Metal-Free, Photo-Catalyzed Oxidation of Benzylic C—H Bonds to Access Carbonyl Functionality

doi:10.6023/cjoc202406015

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (5): 1755-1762.DOI: 10.6023/cjoc202406015 Previous Articles Next Articles

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无金属、光催化氧化苄基C—H键以获得羰基官能团

陈雨佳^a, 刘志林^a, 陈凯^a^,^*(), 向皞月^a^,^b^,^*(), 阳华^a^,^*()

^a 中南大学化学化工学院长沙 410083
^b 河南师范大学化学化工学院河南新乡 453007

收稿日期:2024-06-12 修回日期:2024-08-08 发布日期:2024-09-26
基金资助:
国家自然科学基金(22078370); 国家自然科学基金(22078369); 国家自然科学基金(22003077); 国家自然科学基金基础科学中心项目(72088101); 湖南省自然科学基金(2022JJ20055); 湖南省自然科学基金(2020JJ4682)

Metal-Free, Photo-Catalyzed Oxidation of Benzylic C—H Bonds to Access Carbonyl Functionality

Yu-Jia Chen^a, Zhi-Lin Liu^a, Kai Chen^a^,^*(), Hao-Yue Xiang^a^,^b^,^*(), Hua Yang^a^,^*()

^a College of Chemistry and Chemical Engineering, Central South University, Changsha 410083
^b College of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007

Received:2024-06-12 Revised:2024-08-08 Published:2024-09-26
Contact: * E-mail: kaichen@csu.edu.cn; hyangchem@csu.edu.cn; xianghaoyue@csu.edu.cn
Supported by:
National Natural Science Foundation of China(22078370); National Natural Science Foundation of China(22078369); National Natural Science Foundation of China(22003077); Basic Science Center Project for National Natural Science Foundation of China(72088101); Natural Science Foundation of Hunan Province(2022JJ20055); Natural Science Foundation of Hunan Province(2020JJ4682)

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Abstract

A general metal-free photochemcial oxidation of benzylic C—H bonds has been successfully accomplished via a hydrogen atom transfer (HAT) process. A range of high value-added aromatic ketones were facilely synthesized with high chemoselectivity under mild conditions. Moreover, the mild conditions by using air as the oxidant render the developed protocol more ecofriendly and environmentally sustainable.

Key words: photocatalysis, hydrogen atom transfer (HAT), benzyl position, oxidation

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Yu-Jia Chen, Zhi-Lin Liu, Kai Chen, Hao-Yue Xiang, Hua Yang. Metal-Free, Photo-Catalyzed Oxidation of Benzylic C—H Bonds to Access Carbonyl Functionality[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1755-1762.

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References 10

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Entry	Solvent	PC	Yield/%
Entry	Solvent	PC	2a		2a'
1	1,4-Dioxane (0.2 mol/L)	PC I	36		12
2	1,4-Dioxane (0.2 mol/L)	PC II	<10		0
3	1,4-Dioxane (0.2 mol/L)	PC III	<10		0
4	1,4-Dioxane (0.2 mol/L)	PC IV	<10		0
5	DMA (0.2 mol/L)	PC I	30		0
6	CH₃CN (0.2 mol/L)	PC I	30		30
7	THF (0.2 mol/L)	PC I	Trace		Trace
8	DCE (0.2 mol/L)	PC I	Complex		—
9	DMSO (0.2 mol/L)	PC I	Trace	Trace
10	1,4-Dioxane (0.1 mol/L)	PC I	61	0
11^c	1,4-Dioxane (0.1 mol/L)	PC I	90	0
12	1,4-Dioxane (0.1 mol/L)	—	0	0
13^d	1,4-Dioxane (0.1 mol/L)	PC I	0	0

Entry	Solvent	PC	Yield/%
Entry	Solvent	PC	2a		2a'
1	1,4-Dioxane (0.2 mol/L)	PC I	36		12
2	1,4-Dioxane (0.2 mol/L)	PC II	<10		0
3	1,4-Dioxane (0.2 mol/L)	PC III	<10		0
4	1,4-Dioxane (0.2 mol/L)	PC IV	<10		0
5	DMA (0.2 mol/L)	PC I	30		0
6	CH₃CN (0.2 mol/L)	PC I	30		30
7	THF (0.2 mol/L)	PC I	Trace		Trace
8	DCE (0.2 mol/L)	PC I	Complex		—
9	DMSO (0.2 mol/L)	PC I	Trace	Trace
10	1,4-Dioxane (0.1 mol/L)	PC I	61	0
11^c	1,4-Dioxane (0.1 mol/L)	PC I	90	0
12	1,4-Dioxane (0.1 mol/L)	—	0	0
13^d	1,4-Dioxane (0.1 mol/L)	PC I	0	0

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无金属、光催化氧化苄基C—H键以获得羰基官能团

Metal-Free, Photo-Catalyzed Oxidation of Benzylic C—H Bonds to Access Carbonyl Functionality

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