The robustness of iron catalysis enabling the oxidative coupling reactions of enamides with formamides is described. Routing from readily accessible feedstocks, the efficient approach is implemented to furnish a broad array of value-added N-acyl enamine amide derivatives, which serve as versatile precursors of biologically relevant N-heterocycles including pyrimidin-4-ones and 4-hydroxypyridin-2-ones. Preliminary mechanistic studies supported the notion that this direct carbamoylation reaction proceeded through an aminoacyl radical species.

Enantioselective desymmetrization of meso-epoxides by 2-mercaptobenzothiazoles was realized by using the pentacarboxycyclopentadiene-based chiral Brønsted acid in combination of N -isopropylaniline as amine additive to give up to 90.5:9.5 er of the ring opening products.

The enantioselective protonation of silyl enol ethers was realized in the presence of a pentacarboxycyclopenta-1,3-diene-based chiral Brønsted acid catalyst with water as an achiral proton source to give the corresponding α-aryl ketones in good yields and up to 75% ee.

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