可见光介导的羰基α位C—H官能团化反应合成萘咪酮类衍生物

doi:10.6023/cjoc202406051

摘要/Abstract

开发了一种以曙红Y (Esoin Y)为光催化剂的可见光诱导的普适和实用的羰基α位C—H官能团化策略. 这种温和的转化为制备具有潜在生物活性的萘咪酮类衍生物提供了一种操作简单、底物范围广且高原子经济的高效便捷的方法. 机制研究表明该策略涉及自由基反应机制.

关键词: 可见光催化, C—H官能团化, C—S偶联, C—O偶联

A universal and practical visible-light-induced α-functionalization of carbonyl compounds is demonstrated using Esoin Y as photocatalyst. This mild transformation provides an efficient and convenient approach for the synthesis of potentially bioactive nafimidone derivatives with operational simplicity, a broad substrate scope and high atom economy. The mechanistic studies reveal that a free radical pathway mechanism is responsible for this transformation.

Key words: visible-light catalysis, C—H functionalization, C—S coupling reaction, C—O coupling reaction

引用此文

沈佳斌, 沈超, 章鹏飞. 可见光介导的羰基α位C—H官能团化反应合成萘咪酮类衍生物[J]. 有机化学, 2025, 45(2): 677-685.

Jiabin Shen, Chao Shen, Pengfei Zhang. Synthesis of Nafimidone Derivatives by Visible-Light-Induced α-C—H Functionalization of Carbonyl[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 677-685.

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参考文献 18

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Entry	Metal-catalyst	Photocatalyst	Base	Solvent	Yield^b/%
1	CuI	Fluorescein	Et₃N	MeCN	65
2	CuCl	Fluorescein	Et₃N	MeCN	54
3	CuCl₂	Fluorescein	Et₃N	MeCN	43
4	Cu₂O	Fluorescein	Et₃N	MeCN	14
5	CuO	Fluorescein	Et₃N	MeCN	17
6	—	Fluorescein	Et₃N	MeCN	Trace
7	CuI	Rose Bengal	Et₃N	MeCN	54
8	CuI	9-Fluorenone	Et₃N	MeCN	71
9	CuI	Mes-Acr^＋	Et₃N	MeCN	43
10	CuI	—	Et₃N	MeCN	Trace
11	CuI	Eosin Y	Et₃N	MeCN	76
12	CuI	Eosin Y	DMAP	MeCN	87
13	CuI	Eosin Y	NaOH	MeCN	64
14	CuI	Eosin Y	KOH	MeCN	67
15	CuI	Eosin Y	K₂HPO₄	MeCN	51
16	CuI	Eosin Y	NaHCO₃	MeCN	47
17	CuI	Eosin Y	DMAP	THF	52
18	CuI	Eosin Y	DMAP	DCE	63
19	CuI	Eosin Y	DMAP	DMSO	74
20	CuI	Eosin Y	DMAP	DMF	68
21	CuI	Eosin Y	DMAP	Dioxane	56
22^c	CuI	Eosin Y	DMAP	MeCN	86
23^d	CuI	Eosin Y	DMAP	MeCN	52
24^e	CuI	Eosin Y	DMAP	MeCN	87
25^f	CuI	Eosin Y	DMAP	MeCN	64
26^g	CuI	Eosin Y	DMAP	MeCN	87
27^h	CuI	Eosin Y	DMAP	MeCN	61
28ⁱ	CuI	Eosin Y	DMAP	MeCN	Trace
29^j	CuI	Eosin Y	DMAP	MeCN	Trace

Entry	Metal-catalyst	Photocatalyst	Base	Solvent	Yield^b/%
1	CuI	Fluorescein	Et₃N	MeCN	65
2	CuCl	Fluorescein	Et₃N	MeCN	54
3	CuCl₂	Fluorescein	Et₃N	MeCN	43
4	Cu₂O	Fluorescein	Et₃N	MeCN	14
5	CuO	Fluorescein	Et₃N	MeCN	17
6	—	Fluorescein	Et₃N	MeCN	Trace
7	CuI	Rose Bengal	Et₃N	MeCN	54
8	CuI	9-Fluorenone	Et₃N	MeCN	71
9	CuI	Mes-Acr^＋	Et₃N	MeCN	43
10	CuI	—	Et₃N	MeCN	Trace
11	CuI	Eosin Y	Et₃N	MeCN	76
12	CuI	Eosin Y	DMAP	MeCN	87
13	CuI	Eosin Y	NaOH	MeCN	64
14	CuI	Eosin Y	KOH	MeCN	67
15	CuI	Eosin Y	K₂HPO₄	MeCN	51
16	CuI	Eosin Y	NaHCO₃	MeCN	47
17	CuI	Eosin Y	DMAP	THF	52
18	CuI	Eosin Y	DMAP	DCE	63
19	CuI	Eosin Y	DMAP	DMSO	74
20	CuI	Eosin Y	DMAP	DMF	68
21	CuI	Eosin Y	DMAP	Dioxane	56
22^c	CuI	Eosin Y	DMAP	MeCN	86
23^d	CuI	Eosin Y	DMAP	MeCN	52
24^e	CuI	Eosin Y	DMAP	MeCN	87
25^f	CuI	Eosin Y	DMAP	MeCN	64
26^g	CuI	Eosin Y	DMAP	MeCN	87
27^h	CuI	Eosin Y	DMAP	MeCN	61
28ⁱ	CuI	Eosin Y	DMAP	MeCN	Trace
29^j	CuI	Eosin Y	DMAP	MeCN	Trace