Preparation of enantioenriched helical- and axial-chiral molecules by dynamic asymmetric induction.

Dynamic asymmetric induction (DYASIN) of racemic dynamic chiral heterohelicenes afforded their highly enantioenriched forms (up to 96% ep) in quantitative yields. These heterohelicenes were readily converted into semi-static axial-chiral 1,1'-binaphthyl derivatives in a stereospecific manner.

Development of a safely handleable synthetic equivalent of cyanonitrile oxide by 1,3-dipolar cycloaddition of nitroacetonitrile.

Dianionic cyano-aci-nitroacetate affords 3-cyanoisoxazol(in)es upon heating with a range of dipolarophiles in the presence of hydrochloric acid. In this reaction, nitroacetonitrile is formed as an intermediate active species, which serves as a synthetic equivalent of cyanonitrile oxide that can participate in a 1,3-dipolar cycloaddition reaction.