What question did this study set out to answer?

To establish an efficient asymmetric synthetic route to 1,4-diketone derivatives featuring a challenging acyclic quaternary carbon stereocenter.

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March 25, 2026

Asymmetric Construction of 1,4-Diketone Derivatives Containing a Less Accessible Acyclic Quaternary Carbon Stereocenter via Michael Addition/Rearrangement Cascade

Key Points

To establish an efficient asymmetric synthetic route to 1,4-diketone derivatives featuring a challenging acyclic quaternary carbon stereocenter.
Utilized β,β-disubstituted enesulfinamides in conjugate addition to α-substituted nitroolefins.
Conducted a transposition of the sulfinylamino group.
Demonstrated the synthetic application through the formal synthesis of hamigeran B.
Successfully synthesized γ-imino ketone products with acyclic quaternary stereocenters.
Achieved high stereoselectivity in the conjugate addition process.
Provided a novel synthetic pathway not reliant on conventional C-C bond formation.

Abstract

The stereoselective conjugate addition of β,β-disubstituted enesulfinamides to α-substituted nitroolefins, followed by transposition of sulfinylamino group, provides an efficient asymmetric synthetic route to 1,4-diketone derivatives. The resulting γ-imino ketone products feature an acyclic quaternary stereocenter bearing two sterically and electronically similar substituents (e.g., methyl and ethyl groups), which are challenging to construct by the conventional synthetic protocols involving C-C bond formation. The synthetic application of the described protocol was demonstrated by the asymmetric formal synthesis of the natural product hamigeran B.

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