Study On Asymmetric Catalytic Reactions Based On Secondary And Tertiary Alcohols Catalyzed By Br(?)nsted Acid

Chiral phosphoric acid and chiral imidodiphosphoric acid catalysts,owing to their strong acidity,excellent ability to activate reactants and strong chiral control ability,are very important Br(?)nsted acids in asymmetric catalysis of small organic molecules and has become a hot spot of research in this field.In this paper,we studied the asymmetric catalytic reactions containing asymmetric cycloaddition reaction and direct substitution reaction involving some alcohols under these catalysts catalyzing.The asymmetric consecutive cycloaddition of 3-hydroxy-3-indolyl-oxide indole to(E)-1-styryl-2-naphthol was catalyzed by chiral imidodiphosphoric acid to prepare novel bisspirocompounds with five consecutive chiral centers.Through the optimization of the reaction conditions,36 reaction examples were expanded with up to 93%yield,>19:1 d.r.diastereoselectivity and 99%ee value.The asymmetric oxa Diels-Alder reaction of(E)-1-styryl-2-naphthol with in situ o-quinone metheides was successfully carried out by employing Br(?)nsted H₈-BINOL type imidodiphosphoric acid as catalyst.Enantio-riched triaryl chromane with three consecutive chiral centers were successfully synthesized by one-step reaction.We screened and optimized the reaction conditions,and finally synthesized the optically pure chromane with up to 93%yield,98%ee value and>19:1 d.r..Chiral phosphoric acid was empolyed as a catalyst to catalyze the asymmetric conjugate addition of indolin-7-ylmethanol and 3-styryl-indole and 2',7-Bis(indole)compounds with optical purity were prepared.This method has good applicability,with the yield as high as 99%and 88%ee value,expanding 29 examples.It greatly enriched the kinds of biological bisindoles.