Photoinduced FeCl3‑catalyzed Cross-Dehydrogenative Alkylation of Benzoxazin-2-ones with Alkanes

doi:10.6023/A24100329

Acta Chimica Sinica ›› 2024, Vol. 82 ›› Issue (11): 1109-1113.DOI: 10.6023/A24100329 Previous Articles Next Articles

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可见光诱导氯化铁催化苯并噁嗪-2-酮与烷烃的脱氢偶联烷基化反应

辛翠^a, 蒋俊^c^,^d, 邓紫微^a^,^*(), 欧丽娟^b^,^*(), 何卫民^c^,^*()

a 湖南警察学院食药环及毒品检验技术湖南省普通高等学校重点实验室长沙 410138
b 湖南工学院材料科学与工程学院衡阳 421002
c 南华大学化学化工学院衡阳 421001
d 南京林业大学林木生物质低碳高效利用国家工程研究中心南京 210037

投稿日期:2024-10-29 发布日期:2024-11-19
基金资助:
湖南省教育厅科学研究项目(22B0944)

Photoinduced FeCl₃‑catalyzed Cross-Dehydrogenative Alkylation of Benzoxazin-2-ones with Alkanes

Cui Xin^a, Jun Jiang^c^,^d, Zi-Wei Deng^a(), Li-Juan Ou^b(), Wei-Min He^c()

a Key Laboratory of Food & Environment & Drug Monitoring and Testing of Universities in Hunan Province, Hunan Police Academy, Changsha 410138, China
b School of Materials Science and Engineering, Hunan Institute of Technology, Hengyang 421002, China
c School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China
d National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass, Nanjing Forestry University, Nanjing 210037, China

Received:2024-10-29 Published:2024-11-19
Contact: ^*E-mail: 305455334@qq.com; oulijuanann@163.com; weiminhe@usc.edu.cn
About author:
^†These authors contributed equally to this work.
Supported by:
Scientific Research Fund of Hunan Provincial Education Department(22B0944)

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Abstract

Homogeneous visible-light photoredox catalysis has emerged as a powerful tool in modern organic synthesis, which utilizes inexhaustible light to facilitate carbon-carbon and carbon-heteroatom bond formation under eco-friendly and mild conditions. Due to the incapablity of most organic compounds to absorb visible light, homogeneous photocatalysts such as precious metals (rhodium and iridium-complexes) and elaborate organic dyes were often employed through their visible light-driven electron/energy transfer to sensitize organic molecules in photoredox catalysis. However, these photocatalysts are not conducive to large-scale production due to the relatively high cost. Iron is an ideal candidate for economical and eco-friendly catalysis because of its abundant availability and nontoxicity. Recently, iron-photocatalyzed bond formation reactions via ligand-to-metal charge transfer (LMCT) have attracted huge attention. Functionalized benzoxazin-2-ones are important N-heterocycles found in many natural products, bioactive molecules and pharmaceuticals. Among these benzoxazin-2-one derivatives, alkylated benzoxazin-2-ones have received significant attention due to their valuable biological and pharmacological activities. From a synthetic point of view, the direct C—H alkylation of benzoxazin-2-ones represents one of the most straightforward and efficient methods for producing alkylated benzoxazin-2-ones due to its high atom and step economy. Alkanes are low cost and abundant feedstock materials, which have been widely used as the alkylation reagents in organic synthesis. In the present work, we report the development of iron-catalyzed C—H alkylation of benzoxazin-2-ones with alkanes via photoinduced LMCT. With FeCl₃ as the photocatalyst, ambient air as the oxidant, tetrabutylammonium chloride as the promoter, a series of 3-alkylbenzoxazin-2-ones were efficiently synthesized under mild and eco-friendly conditions. The chlorine radical generated in situ serves as a hydrogen atom-transfer reagent. In addition, the present reaction can be smoothly scaled-up to gram level, which indicates it could be applied in industrial synthesis of pharmaceuticals.

Key words: photocatalysis, alkane, benzoxazin-2-ones, alkylation, ligand-to-metal charge transfer

Cite this article

Cui Xin, Jun Jiang, Zi-Wei Deng, Li-Juan Ou, Wei-Min He. Photoinduced FeCl₃‑catalyzed Cross-Dehydrogenative Alkylation of Benzoxazin-2-ones with Alkanes[J]. Acta Chimica Sinica, 2024, 82(11): 1109-1113.

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Fig. & Tab. 7

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Entry		Variations from the standard condition	Yield^b/%
1		None	87
2		FeCl₂, CeCl₃ or CuCl₂ was used	56, 23, 12
3		Fe(acac)₃, Fe(NO₃)₃ or Fe₂(SO₄)₃ was used	14, 19, 71
4		TBABr or LiCl was used	51, 68
5		DCM, THF, DMSO or DMF was used	all trace
6		455 nm LED or 520 nm LED was used	15, 21
7		455 nm LED (5 W) was used	52
8		O₂ was used	84
9	N₂ was used		N.R.
10	Without catalyst, TBACl or light		N.R.

Entry		Variations from the standard condition	Yield^b/%
1		None	87
2		FeCl₂, CeCl₃ or CuCl₂ was used	56, 23, 12
3		Fe(acac)₃, Fe(NO₃)₃ or Fe₂(SO₄)₃ was used	14, 19, 71
4		TBABr or LiCl was used	51, 68
5		DCM, THF, DMSO or DMF was used	all trace
6		455 nm LED or 520 nm LED was used	15, 21
7		455 nm LED (5 W) was used	52
8		O₂ was used	84
9	N₂ was used		N.R.
10	Without catalyst, TBACl or light		N.R.

可见光诱导氯化铁催化苯并噁嗪-2-酮与烷烃的脱氢偶联烷基化反应

Photoinduced FeCl₃‑catalyzed Cross-Dehydrogenative Alkylation of Benzoxazin-2-ones with Alkanes

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