A new cyclopeptide, ophiorrhisine A (1), a new tetrahydroisoquinoline alkaloid, 7′,10-dide-O-methylcephaeline (2), two known β-carboline alkaloids, and four known tetrahydroisoquinoline alkaloids were isolated from Ophiorrhiza nutans (Rubiaceae). Compound 1 is a tetrapeptide possessing a 14-membered paracyclophane ring and a novel N,N,N-trimethyltyrosine residue in the side chain. The stereochemistry at the aryl–alkyl ether bond was different from that of other known 14-membered paracyclophanes. The structure of 2 was established by spectroscopic analysis and semisynthesis.

•An organocatalyzed asymmetric intramolecular aza-Michael addition of linear dienone was developed.•A new synthetic method of chiral 4-arylquinolizidinone was developed.•A novel and efficient total synthesis of lythraceous alkaloid, lasubine I, was accomplished.A new procedure for the asymmetric total synthesis of lythraceous alkaloids with a 4-arylquinolizidine skeleton was developed, which involved an organocatalyzed asymmetric intramolecular aza-Michael addition.

Sarpagine-related indole alkaloids (−)-hydroxygardnerine, (+)-hydroxygardnutine, (−)-gardnerine, (+)-(E)-16-epi-normacusine B, and (−)-koumine were divergently synthesized via a common intermediate possessing a piperidine ring with an exocyclic (E)-ethylidene side chain, which was constructed by a gold(I)-catalyzed 6-exo-dig cyclization strategy.

A new monoterpenoid indole alkaloid, kopsiyunnanine K, was isolated from Kopsia arborea. Its intriguing rearranged structure and absolute configuration, which were inferred from spectral data and a possible biosynthetic pathway, were determined on the basis of a 13-step asymmetric total synthesis.

A total synthesis of indole alkaloids, (±)-conolidine and (±)-apparicine, was accomplished via a gold(I)-catalyzed 6-exo-dig cyclization to construct a piperidine ring bearing an exocyclic (E)-ethylidene appendage.

Two new indole alkaloids having unusual skeletons were isolated from Yunnan Kopsia arborea. Kopsiyunnanine L has a novel 2,3,4,5-tetrahydro-1H-benzazepine skeleton rearranged from a Strychnos-type monoterpenoid indole alkaloid. Kopsiyunnanine M is a new type of bisindole alkaloid consisting of two Strychnos-type alkaloids.

The first asymmetric total synthesis of lycoposerramine-R, a Lycopodium alkaloid possessing a novel skeleton, was accomplished by a strategy featuring the stereoselective intramolecular aldol cyclization giving a cis-fused 5/6 bicyclic skeleton and a new method for the construction of the pyridone ring via the aza-Wittig reaction.

The total synthesis of (±)-lycoposerramine-R, a novel skeletal type of Lycopodium alkaloid, was accomplished via the Diels–Alder reaction, the stereoselective introduction of a methyl group, the regio- and stereoselective reductive amination, and the construction of a pyridone ring.

The first asymmetric total synthesis of (+)-flabellidine (2) and the shortest total synthesis of (−)-lycodine (3) were accomplished by a strategy featuring the one-pot construction of a tetracyclic lycodine skeleton from a linear precursor, which was inspired by the biosynthetic consideration of Lycopodium alkaloids.

A new pentacyclic indole alkaloid, kopsiyunnanine E, was isolated from Yunnan Kopsia arborea, and its structure, which was inferred from spectroscopic data, was established by a 16-step asymmetric total synthesis that proved that the natural alkaloid was not enantiomerically pure.

The first asymmetric total synthesis of lycoposerramine-R, a Lycopodium alkaloid possessing a novel skeleton, was accomplished by a strategy featuring the stereoselective intramolecular aldol cyclization giving a cis-fused 5/6 bicyclic skeleton and a new method for the construction of the pyridone ring via the aza-Wittig reaction.