Triphenylamine-Based Ordered Mesoporous Polymer as a Metal-Free Photocatalyst for Oxidation of Thiols to Disulfide

doi:10.6023/cjoc202308006

Abstract

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

Cite this article

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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Fig. & Tab. 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

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

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

Figure 1. Evaluation of the recyclability of TPA-MPs

Figure 2. EPR spectra

Scheme 1. Proposed reaction mechanism

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