Aromatic methyl ketones and cyclic asymmetric ketones underwent hydrophosphorylation with P-stereogenic H-P species in the presence of potassium carbonate to produce P,C-stereogenic tertiary α-hydroxyl phosphinates in excellent yields with up to 99 : 1 dr. The diastereoselectivity was induced by a reversible conversion of less stable stereomer of product to that of a more stable one via an equilibrium, which was confirmed by aldehyde/ketone exchanging reaction. Toward the exchange, aliphatic or aldehyde carbonyl were more active than aromatic or ketone carbonyls, respectively. The stability difference between the two diastereomers was controlled by the sizes of substituents linking to phosphorus or α-carbon.

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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).