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Herein, we describe a new catalysis platform, supramolecular carbon‐bonding catalysis, which exploits the highly directional weak interactions between carbon centers of catalysts and electron donors to drive chemical reactions. To demonstrate this catalysis approach, we discovered a class of cyclopropane derivatives incorporated with carbonyl, ester and cyano groups as catalysts which showed general catalysis capability in different types of benchmark reactions. Among these typical examples, a challenging tail‐to‐head terpene cyclization can be achieved by supramolecular carbon‐bonding catalysis. The co‐crystal structures of catalyst and electron donors, comparison experiments, and titrations support a catalysis mode of carbon‐bonding activation of Lewis basic reactants. [ABSTRACT FROM AUTHOR]

Herein, we describe a new catalysis platform, supramolecular carbon‐bonding catalysis, which exploits the highly directional weak interactions between carbon centers of catalysts and electron donors to drive chemical reactions. To demonstrate this catalysis approach, we discovered a class of cyclopropane derivatives incorporated with carbonyl, ester and cyano groups as catalysts which showed general catalysis capability in different types of benchmark reactions. Among these typical examples, a challenging tail‐to‐head terpene cyclization can be achieved by supramolecular carbon‐bonding catalysis. The co‐crystal structures of catalyst and electron donors, comparison experiments, and titrations support a catalysis mode of carbon‐bonding activation of Lewis basic reactants. [ABSTRACT FROM AUTHOR]

The selective oxidation of aniline to metastable and valuable azoxybenzene, azobenzene or nitrosobenzene has important practical significance in organic synthesis. However, uncontrollable selectivity and laborious synthesis of the expensive required catalysts severely hinders the uptake of these reactions in industrial settings. Herein, we have pioneered the discovery of Zr(OH)4 as an efficient heterogeneous catalyst capable of the selective oxidation of aniline, using either peroxide or O2 as oxidant, to selectively obtain various azoxybenzenes, symmetric/unsymmetric azobenzenes, as well as nitrosobenzenes, by simply regulating the reaction solvent, without the need for additives. Mechanistic experiments and DFT calculations demonstrate that the activation of H2O2 and O2 is primarily achieved by the bridging hydroxyl and terminal hydroxyl groups of Zr(OH)4, respectively. The present work provides an economical and environmentally friendly strategy for the selective oxidation of aniline in industrial applications. [ABSTRACT FROM AUTHOR]

The selective oxidation of aniline to metastable and valuable azoxybenzene, azobenzene or nitrosobenzene has important practical significance in organic synthesis. However, uncontrollable selectivity and laborious synthesis of the expensive required catalysts severely hinders the uptake of these reactions in industrial settings. Herein, we have pioneered the discovery of Zr(OH)4 as an efficient heterogeneous catalyst capable of the selective oxidation of aniline, using either peroxide or O2 as oxidant, to selectively obtain various azoxybenzenes, symmetric/unsymmetric azobenzenes, as well as nitrosobenzenes, by simply regulating the reaction solvent, without the need for additives. Mechanistic experiments and DFT calculations demonstrate that the activation of H2O2 and O2 is primarily achieved by the bridging hydroxyl and terminal hydroxyl groups of Zr(OH)4, respectively. The present work provides an economical and environmentally friendly strategy for the selective oxidation of aniline in industrial applications. [ABSTRACT FROM AUTHOR]