Catalytic Ammonia Oxidation to Dinitrogen by a Nickel Complex

We report a nickel complex for catalytic oxidation of ammonia to dinitrogen under ambient conditions. Using the aryloxyl radical 2,4,6-tri-tert-butylphenoxyl (^tBu₃ArO⋅) as a H atom acceptor to cleave the N−H bond of a coordinated NH₃ ligand up to 56 equiv of N₂ per Ni center can be generated. Employing the N-oxyl radical 2,2,6,6-(tetramethylpiperidin-1-yl)oxyl (TEMPO⋅) as the H-atom acceptor, up to 15 equiv of N₂ per Ni center are formed. A bridging Ni-hydrazine product identified by isotopic nitrogen (¹⁵N) studies and supported by computational models indicates the N−N bond forming step occurs by bimetallic homocoupling of two paramagnetic [Ni]−NH₂ fragments. Ni-mediated hydrazine disproportionation to N₂ and NH₃ completes the catalytic cycle.     

Catalytic Fehling's Reaction: An Efficient Aerobic Oxidation of Aldehyde Catalyzed by Copper in Water

The first example of homogeneous copper‐catalyzed aerobic oxidation of aldehydes is reported. This method utilizes atmospheric oxygen as the sole oxidant, proceeds under extremely mild aqueous conditions, and covers a wide range of various functionalized aldehydes. Chromatography is generally not necessary for product purification.     

Site-Selective 1,2-Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis

A modular, site-selective 1,2-dicarbofunctionalization of vinyl boronates with organic halides through dual catalysis is described. This reaction proceeds under mild conditions and is characterized by excellent chemo- and regioselectivity. It thus represents a complementary new technique for preparing densely functionalized alkyl boron architectures from simple and accessible precursors.