The Atropisomer-Selective Ring Cleavage of Helically Distorted, Configuratively Unstable Biaryl Lactones with a Chiral Metallated N -Nucleophile - the Complete PM3 Mechanistic Course and its Video Presentation

摘要: The complete mechanistic sequence of the atropo-diastereoselective ring opening reaction configuratively unstable lactone-bridged biaryls with chiral 2R,5R-1-lithio-2,5-dimethylpyrrolidine was calculated using semiempirical PM3 method. It shown that stereochemically deciding key step is first attack nucleophile to carbon atom lactone moiety. diastereoselectivity this synthetically useful and mechanistically challenging biaryl synthesis found originate from a dynamic kinetic resolution axially chiral, but substrates. For further understanding complex stereochemical process, geometries resulting IRC-calculations have been visualized are presented as an Quicktime-movie.