Radical-Dearomative Generation of Cyclohexadienyl Pd(II) toward the 3D Transformation of Nonactivated Phenyl Rings
- PMID: 38102822
- PMCID: PMC10916580
- DOI: 10.1002/advs.202307074
Radical-Dearomative Generation of Cyclohexadienyl Pd(II) toward the 3D Transformation of Nonactivated Phenyl Rings
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.
Keywords: carboamination; cyclohexadienyl Pd(II); radical dearomatization; trieneylation.
© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.
Conflict of interest statement
The authors declare no conflict of interest.
Figures
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