A trienamine-mediated asymmetric Diels− Alder reaction using a 5-nitro-2,3-dihydro-4-pyridone derivative as a dienophile in the presence of a secondary amine organocatalyst derived from cis-hydroxyproline was discovered. The reaction provides optically active octahydroquinolines through an endo-selective [4 + 2] cyclization pathway. The following stereoselective denitration, isomerization, and/ or hydrogenation generated divergent stereoisomers of decahydroquinolines, which are useful synthons for the total synthesis of Lycopodium alkaloids. Letter pubs.acs.org/OrgLett

The first asymmetric total synthesis of the Lycopodium alkaloid senepodine F, which contains a decahydroquinoline ring (AB-ring) and a quinolizidine ring (CD-ring) connected by a methylene tether, has been achieved. The key steps of this synthesis include an organocatalytic asymmetric Diels−Alder reaction, a diastereoselective intramolecular aza-Michael reaction, and an intramolecular S N 2 cyclization to construct multisubstituted nitrogen-containing heterocycles. In addition, our total synthesis led to the stereochemical reassignment on the decahydroquinoline ring of senepodine F.