Metrics & MoreArticle Recommendations * sı Supporting InformationABSTRACT: [RuCl 2 (p-cymene)] 2 /AgNO 3 -catalyzed intramolecular double hydrofunctionalization of internal alkynes having nitrogen and oxygen nucleophilic groups at appropriate positions provided a series of spirocyclic hemiaminal ether derivatives in good to excellent yields. The product spiro-hemiaminal ethers underwent Lewis acid-mediated chemoselective cleavage, and in situ-generated iminium/oxocarbenium ions could be trapped with nucleophiles to afford a range of nitrogen and oxygen heterocycles.

A Au-catalyzed tandem alkyne hydroamination/iminium ion formation/allylation reaction was developed for expedient access to pyrrolidine derivatives bearing a tetrasubstituted carbon stereocenter. The tandem reaction was successfully applied to a 12-step asymmetric synthesis of (−)-lepadiformine A, a marine cytotoxic tricyclic alkaloid.

Collective asymmetric total synthesis of marine tricyclic alkaloids, cylindricines A−H, and the proposed structures of cylindricines I and J was achieved in a concise manner from a single common spirocyclic pyrrolidine intermediate. A tandem chemoselective oxidation/intramolecular aza-Michael addition/epimerization was exploited to complete the tricyclic skeleton. This work provides a versatile synthetic entry to the cylindricine family of marine tricyclic alkaloids.

Collective asymmetric total synthesis of marine tricyclic alkaloids, cylindricines A–H, and the proposed structures of cylindricine I and J, was achieved in a concise manner from a single common spirocyclic pyrrolidine intermediate. A tandem chemoselective oxidation/intramolecular aza-Michael addition/epimerization was exploited to complete the tricyclic skeleton. This work provides a versatile synthetic entry to the cylindricine family of marine tricyclic alkaloids.