Citation: Yunqiang Li, Yongxian Huang, Sinuo Li, He Huang, Zhiwei Jiao. Elaborating azaaryl alkanes enabled by photoredox/palladium dual catalyzed dialkylation of azaaryl alkenes[J]. Chinese Chemical Letters, ;2025, 36(4): 110051. doi: 10.1016/j.cclet.2024.110051 shu

Elaborating azaaryl alkanes enabled by photoredox/palladium dual catalyzed dialkylation of azaaryl alkenes

MOE Laboratory of Bioinorganic and Synthetic Chemistry, GBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China

jiaozhw@mail.sysu.edu.cn

Received Date: 26 February 2024
Revised Date: 13 May 2024
Accepted Date: 24 May 2024
Available Online: 24 May 2024

Figures(7)

A general process for the construction of azaaryl alkanes was achieved by employing the photoredox/palladium dual catalysis under mild visible light irradiation. The palladium catalyst ligated with a diphosphamide ligand exhibited high effectiveness in facilitating the modular three-components transformation. Furthermore, the cascade transformation was not restricted to constructing tertiary carbon centers; it also encompassed the synthesis of more challenging quaternary carbon centers with sixteen representative azaarene-derived substrates as reactants. In addition, alkyl 1,4-dihydropyridines (DHP), alkyl BF₃K, and alkyl carboxylic acids were identified as precursors for alkyl radicals. Mechanistic investigations revealed the involvement of two different active benzylic nucleophiles in the cascade transformation. One is azabenzylic radical, which generate the terminal product through an “inner sphere” reductive elimination process. The other is azabenzylic anions, generated through visible light induced radical anion cross-over, leading to the formation of terminal products via an “outer sphere” reaction pathway. The efficiency of current modular transformation was also demonstarted by the concise of oliceridine, a prominent USFDA drug for pain management.
- Palladium catalysis,
- Azaarenes,
- Photocatalysis,
- Three-components reaction,
- Radical-anion crossover,
- Oliceridine
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