Michael addition-based cyclization strategy in the total synthesis of Lycopodium alkaloids

Enantioselective Total Synthesis of (+)-Sieboldine A and Analogues Thereof

“…In 2020, the Tu group accomplished a 24-step total synthesis of (±)-sieboldine A via a previously reported intermediate 14 possessing an A/B/D tricyclic system and vicinal quaternary centers (Figure c) . Herein, we report our recently accomplished 11-step enantioselective total synthesis of (+)-sieboldine A based on our achievements in the continuous study of the total synthesis of Lycopodium alkaloids (Figure d) as well as its expansion to the preparation and biological evaluation of artificial full-skeleton analogues of (+)-sieboldine A.…”

Machine learning and semi-empirical calculations: a synergistic approach to rapid, accurate, and mechanism-based reaction barrier prediction

“…Michael additions are one of the most efficient and prevalent methods for formation of C-C bonds in organic and biosynthesis, 72 nding important applications in asymmetric catalysis 5,[73][74][75] and several natural product syntheses. 72,[76][77][78][79] Among the many classes of these versatile reactions, the nitro-Michael addition is one of the most useful; 80-84 insertion of the nitro group into the organic framework via Michael addition enables a variety of synthetically important stereoselective reactions, 85 and the resulting nitro compounds can be the precursor for an assortment of highly useful chemical functionalities, including pyrrolidines, lactones, aminocarbonyls, and aminoalkanes. 86…”

Unified Total Synthesis of Tetracyclic Diquinane Lycopodium Alkaloids (+)-Paniculatine, (−)-Magellanine, and (+)-Magellaninone

“…Very recently, the Qiu group reported a concise total synthesis of (+)-paniculatine employing Hosomi-Sakurai allylation and intramolecular Michael addition of enolate to unsaturated amide . Herein, we wish to report a new addition to the unified syntheses of (+)-paniculatine, (−)-magellanine, and (+)-magellaninone starting from commercially available (5 R )-methylcyclohex-2-en-1-one ( 13 ) on the basis of our continuous study on total synthesis of Lycopodium alkaloids …”