Ph2O-Mediated CeO2-Photocatalyzed Semi-Heterogeneous Fluoroalkylation of 2-Isocyanobiaryls

doi:10.6023/A25060202

Abstract

The strategic incorporation of fluoroalkyl moieties into organic architectures, commonly referred to as fluoroalkylation, has emerged as a transformative methodology in synthetic chemistry over recent decades. By introducing the fluoroalkyl group, the altered chemical and physical properties could lead to biological and pharmacological benefits, such as greater lipophilicity, enhanced metabolic stability, and bioavailability. Among various fluoroalkylation agents, sodium fluoroalkylsulfinates have emerged as particularly promising reagents owing to their cost-effectiveness, commercial accessibility, and versatile utility in diverse synthetic methodologies. Phenanthridine is one of the most vital fused N-heterocycles frequently found in a range of natural products, synthetic pharmaceuticals and valuable materials. Among numerous phenanthridine derivatives, 6-fluoroalkylphenanthridines display a wide spectrum of interesting biological activities and physicochemical properties. The radical fluoroalkylation of 2-isocyanobiaryls has been considered as an efficient and atom-economic strategy for the rapid construction of 6-fluoroalkylphenanthridine compounds. Visible-light photocatalysis has become a highly versatile tool in green organic synthesis, which employs inexhaustible visible light energy to promote the organic transformations under very mild conditions. The redox-mediated intrinsic semiconductor photocatalysis, which fully utilized the photo-generated electrons and holes for the organic transformation process, leading to not only solving the inherent limitations of intrinsic semiconductor catalysis but also improving the catalytic efficiency of organic transformation. In the present work, we report the development of redox-mediated intrinsic semiconductor photocatalytic semi-heterogeneous fluoroalkylation of 2-isocyanobiaryls with sodium fluoroalkylsulfinates. With CeO₂ as the heterogeneous photocatalyst, diphenyl ether as the homogeneous redox mediator, dimethyl sulfoxide (DMSO) as the solvent, a series of 6-fluoroalkyl-phenanthridines were efficiently synthesized. The CeO₂ was easily recovered from the reaction mixture and reused several times, paving the way for larger-scale industrial applications of this type of photocatalytic fluoroalkylation reactions.

Key words: visible-light photocatalysis, semiconductor photocatalyst, redox mediator, 2-isocyanobiaryl, fluoroalkylation

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Qionghui Peng, Jia Peng, Yingli Cai, Zuli Wang, Rongnan Yi, Chao Shen, Weimin He. Ph₂O-Mediated CeO₂-Photocatalyzed Semi-Heterogeneous Fluoroalkylation of 2-Isocyanobiaryls[J]. Acta Chimica Sinica, 2025, 83(9): 1013-1017.

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References 22

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Entry	Varying from the standard conditions	Yield^b/%
1	None	73
2	g-C₃N₄, Fe₂O₃, BiVO₄ instead of CeO₂	36, 45, 32
3	CdO, MoO_2,ZnO instead of CeO₂	41, 34, 38
4	Without semiconductor photocatalyst	N.R.
5	NHPI, Cp₂Fe, Ph₃N instead of Ph₂O	41, 28, 31
6	Without redox catalyst	33
7	Purple LED instead of blue LED	39
8	Green LED instead of blue LED	N.R.
9	White LED instead of blue LED	N.R.
10	LED (12 W), LED (8 W) instead of LED (10 W)	72, 63
11	Acetone, EtOAc, DMF instead of DMSO	21, trace, 50
12	Without air or light	N.R.

Entry	Varying from the standard conditions	Yield^b/%
1	None	73
2	g-C₃N₄, Fe₂O₃, BiVO₄ instead of CeO₂	36, 45, 32
3	CdO, MoO_2,ZnO instead of CeO₂	41, 34, 38
4	Without semiconductor photocatalyst	N.R.
5	NHPI, Cp₂Fe, Ph₃N instead of Ph₂O	41, 28, 31
6	Without redox catalyst	33
7	Purple LED instead of blue LED	39
8	Green LED instead of blue LED	N.R.
9	White LED instead of blue LED	N.R.
10	LED (12 W), LED (8 W) instead of LED (10 W)	72, 63
11	Acetone, EtOAc, DMF instead of DMSO	21, trace, 50
12	Without air or light	N.R.

二苯醚介导氧化铈半多相光催化2-异腈基联苯氟烷基化反应

Ph₂O-Mediated CeO₂-Photocatalyzed Semi-Heterogeneous Fluoroalkylation of 2-Isocyanobiaryls

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