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[reaction: see text] Design and synthesis of a novel family of furancarbothioamide-based palladacycles are reported herein. These palladacycles are thermally stable, not sensitive to air or moisture, and are applied effectively in the Heck reaction of aryl halides with terminal olefins and in the Suzuki reaction of aryl halides with arylboronic acids. These reactions were performed under aerobic conditions, leading to turnover numbers (TONs) up to 1 x 10(5).

Open the cage if you dare: The azahomoazafullerene 1 was prepared from a tert‐butylperoxy‐substituted azafullerene derivative C59NBr(OOtBu)4. Singlet oxygen added to 1 to form an open‐cage azafullerene 2 with a ketoimide moiety on the rim of the orifice. The MALDI‐TOF mass spectrum of the product of the hydrolysis of 1 showed a clear signal for the diazafullerene C58N2 (see structure 3).

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