Enantioselective Synthesis of [<i>b</i>]‐Annulated Azepane Scaffolds

Cyclopenta-, benzo-, and cyclohepta[b]-annulated azepane scaffolds were prepared in two steps from optically active cyclic α-allyl-β-oxoesters. The first step was ruthenium-catalyzed olefin cross metathesis with acrylonitrile. second palladium-catalyzed dihydrogenation which consists of three consecutive processes: hydrogenation the C−C double C−N triple bonds followed by reductive amination via iminium ion formed situ primary amino function endocyclic carbonyl group. This last gave, stereoselectively, annulated azepanes relative trans-configuration. ester group define points for further diversification scaffolds. trifluoroacetyl derivatives allowed to establish enantiopurity products be 97–98 % ee GLC on a chiral phase. trans-configurations one case also absolute (R,R)-configuration established X-ray crystallography.