空气氛围下可见光诱导的硫酚氧化脱氢偶联

doi:10.6023/cjoc202111037

摘要/Abstract

α-硫醚化羰基化合物广泛存在于自然界和各行业领域, 是合成杂环的重要中间体, 传统的羰基硫醚合成方法通常需要将底物预功能化, 将其从亲核试剂转化为亲电试剂, 合成方法繁琐复杂, 因此探索一种新型的羰基化合物的硫醚化反应非常重要. 开发了一种在可见光条件下, 利用酮类化合物和硫酚的氧化脱氢偶联反应合成硫醚化合物的方法. 在光催化体系下, 无需任何金属, 该反应使用廉价易得的空气作为氧化剂, 成功实现高原子经济性和广泛的底物适用范围, 为C—S键的直接构建提供了更为简便的方法.

关键词: 可见光诱导, C—S键构建, 脱氢偶联, 硫醚

α-Thioetherified carbonyl compounds widely exist in nature and various industries. They are important intermediates for the synthesis of heterocycles. The traditional synthesis methods of carbonyl thioethers usually need the pre- functionalization of substrates to convert them from nucleophiles to electrophiles. The synthesis methods are cumbersome and complex. Therefore, it is very important to explore a new thioetherification reaction of carbonyl compounds. The synthesis of thioether compounds by oxidative dehydrogenation coupling reaction of ketones and thiophenols under visible light was developed. In the photocatalytic system, without any metal, the reaction successfully realizes high atomic economy and wide substrate application range using cheap and easily available air as oxidant, and provides a simpler method for the direct construction of C—S bond.

Key words: photocatalysis, C—S bond construction, dehydrogenation coupling, thioether

引用此文

陈幸, 周璇, 姬小趁, 黄华文. 空气氛围下可见光诱导的硫酚氧化脱氢偶联[J]. 有机化学, 2021, 41(12): 4704-4711.

Xing Chen, Xuan Zhou, Xiaochen Ji, Huawen Huang. Visible Light-Induced Aerobic Oxidative Dehydrogenative Coupling of Thiophenols[J]. Chinese Journal of Organic Chemistry, 2021, 41(12): 4704-4711.

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Entry	Photocatalyst	Additive	Solvent	Yield^a/%
1	Rose Bengal	TBAB	CH₃CN	15
2	Rose Bengal	TBAI	CH₃CN	50
3	Rose Bengal	NH₄I	CH₃CN	38
4	Rose Bengal	KI	CH₃CN	43
5	Rose Bengal	I₂	CH₃CN	87
6	Rose Bengal	NaI	CH₃CN	93, 78^b
7 ^c	Rose Bengal	NaI	CH₃CN	60
8	Ru(bpy)₃Cl₂•6H₂O	NaI	CH₃CN	45
9	Ir(ppy)₃	NaI	CH₃CN	32
10	Eosin Y	NaI	CH₃CN	26
11	Rose Bengal	NaI	CH₂Cl₂	80
12	Rose Bengal	NaI	Acetone	81
13	Rose Bengal	NaI	DCE	78
14^d	Rose Bengal	NaI	CH₃CN	37
15^e	Rose Bengal	NaI	CH₃CN	71
16	—	NaI	CH₃CN	nd
17	Rose Bengal	—	CH₃CN	5
18^f	Rose Bengal	NaI	CH₃CN	nd
19^g	Rose Bengal	NaI	CH₃CN	10

Entry	Photocatalyst	Additive	Solvent	Yield^a/%
1	Rose Bengal	TBAB	CH₃CN	15
2	Rose Bengal	TBAI	CH₃CN	50
3	Rose Bengal	NH₄I	CH₃CN	38
4	Rose Bengal	KI	CH₃CN	43
5	Rose Bengal	I₂	CH₃CN	87
6	Rose Bengal	NaI	CH₃CN	93, 78^b
7 ^c	Rose Bengal	NaI	CH₃CN	60
8	Ru(bpy)₃Cl₂•6H₂O	NaI	CH₃CN	45
9	Ir(ppy)₃	NaI	CH₃CN	32
10	Eosin Y	NaI	CH₃CN	26
11	Rose Bengal	NaI	CH₂Cl₂	80
12	Rose Bengal	NaI	Acetone	81
13	Rose Bengal	NaI	DCE	78
14^d	Rose Bengal	NaI	CH₃CN	37
15^e	Rose Bengal	NaI	CH₃CN	71
16	—	NaI	CH₃CN	nd
17	Rose Bengal	—	CH₃CN	5
18^f	Rose Bengal	NaI	CH₃CN	nd
19^g	Rose Bengal	NaI	CH₃CN	10