No abstract

A method for catalytic asymmetric alkylation of conjugated dienyl amides has been developed and it allows efficient and high-yielding transformations of a wide range of polyconjugated amides into the corresponding chiral products. Smooth addition of organomagnesium reagents to relatively unreactive dienyl amides with excellent 1,6- and 1,4-selectivities, as well as enantioselectivites above 90 %, is achieved owing to the complementary action of the Lewis acid and a chiral copper-based catalyst.

We describe a general catalytic methodology for the enantioselective dearomative alkylation of pyridine derivatives with Grignard reagents, allowing direct access to nearly enantiopure chiral dihydro-4-pyridones with yields up to 98%. The methodology involves dearomatization of in situ-formed N -acylpyridinium salts, employing alkyl organomagnesium reagents as nucleophiles and a chiral copper (I) complex as the catalyst. Computational and mechanistic studies provide insights into the origin of the reactivity and enantioselectivity of the catalytic process.

A method for catalytic asymmetric alkylation of conjugated dienyl amides has been developed and it allows efficient and high‐yielding transformations of a wide range of polyconjugated amides into the corresponding chiral products. Smooth addition of organomagnesium reagents to relatively unreactive dienyl amides with excellent 1,6‐ and 1,4‐selectivities, as well as enantioselectivites above 90 %, is achieved owing to the complementary action of the Lewis acid and a chiral copper‐based catalyst.