Baoling Wang

Amide-assisted radical strategy: metal-free direct fluorination of arenes in aqueous media

A metal- and initiator-free direct fluorination of arenes with the assistance of an amide group is developed. This reaction proceeded under simple aqueous conditions with good functional group tolerance and ortho–para selectivity, and is highly practical because it could be readily scaled up to a multigram-scale. At this stage, an exclusive mechanism could not be proposed, and several possibilities have been discussed. The possibility of the amide-assisted radical chain mechanism has been supported by experimental and computational investigations as well as a seminal work.

Silver-Catalyzed Radical Arylphosphorylation of Unactivated Alkenes: Synthesis of 3-Phosphonoalkyl Indolines

A silver-catalyzed phosphorylation/cyclization cascade of N-allyl anilines was developed, allowing direct access to 3-phosphonoalkyl indolines, which were previously obtainable only via tedious procedures under harsh/toxic conditions. The unactivated double bond serves as the radical acceptor, whereas H-phosphonates or -phosphine oxides act as the radical precursor. This protocol features simple operation, broad substrate scope, and great exo selectivity, and a gram-scale synthesis could be readily carried out.

Asymmetrically decorated POM framework formed by a chiral polyanion

Abstract Reactions of NaH2AsO4 with C-type polyanion precursor lead to a new compound, (NH4)15[As2Fe6Mo22O85AsO2(OH)2]·31.5H2O (1). Compound 1 was characterized by elemental analysis, infrared spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. Structural analysis reveals that AsO2(OH)2− asymmetrically decorated the POM framework, constituting the first inorganic anion asymmetrically decorating a POM. AC measurements of the frequency-dependent χ′′ below 5 K indicated a slow magnetization relaxation in 1, resembling typical single-molecule-magnet behavior. Photocatalytic experiments indicated that introduction of AsO2(OH)2− may offer new active sites and enhanced the overall photocatalytic activity compared with the C-type precursor.

Metal-free and selective cleavage of unstrained carbon–carbon single bonds: Synthesis of β-ketosulfones from β-chlorohydrins and sodium sulfinates

ABSTRACT A metal-free protocol for the selective cleavage of unstrained C–C single bonds was developed. Under the catalysis of KI and in the presence of NaHCO3, the readily available α-chloro-β-hydroxy ketones underwent bond breaking and sulfonylation smoothly to afford β-ketosulfones with high efficiency and broad substrate scope. Mechanism investigations, both experimental and theoretical, showed that a retro-aldol cleavage/nucleophilic substitution sequence might be involved. GRAPHICAL ABSTRACT