Photocatalytic Activation of C(sp3)—H Bonds to Form C—S Bonds Catalyzed by (Oxybis(4,1-phenylene))bis(phenylmethanone)

doi:10.6023/cjoc202210018

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (8): 2848-2854.DOI: 10.6023/cjoc202210018 Previous Articles Next Articles

光促进双(4-二苯甲酮)苯醚催化C(sp³)—H键活化构建C—S键

王灵娜^a, 刘晓庆^a, 林钢^a, 金泓颖^a, 焦民均^a, 刘雪粉^b, 罗书平^a^,^*()

a 浙江工业大学绿色化学合成技术国家重点实验室培育基地杭州 310014
b 杭州师范大学工学院杭州 310014

收稿日期:2022-10-18 修回日期:2023-01-09 发布日期:2023-04-21
基金资助:
国家自然科学基金(21376222); 浙江省自然科学基金(LY18B060011)

Photocatalytic Activation of C(sp³)—H Bonds to Form C—S Bonds Catalyzed by (Oxybis(4,1-phenylene))bis(phenylmethanone)

Lingna Wang^a, Xiaoqing Liu^a, Gang Lin^a, Hongying Jin^a, Minjun Jiao^a, Xuefen Liu^b, Shuping Luo^a()

a State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014
b Institute of Technology, Hangzhou Normal University, Hangzhou 310014

Received:2022-10-18 Revised:2023-01-09 Published:2023-04-21
Contact: *E-mail: luoshuping@zjut.edu.cn
Supported by:
The National Natural Science Foundation(21376222); The Natural Science Foundation of Zhejiang Province(LY18B060011)

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Abstract

The photocatalytic C(sp³)—H bond activated thioetherification of toluene and its derivatives was carried out with diaryl disulfide as sulfur source, and a series of thioether compounds with 45%~93% yields. Among them, the catalysis of new hydrogen atom transfer (HAT) photosensitizer of (oxybis(4,1-phenylene))bis(phenylmethanone) showed excellent light conversion efficiency, up to 9.3×10^－1 mmol•kW^－1•h^－1. Compared with benzophenone (1.7×10^－1 mmol•kW^－1•h^－1), the light conversion efficiency was 5 times higher. In addition, through the study of the reaction mechanism, the possible mechanism of the benzophenone analogs in the three-line excited state grab hydrogen atoms of toluene methyl to obtain benzyl radicals, then diphenyl sulfide is homolytically cleaved by LEDs irradiation to obtain sulfur radicals, and the bond formation reaction is carried out to obtain sulfide compounds. At the same time, another part of the sulfur radicals under alkali auxiliary through single electron oxidation of benzyl alcohol free radicals returns to the state of benzophenone, completing the photocatalytic cycle.

Key words: photocatalysis, organic photosensitizer, C(sp³)—H bond activation, thioetherification

Cite this article

Lingna Wang, Xiaoqing Liu, Gang Lin, Hongying Jin, Minjun Jiao, Xuefen Liu, Shuping Luo. Photocatalytic Activation of C(sp³)—H Bonds to Form C—S Bonds Catalyzed by (Oxybis(4,1-phenylene))bis(phenylmethanone)[J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2848-2854.

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References 23

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Entry	Photocatalyst (mol%)	Wavelength/ nm	Base	Yield^b/%
1^a	PC1 (5)	365	—	n.r.
2^c	PC1 (5)	—	Na₂CO₃	n.r.
3^d	— (0)	365	Na₂CO₃	n.r.
4^e	PC1 (5)	Natural light	Na₂CO₃	t.r.
5^f	PC1 (5)	365	Na₂CO₃	t.r.
6^g^,^h^,ⁱ	PC0 (5)	365	K₂HPO₄	17
7	PC1 (5)	365	K₂HPO₄	71
8	PC2 (5)	365	K₂HPO₄	54
9	PC3 (5)	365	K₂HPO₄	66
10	PC4 (5)	365	K₂HPO₄	49
11	PC1 (2)	365	K₂HPO₄	43
12	PC1 (10)	365	K₂HPO₄	59
13	PC1 (20)	365	K₂HPO₄	70
14	PC1 (30)	365	K₂HPO₄	68
15	PC1 (5)	365	Na₂CO₃	83
16	PC1 (5)	365	Et₃N	t.r.
17	PC1 (5)	365	2,6-Lutidine	12
18	PC1 (5)	395	Na₂CO₃	70
19	PC1 (5)	450	Na₂CO₃	t.r.
20^j^,^k	PC1 (5)	365	Na₂CO₃	t.r./75%

Entry	Photocatalyst (mol%)	Wavelength/ nm	Base	Yield^b/%
1^a	PC1 (5)	365	—	n.r.
2^c	PC1 (5)	—	Na₂CO₃	n.r.
3^d	— (0)	365	Na₂CO₃	n.r.
4^e	PC1 (5)	Natural light	Na₂CO₃	t.r.
5^f	PC1 (5)	365	Na₂CO₃	t.r.
6^g^,^h^,ⁱ	PC0 (5)	365	K₂HPO₄	17
7	PC1 (5)	365	K₂HPO₄	71
8	PC2 (5)	365	K₂HPO₄	54
9	PC3 (5)	365	K₂HPO₄	66
10	PC4 (5)	365	K₂HPO₄	49
11	PC1 (2)	365	K₂HPO₄	43
12	PC1 (10)	365	K₂HPO₄	59
13	PC1 (20)	365	K₂HPO₄	70
14	PC1 (30)	365	K₂HPO₄	68
15	PC1 (5)	365	Na₂CO₃	83
16	PC1 (5)	365	Et₃N	t.r.
17	PC1 (5)	365	2,6-Lutidine	12
18	PC1 (5)	395	Na₂CO₃	70
19	PC1 (5)	450	Na₂CO₃	t.r.
20^j^,^k	PC1 (5)	365	Na₂CO₃	t.r./75%

光促进双(4-二苯甲酮)苯醚催化C(sp³)—H键活化构建C—S键

Photocatalytic Activation of C(sp³)—H Bonds to Form C—S Bonds Catalyzed by (Oxybis(4,1-phenylene))bis(phenylmethanone)

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光促进双(4-二苯甲酮)苯醚催化C(sp3)—H键活化构建C—S键