Palladium‐Catalyzed Stagewise Strain‐Release‐Driven C−C Activation of Bicyclo[1.1.1]pentanyl Alcohols. (11th April 2022)

• Record Type: Journal Article
• Authors: Yu, Songjie; Ai, Yinan; Hu, Lingfei; Lu, Gang; Duan, Chunying; Ma, Yue
• Is Part Of: Angewandte Chemie. Volume 134:Number 24(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-04-11
• Subjects: C−C Activation -- Cyclobutanones -- Palladium Catalysis -- Polycyclic Alcohols -- Strain Release; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202200052
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A palladium‐catalyzed chemoselective coupling of readily available bicyclo[1.1.1]pentanyl alcohols (BCP−OH) with various halides is reported, which offers expedient approaches to a wide range of cyclobutanone and β, γ‐enone skeletons via single or double C−C activation. The chemistry shows a broad substrate scope in terms of both the range of BCP−OH and halides including a series of natural product derivatives. Moreover, dependency of reaction chemodivergence on base additive has been investigated through experimental and density functional theory (DFT) studies, which is expected to significantly enrich the reaction modes and increase the synthetic potential of BCP−OH in preparing more complex molecules. Abstract : The use of strained bicyclo[1.1.1]pentanyl alcohols (BCP−OH) for the synthesis of a library of cyclobutanone and β, γ‐enone scaffolds through palladium‐catalyzed chemoselective C−C activation is described. Both experimental and DFT studies provided insights into the crucial stabilizing effect of base additives on the palladium‐carbon intermediates.