On mixing (R SO ) CH (R =perfluoroalkyl), paraformaldehyde, and substituted pyridines, a three-component reaction proceeded smoothly to give unusual zwitterions bearing both pyridinium and stabilized carbanion moieties in good to excellent yields. Of these, 2-fluoropyridinium derivatives rapidly dissociated in acetonitrile to give equilibrium mixtures of the zwitterions and (R SO ) C=CH /2-fluoropyridine, as confirmed by detailed variable-temperature NMR studies. The dynamic behavior of such 2-fluoropyridinium compounds allows them to be used as shelf-stable, easy-to-handle sources of (R SO ) C=CH . With these reagents, strongly acidic carbon acids (R SO ) CHR were synthesized, which served as a new type of acid catalysts. Moreover, C-C bond-forming reactions with a ketene silyl acetal proceeded efficiently with Tf C=CH generated in situ.

Asymmetric catalytic activities of various organocatalysts bearing double hydrogen-bonding donor units showing different pK a values were examined for direct aldol reactions of cyclohexanone with aromatic aldehydes. Organocatalyst with motif exhibiting the highest acidity resulted in the corresponding aldol products with the highest enantioselectivity. A good correlation has been observed between the asymmetric catalytic activity for direct aldol reactions and acidities of double hydrogen-bonding donating units.

A shelf‐stable, easy‐to‐handle reagent for the in situ generation of the highly electrophilic alkene (RfSO2)2C=CH2 was developed. By using this reagent, a new type of superacidic molecule was successfully synthesized. The authors also found some synthetic reactions catalyzed by the alkene. Detailed NMR studies revealed a rapid decomposition rate (milliseconds order) of the reagent to generate (RfSO2)2C=CH2/2‐fluoropyridine. In this picture, the rapid formation of (RfSO2)2C=CH2 is represented by cracking open a raw egg. This egg is also a symbol for the birth of new chemistry. More information can be found in the Full Paper by H. Yanai, T. Matusmoto et al. on page 8203.