Benzoazabicyclo[4.3.1] derivatives by intramolecular Michael addition of piperidinone enolates to enoates

Piperidinones with a 2-bromobenzyl substituent in the 5-position were subjected to a Heck coupling reaction with ethyl acrylate resulting in the highly functionalized cinnamates 9a-d. A subsequent deprotonation of the piperidinones using NaN(SiM3)2 in THF induced an intramolecular Michael addition of the enolate to the cinnamate part. In this way, a range of novel 2,6-methano-4H-4-benzazonines 10-13 were obtained. In each case, a separable mixture of endo/exo-diastereomers was obtained.

Graphical abstractA novel synthesis of 2,6-methano-4H-4-benzazonines is described.Download full-size image