Radical‐Dearomative Generation of Cyclohexadienyl Pd(II) toward the 3D Transformation of Nonactivated Phenyl Rings

Autor: Qi Fan, Kai Jiang, Bo Liu, Huanfeng Jiang, Xiaohui Cao, Biaolin Yin
Jazyk: angličtina
Rok vydání: 2024
Předmět:
Zdroj: Advanced Science, Vol 11, Iss 9, Pp n/a-n/a (2024)
Druh dokumentu: article
ISSN: 2198-3844
DOI: 10.1002/advs.202307074
Popis: Abstract Traditional palladium‐catalyzed dearomatization of (hetero)arenes takes place via an ionic pathway and usually requires elevated temperatures to overcome the energy barrier of the dearomative insertion step. Herein, a combination of the radical and two‐electron pathways is disclosed, which enables room temperature dearomative 3D transformations of nonactivated phenyl rings with Pd(0) as the catalyst. Experimental results together with density functional theory (DFT) calculations indicate a versatile π‐allyl Pd(II) species, cyclohexadienyl Pd(II), possibly is involved in the dearomatization. This species is generated by combining the cyclohexadienyl radical and Pd(I). The cyclohexadienyl Pd(II) provides chemoselective (carboamination and trieneylation), regioselective (1,2‐carboamination), and diastereoselective (carbonyl‐group directed face selectivity) conversions.
Databáze: Directory of Open Access Journals
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