This report describes a configuration-dependent [6 + 8 + 5] fused ring formation via a tandem cyclic N-acyliminium nucleophilic addition reaction. Cyclization of the acyclic precursor prepared on a solid phase using l-Ser and a racemic mixture of Fmoc- trans-2-aminocyclohexanecarboxylic acid predominantly yielded the cyclic diastereomer with the (1 R,2 R)-2-aminocyclohexane moiety rather than the tricyclic diastereomer from the (1 S,2 S)-enantiomer. In contrast, the model compound prepared with d-Ser predominantly cyclized with the (1 S,2 S)-2-aminocyclohexanecarboxylic acid substrate. The outcome of the cyclization was not influenced by the type of resin, the spacer, or the N-substituent. The analogous synthesis of the [6 + 7 + 5] fused ring system yielded inseparable diastereomers in a 1:0.6 ratio.