Enantioselective Total Synthesis of (+)-Stephadiamine through Bioinspired Aza-Benzilic Acid Type Rearrangement
Minami Odagi, Taisei Matoba, Keisuke Hosoya, Kazuo Nagasawa
Abstract
We report the first enantioselective total syntheses of the hasubanan alkaloid (-)-metaphanine and the norhasubanan alkaloid (+)-stephadiamine. Key features of these syntheses include diastereoselective oxidative phenolic coupling reaction and subsequent regioselective intramolecular aza-Michael reaction, which efficiently construct the hasubanan skeleton with the all-carbon quaternary stereogenic center at C13. Based on our hypothesis regarding the biosynthetic pathway of (+)-stephadiamine, we found that (-)-metaphanine is easily converted to (+)-stephadiamine via aza-benzilic acid type rearrangement reaction.
Topics & Concepts
ChemistryStereocenterEnantioselective synthesisRegioselectivityIntramolecular forceTotal synthesisStereochemistryQuaternary carbonAlkaloidStereoisomerismOrganic chemistryMoleculeCatalysisAlkaloids: synthesis and pharmacologyChemical synthesis and alkaloidsAdvanced Synthetic Organic Chemistry