Part 1: study toward the total synthesis of acutumine ; : Part 2: asymmetric intramolecular hydroamination catalyzed by group 3 metal complexes

TL;DRAbstract

Acutumine 1 is a tetracylic alkaloid isolated from Menispermum daurcum, which exhibits selective T-Cell cytotoxicity. It is potentially useful for specific therapy T-Cell related Leukemia and lymphoma. Acutumine is a highly functionalized tetracyclic natural product, containing a [4.3.3]-propellane core and a 5,5-spirocycle. The synthesis of the 5,5-spirocycle is prepared via enantioselective Pd II/IV catalyzed chloro-induced semi pinacol rearrangment. However, studies showed Pd catalyst functioned as Lewis acid to oxidant, PhI(OAc) 2 rather than forming a Pi-complex with the substrate as proposed. Fortunately, the preparation of the spirocycle can be accomplished from an asymmetric Pd II /Brønsted acid cocatalyzed semi pinacol rearrangement via direct allylic C-H activation. [4.3.3] propellane core was concisely synthesized in eight step sequences featuring a phosphoric Brønsted acid catalyzed aldol condensation and radical N-cyclization as the key transformations. Hydroamination, the

Chat with Paper

AI Agents for this Paper