Metal‐Free Oxidative B−N Coupling of nido‐Carborane with N‐Heterocycles

A general method for the oxidative substitution of nido‐carborane (7,8‐C₂B₉H₁₂^?) with N‐heterocycles has been developed by using 2,3‐dichloro‐5,6‐dicyanobenzoquinone (DDQ) as an oxidant. This metal‐free B?N coupling strategy, in both inter‐ and intramolecular fashions, gave rise to a wide array of charge‐compensated, boron‐substituted nido‐carboranes in high yields (up to 97 %) with excellent functional‐group tolerance under mild reaction conditions. The reaction mechanism was investigated by density‐functional theory (DFT) calculations. A successive single‐electron transfer (SET), B?H hydrogen‐atom transfer (HAT), and nucleophilic attack pathway is proposed. This method provides a new approach to nitrogen‐containing carboranes with potential applications in medicine and materials.     

Cage‐like Fe,Na‐Germsesquioxanes: Structure,Magnetism, and Catalytic Activity

A series of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage‐like architectures have a unique type of molecular topology consisting of the hexairon oxo {Fe₆O₁₉} core surrounded in a triangular manner by three cyclic germoxanolates [PhGe(O)O]₅. This structural organization induces antiferromagnetic interactions between the Fe^III ions through the oxygen atoms. Evaluated for this first time in catalysis, these compounds showed a high catalytic activity in the oxidation of alkanes and the oxidative formation of benzamides from alcohols.     

Visible‐Light‐Promoted Iron‐Catalyzed C(sp2)–C(sp3) Kumada Cross‐Coupling in Flow

A continuous‐flow, visible‐light‐promoted method has been developed to overcome the limitations of iron‐catalyzed Kumada–Corriu cross‐coupling reactions. A variety of strongly electron rich aryl chlorides, previously hardly reactive, could be efficiently coupled with aliphatic Grignard reagents at room temperature in high yields and within a few minutes’ residence time, considerably enhancing the applicability of this iron‐catalyzed reaction. The robustness of this protocol was demonstrated on a multigram scale, thus providing the potential for future pharmaceutical application.