大学材料科学工程学院下一代物质转化研究所福建厦门 361021
b 中国科学院上海有机化学研究所金属有机化学国家重点实验室和有机氟化学重点实验室上海 200032
c 河南师范大学化学化工学院河南新乡 453007

收稿日期:2022-10-26 修回日期:2022-11-30 发布日期:2022-12-21
通讯作者: 宋秋玲
基金资助:
国家自然科学基金(21931013)

Difluorocarbene-Enabled Synthesis of 3-Substituted-2-oxoindoles from o-Vinylanilines

Hua Huang^a, Xin Li^a, Jianke Su^a, Qiuling Song^a^,^b^,^c()

a Institute of Next Generation Matter Transformation, College of Material Sciences Engineering, Huaqiao University, Xiamen, Fujian 361021
b State Key Laboratory of Organometallic Chemistry and Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
c School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007

Received:2022-10-26 Revised:2022-11-30 Published:2022-12-21
Contact: Qiuling Song
Supported by:
National Natural Science Foundation(21931013)

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摘要/Abstract

开发了一种新型的无需过渡金属参与的合成1-烷基-3-(2-氧代-2-芳基/烷基-乙基)吲哚酮的方法. 这项工作揭示了氧吲哚骨架可以直接由邻乙烯基苯胺和市售的卤代二氟烷基试剂通过C—N裂解/新C—N键和C—C键形成来构建. 该反应具有高效和优异的官能团兼容性, 在药物分子和天然产物的后期修饰中具有巨大潜力.

关键词: 卤代二氟试剂, 3-取代吲哚酮, 二氟卡宾

A novel transition-metal-free protocol for the synthesis of 1-alkyl-3-(2-oxo-2-aryl/alkyl-ethyl)indolin-2-ones is developed. This work reveals that oxoindole skeletons can be directly constructed from ortho-vinylanilines and commercially available halogenated difluoroalkyl reagents via a C—N cleavage/new C—N bonds and C—C bond formation cascade. This reaction portrays high efficiency and excellent functional group compatibility, and has great potential in the late-stage modifications of pharmaceutical molecules and natural products.

Key words: halo difluoro reagent, 3-substituted 2-oxindole, difluorocarbene

引用此文

黄华, 李鑫, 苏建科, 宋秋玲. 二氟卡宾参与下从邻乙烯基苯胺出发构建3-取代吲哚酮类化合物[J]. 有机化学, 2023, 43(3): 1146-1156.

Hua Huang, Xin Li, Jianke Su, Qiuling Song. Difluorocarbene-Enabled Synthesis of 3-Substituted-2-oxoindoles from o-Vinylanilines[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1146-1156.

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Entry	Base	[∶CF₂]	Solvent	T/℃	Yield^b/%
1	K₂CO₃	2a	CH₃CN	90	76
2	KOH	2a	CH₃CN	90	45
3	Na₂CO₃	2a	CH₃CN	90	61
4	Na₃PO₄	2a	CH₃CN	90	56
5	K₃PO₄	2a	CH₃CN	90	93 (90^c)
6	K₃PO₄	2a	THF	90	15
7	K₃PO₄	2a	DME	90	Trace
8	K₃PO₄	2a	Toluene	90	n.r.
9	K₃PO₄	2b	CH₃CN	90	88
10	K₃PO₄	2c	CH₃CN	90	66
11	K₃PO₄	2d	CH₃CN	90	Trace
12	K₃PO₄	2e	CH₃CN	90	49
13	K₃PO₄	2a	CH₃CN	80	81
14	K₃PO₄	2a	CH₃CN	100	93
15	K₃PO₄	2a	CH₃CN	110	88

Entry	Base	[∶CF₂]	Solvent	T/℃	Yield^b/%
1	K₂CO₃	2a	CH₃CN	90	76
2	KOH	2a	CH₃CN	90	45
3	Na₂CO₃	2a	CH₃CN	90	61
4	Na₃PO₄	2a	CH₃CN	90	56
5	K₃PO₄	2a	CH₃CN	90	93 (90^c)
6	K₃PO₄	2a	THF	90	15
7	K₃PO₄	2a	DME	90	Trace
8	K₃PO₄	2a	Toluene	90	n.r.
9	K₃PO₄	2b	CH₃CN	90	88
10	K₃PO₄	2c	CH₃CN	90	66
11	K₃PO₄	2d	CH₃CN	90	Trace
12	K₃PO₄	2e	CH₃CN	90	49
13	K₃PO₄	2a	CH₃CN	80	81
14	K₃PO₄	2a	CH₃CN	100	93
15	K₃PO₄	2a	CH₃CN	110	88

二氟卡宾参与下从邻乙烯基苯胺出发构建3-取代吲哚酮类化合物

Difluorocarbene-Enabled Synthesis of 3-Substituted-2-oxoindoles from o-Vinylanilines

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