Organocatalyzed Intramolecular Michael Addition of Morita–Baylis–Hillman Adducts of β‐Arylnitroethylenes: An Entry to 3‐Aryl‐4‐nitrocyclohexanones

Abstract

The synthesis of 3‐aryl‐4‐nitrocyclohexanones has been achieved from the Morita–Baylis–Hillman adducts of β‐arylnitroethylenes. The strategy involves proline‐catalyzed diastereoselective intramolecular Michael addition to obtain 3,4‐trans‐disubstituted cyclohexanones. This method provides a facile access to (±)‐epibatidine analogues.

An Asymmetric Intramolecular Rauhut-Currier Reaction Initiated by Chiral Selenolate-BINOL Complexes

“…With promising results obtained under achiral conditions, we decided to move to the asymmetric version of the IRC reaction. In search of chiral additives, we first analyze the role of chiral amines: (1R,2R)-1,2-diphenylethane-1,2-diamine (6) [21], L-proline (7) [22], (R)-2-(diphenylhydroxymethyl)pyrrolidine ( 8), (R)-BINAM ( 9) and other compounds including (S)-t-BuBOX (10), (R)-PhBOX (11), (R)-BnBOX (12), (S,S)-Trost catalyst ( 13) and (S)-BINOL (Scheme 3). The main reaction conditions assume the addition of water to a selenolate generated in situ, followed by equimolar amount of substrate, and t-BuOK.…”