Metal-Free Photocatalytic Hydrosilylation of Olefins in the Presence of Photoinitiator

A convenient metal-free photocatalytic hydrosilylation of variety of linear and cyclic alkenes have been investigated. It was found that the free radical type photoinitiator Irgacure 2959 had a better effect...

Experimental and Theoretical Investigations into the Mechanisms of Haliranium Ion π-Ligand Exchange Reactions with Cyclic Alkenes in the Gas Phase

Haliranium ions are intermediates often involved in complex cyclisations, where their structure allows for control over stereospecific outcomes. Extending previous studies into their structure and reactivity in the gas phase,...

Palladium-Catalyzed Anti-Markovnikov Oxidation of Aromatic and Aliphatic Alkenes to Terminal Acetals and Aldehydes

Catalytic anti-Markovnikov (AM) oxidation of terminal alkenes can provide terminally oxyfunctionalized organic compounds. This short review mainly summarizes our recent progress on the Pd-catalyzed AM oxidations of aromatic and aliphatic terminal alkenes to give terminal acetals (oxidative acetalization) and aldehydes (Wacker-type oxidation), along with related reports. These reactions demonstrate the efficacy of the PdCl2(MeCN)2/CuCl/electron-deficient cyclic alkenes/O2 catalytic system. Notably, electron-deficient cyclic alkenes such as p-benzoquinones (BQs) and maleimides are key additives that facilitate nucleophilic attack of oxygen nucleophiles on coordinated terminal alkenes and enhance the AM selectivity. BQs also function to oxidize Pd(0) depending on the reaction conditions. Several other factors that improve the AM selectivity, such as the steric demand of the nucleo­philes, slow substrate addition, and halogen-directing groups, are also discussed.1 Introduction2 Anti-Markovnikov Oxidation of Aromatic Alkenes to Terminal Acetals­3 Anti-Markovnikov Oxidation of Aromatic Alkenes to Aldehydes4 Anti-Markovnikov Oxidation of Aliphatic Alkenes to Terminal Acetals­5 Anti-Markovnikov Oxidation of Aliphatic Alkenes to Aldehydes6 Conclusion