What question did this study set out to answer?

The study aims to develop a synthetic method for 3-RX-dihydropyridin-2(1H)-ones using Rh(II) catalysis.

February 8, 2026The Journal of Organic Chemistry0 citations

Diverse Functionalization of 2-Pyridinones via Rh(II)-Catalyzed X–H Insertion and Subsequent Transformations Using Heterocyclic Diazo Reagents

ELEkaterina Levashova MAMaria Adamchik ITIlya S. Tatarinov

Key Points

The study aims to develop a synthetic method for 3-RX-dihydropyridin-2(1H)-ones using Rh(II) catalysis.
Conducted Rh(II)-catalyzed X-H insertion with 3-diazo-3,6-dihydropyridin-2(1H)-ones.
Utilized diverse X-H substrates including N, O, and S.
Performed base-promoted epimerization for product formation.
Analyzed stereochemical outcomes using DFT calculations.
Achieved high yields of target products with significant functional group tolerance.
Demonstrated smooth Claisen rearrangement for 3-allyloxy-substituted dihydropyridin-2-ones.
Obtained higher diastereoselectivity in resulting polyfunctionalized compounds.

Abstract

Herein, we report a straightforward and diastereoselective synthetic approach to densely substituted 3-RX-dihydropyridin-2(1H)-ones. The method is based on the Rh(II)-catalyzed X-H insertion reaction of previously unreported 3-diazo-3,6-dihydropyridin-2(1H)-ones into a diverse range of X-H substrates (X = N, O, S), followed by base-promoted epimerization. The reaction exhibits broad functional group tolerance in both reaction partners and generally affords the target products in high yields. Furthermore, the resulting 3-allyloxy-substituted dihydropyridin-2-ones were shown to undergo a smooth 3,3-sigmatropic Claisen rearrangement, providing efficient access to polysubstituted 3-oxopiperidin-2-ones with high diastereoselectivity. The observed stereochemical outcome was further rationalized by DFT calculations.

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