Aerobic Oxidations of C₆₀^2– in the Presence of PhCN and PhCH₂CN: Oxygenation versus Dehydrogenation Reactions

Aerobic oxidations of dianionic C₆₀ were examined in PhCN and PhCH₂CN, where dioxygen was activated to O₂^•– via the single-electron transfer from C₆₀^2– and underwent oxygenation and dehydrogenation reactions, respectively. Addition of PhCH₂Br led to further benzylation for the oxygenated product but not for the dehydrogenated one, suggesting that the initial two negative charges were preserved for the intermediates of the oxygenation reaction but not for those of the dehydrogenation reaction

Reductive Benzylation of C₆₀ Imidazoline with a Bulky Addend

Reductive benzylation of C₆₀ imidazoline with a bulky addend affords two 1,2,3,16-adducts (<b>2</b> and <b>4</b>) and one 1,2,3,4-adduct (<b>3</b>). Experimental and computational results indicate that the sterically favored <b>2</b> is more stable than the electronically favored <b>3</b>. However, an opposite stability order is shown for the dianions of <b>2</b> and <b>3</b>

Preparation of a C₇₀ Bis-heterocyclic Derivative with High Chemio- and Regioselectivity

C₇₀ bis-heterocyclic derivative (<b>1</b>) bearing one oxazoline ring and one imidazoline ring with the 2 o’clock configuration is obtained with high chemio- and regioselectivity via the reaction of C₇₀ with hydroxide and benzonitrile quenched with I₂. Further study with benzylation experiment and theoretical calculations indicate that the oxazoline ring is the one first formed on the C₇₀ cage, while the imidazoline ring is the one formed after the addition of I₂ via a radical coupling reaction mechanism

Hydroxide-Initiated Conversion of Aromatic Nitriles to Imidazolines: Fullerenes vs TCNE

Transformation of aromatic nitriles to imidazolines has been achieved under basic conditions with the electron-deficient C₆₀ and C₇₀ fullerenes, but not with the electron-deficient olefin of tetracyanoethylene (TCNE). In situ UV–vis–NIR indicates that the ability of RC₆₀^– to undergo single-electron transfer (SET) to C₆₀ is crucial for the reaction