Syntheses and Application of Ar-BINMOLs with Axial and sp3 Central Chirality in Asymmetric Catalysis

摘要

Very recently,we reported a facile and practical methodology of synthesis of synthetically useful diarylmethanol-based 1,4-diols and enantiomerically pure BINOL-derived diols with axial and sp3 central chirality through neighboring lithium-promoted [1,2]-Wittig Rearrangement.In this asymmetric Wittig rearrangement,the chiral transfer process showed very broad substrate scope in terms of additional aromatic ethers with excellent enantioselectivities (＞99％ee) and yields (84-96％)[1],thus allowing access to a broad of range of chiral 1,1'-binaphthalene-2-α-arylmethanol-2'-ol (Ar-BINMOLs,KLX chiral ligands),that should be considered as an available and attractive chiral source to design and prepare privileged ligands or catalysts.Herein,we also reported the chiroptical properties,as well as the characterization of racemic and chiral Ar-BINMOLs by ESI-MS,NMR Spectroscopy,different scanning calorimetry,and X-ray diffractometry,and its applications in enantioselective Michael reaction of anthrone with trans-β-nitrostyrene and diethylzinc additions to aldehydes as chiral organocatalyst and ligand respectively.