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. 2019 Jan 4;21(1):325-329.
doi: 10.1021/acs.orglett.8b03849. Epub 2018 Dec 21.

Photoinitiated Three-Component α-Perfluoroalkyl-β-heteroarylation of Unactivated Alkenes via Electron Catalysis

Danqing Zheng  1 , Armido Studer  1
Affiliations

Photoinitiated Three-Component α-Perfluoroalkyl-β-heteroarylation of Unactivated Alkenes via Electron Catalysis

Danqing Zheng et al. Org Lett. .

Abstract

A visible-light-initiated α-perfluoroalkyl-β-heteroarylation of various alkenes with perfluoroalkyl iodides and quinoxalin-2(1 H)-ones is presented. This three-component radical cascade reaction allows an efficient synthesis of a range of perfluoroalkyl containing quinoxalin-2(1 H)-one derivatives in moderate to excellent yields under mild conditions. Reactions proceed via acidic aminyl radicals that are readily deprotonated to give the corresponding radical anions able to sustain the radical chain as single electron transfer reducing reagents. Hence, the overall cascade classifies as an electron-catalyzed process.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Different Strategies for Radical Addition to a C=N Bond
Scheme 2
Scheme 2. Difunctionalization of Various Alkenes,
Reaction conditions: 1a (0.2 mmol), 2 (0.5 mmol, 2.5 equiv), 3a (0.4 mmol, 2.0 equiv), DBU (0.6 mmol), NMP (0.5 mL), 5 W blue LED, rt, Ar, 16 h. Isolated yield based on 1a.
Scheme 3
Scheme 3. Varying the Radical Acceptor and the Perfluoroalkyl Iodides,
Reaction conditions: 1 (0.2 mmol), 2d (0.5 mmol, 2.5 equiv), 3 (0.4 mmol, 2.0 equiv), DBU (0.6 mmol), NMP (0.5 mL), 10 W blue LED, rt, Ar, 16 h. Isolated yield based on 1.
Scheme 4
Scheme 4. Radical Clock Experiments and Proposed Mechanism
Scheme 5
Scheme 5. Follow-up Chemistry
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