Photoredox-Catalyzed Acylchlorination of α-CF3 Alkenes with Acyl Chloride and Application as Masked Access to ß-CF3-enones.

We disclose a photocatalytic strategy that simultaneously addresses the construction of trifluoromethylated quaternary carbon centers and the preparation of ß-CF3-enones through radical difunctionalization of α-CF3 alkenes with acyl chlorides. This method is characterized by its broad functional group compatibility, high efficiency, and atom economy. The versatility of this transformation is poised to broaden the applications of α-CF3 alkenes, providing new pathways for the rapid assembly of structurally diverse fluorinated compounds.

Endoplasmic Reticulum-Targeting Quinazolinone-Based Lipophilic Probe for Specific Photoinduced Ferroptosis and Its Induced Lipid Dynamic Regulation.

Lethal lipid peroxidation caused by reactive oxygen species occurs in different types of programmed cell death, especially in ferroptosis. Ferroptosis inducers, which serve as small-molecule probes, can provide insight into the mechanism of ferroptosis and facilitate drug discovery. The classical ferroptosis inducers indirectly lead to lipid peroxidation; thus, it is difficult to explore lipid regulation during the ferroptotic process. In this study, we designed two quinazolinone-based lipophilic probes BODIQPy-TPA and QPy-TPA, which proved to directly induce lipid peroxidation by light irradiation in vitro. The probe BODIQPy-TPA, which was mainly distributed in the endoplasmic reticulum (ER), specifically triggered ferroptosis in B16 and HepG2 cells upon light irradiation. As a comparison, the probe QPy-TPA, which was mainly distributed in lipid droplets (LDs), induced cell death by a nonferroptotic pathway. Further lipidomic analysis revealed that these two probes caused different patterns of lipid regulation and lipid peroxidation, suggesting that ferroptosis might activate distinct lipid regulation.

Visible-Light Photoredox-Catalyzed Divergent 1,2-Diacylation and Hydroacylation of Alkenes with Carboxylic Acid Anhydride.

A photoredox-catalyzed divergent 1,2-dicarbonylation and hydroacylation of alkenes with acid anhydride is presented. This approach offers a mild and efficient entry to 1,4-dicarbonyl compounds bearing all-carbon quaternary centers, exhibiting a broad substrate scope and high functional group compatibility. Hydrocarbonylaltion of alkenes can also be realized by simply introducing a proton source to the reaction system. Mechanism investigations support a radical addition/radical-polar crossover cascade.

Cu(ii)-mediated direct intramolecular cyclopropanation of distal olefinic acetate: access to cyclopropane-fused γ-lactones.

Cyclopropane-fused ring scaffolds represent one of the most appealing structural motifs in organic chemistry due to their wide presence in bioactive molecules and versatility in organic synthesis. These skeletons are typically prepared from olefinic diazo compounds via transition-metal catalysed intramolecular carbenoid insertion, which suffers from prefunctionalization of starting materials and limited substrate scope. Herein, we disclose a practical copper-mediated direct intramolecular cyclopropanation of distal olefinic acetate to synthesize cyclopropane-fused γ-lactones and lactams. This cascade reaction is postulated to proceed through a hydrogen atom transfer event induced radical cyclization and copper-mediated cyclopropanation sequence. The protocol features high atom- and step-economy, excellent diastereoselectivity, broad tolerance of functional groups, and operational simplicity.