A stereo-controlled access to functionalized macrolactams via an aza-Claisen rearrangement

초록

A novel and stereo-controlled method for the preparation of functionalized macrolactams was developed. The process involves stereoselective enol ether formation, followed by an azacyclic ring expansion via an aza-Claisen rearrangement. Herewith, we describe a systematic investigation of an aza-Claisen rearrangement- induced ring expansion of azacycles prepared by appending E/Z-enol ethers to the medium- sized lactams as well as the stereochemical outcome. In addition, the strategy was successfully applied to the total synthesis of fluvirucinine A(1) and 3-epi-fluvirucinine A(1). This method offers an attractive alternative to the intramolecular amide-aldol reaction for the elaboration of beta-alkoxy-alpha-substituted motifs.

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