三苯胺功能化有序介孔聚合物作为无金属光催化剂用于二硫化物合成

doi:10.6023/cjoc202308006

摘要/Abstract

有机二硫化物广泛存在于活性天然产物及药物分子中, 其在生物领域也有广泛的用途. 可见光促进的两分子硫醇间的氧化偶联是制备对称二硫化物绿色、高效和原子经济的方法之一, 但是此类反应所使用的光敏剂(金属配合物、有机小分子及无机半导体等)分别具有价格昂贵、光稳定性差、可见光吸收范围窄及易于被光腐蚀等问题. 因此, 开发价格便宜、稳定性好以及可回收的非金属光催化体系, 降低大规模合成的成本依然是该领域亟需解决的问题. 在此, 报道了一种三苯胺功能化的有序介孔聚合物(TPA-MPs)作为非金属多相光催化剂催化的硫醇/硫酚需氧氧化偶联反应. 该反应可在室温和空气氛围下高效合成多种二硫化物. TPA-MPs催化剂可重复使用6次以上而光催化活性无明显下降. 开发的多相光催化体系具有操作简便、反应条件温和和绿色环保等优点, 并且可以有效放大至克级规模, 为有机二硫化物的合成提供了新颖高效的工具.

关键词: 二硫化物, 光催化, 多相催化, 有序介孔聚合物

Disulfides are widely present in biologically active natural products and pharmaceuticals, and they also have a wide range of applications in life sciences. The visible light-induced oxidative coupling of two thiols is one of the most efficient, atomically economical and green method for the preparation of symmetric disulfides. However, the photocatalysts used in these reactions (metal complexes, small organic molecules and inorganic semiconductors, etc.) are facing problems such as expensive, poor photostability, limited visible-light absorption and photocorrosion. Thus, it is still highly desirable to develop efficient heterogeneous photocatalysts that are free of precious metals, inexpensive, stable and recyclable, to decrease the processing costs in large-scale synthesis. Herein, a triphenylamine-based ordered mesoporous polymers (TPA-MPs) as a metal-free photocatalyst for oxidation of thiols to disulfide was reported. This protocol provides a facile means for the rapid synthesis of a series of disulfides at room temperature under air atmosphere. TPA-MPs can be easily recovered with good retention of photocatalytic activity and reused at least six times. This approach is operationally simple, mild, green, and scalable, providing a facile and efficient access to disulfides.

Key words: disulfides, photoredox catalysis, heterogeneous catalysis, ordered mesoporous polymer

引用此文

刘继宇, 李圣玉, 陈款, 朱茵, 张元. 三苯胺功能化有序介孔聚合物作为无金属光催化剂用于二硫化物合成[J]. 有机化学, 2024, 44(2): 605-612.

Jiyu Liu, Shengyu Li, Kuan Chen, Yin Zhu, Yuan Zhang. Triphenylamine-Based Ordered Mesoporous Polymer as a Metal-Free Photocatalyst for Oxidation of Thiols to Disulfide[J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 605-612.

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图/表 5

Entry	Photocat.	Solvent	Yield^b/%
1	TPA-MPs	CH₃CN	95
2	TPA-MPs	CH₂Cl₂	90
3	TPA-MPs	MeOH	91
4	TPA-MPs	THF	89
5^c	TPA-MPs	CH₃CN	NR-40
6^d	TPA-MPs	CH₃CN	95
7	—	CH₃CN	Trace
8^e	TPA-MPs	CH₃CN	Trace
9^f	TPA-MPs	CH₃CN	Trace

表1. TPA-MPs催化的对甲氧基苯硫酚氧化偶联反应条件优化a

Table 1. Optimization of reaction conditions for the oxidative cross coupling of 4-methoxythiophenol catalyzed by TPA-MPs

表2. TPA-MPs 催化的硫酚和硫醇氧化偶联反应底物适用范围

Table 2. Substrate scope of oxidative cross coupling reaction of thiophenols and thiols catalyzed by TPA-MPs

图1. TPA-MPs循环能力测试

Figure 1. Evaluation of the recyclability of TPA-MPs

图2. 电子顺磁共振谱

Figure 2. EPR spectra

图式1. 建议反应机理

Scheme 1. Proposed reaction mechanism

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