Concise Unified Access to (-)-8-Deoxy-13-dehydroserratinine, (+)-Fawcettimine, (+)-Fawcettidine, and (-)-8-Deoxyserratinine Using a Direct Intramolecular Reductive Coupling.

A short, scalable, and collective total synthesis of four fawcettimine-type Lycopodium alkaloids in eight or nine steps is disclosed. A dense multi-small-ring spiro-α-aminocyclopentanone successfully served as the key intermediate, which was directly accessed by a LiDBB-mediated intramolecular reductive coupling of the aliphatic imine and an ester-carbonyl. Compared to those that employ classical Heathcock intermediate(s) containing a nine-membered ring, the new strategy shows the significant improvement of the synthetic step and redox economies as well as excellent stereochemical control.