The pot‐economical, highly enantioselective synthesis of axially chiral biaryls was developed by using one‐pot organocatalyst‐mediated domino and aromatization reactions as key steps. The axial information of the precursor, which also has central chirality, was completely inverted in the final biaryls. The inversion of the axial information occurred in the conversion of the central chirality to the axial chirality of an oxidative aromatization step.

At hree-pot synthetic method that featurest he use of an organocatalyst as the key step was developed for the preparation of biaryl atropisomers. Thef irst reaction is an asymmetricd omino Michael-Henry reactionc atalyzed by diphenylprolinol silyl ether to affordt he substituted nitrocyclohexanecarbaldehyde with four stereogenic centersa nd one defined configuration of as tereogenic axis with excellent enantioselectivity.R emovalo ft he central chirality from the dominop roducts afforded biaryl atropisomers having axial chirality with excellent enantioselectivity.Scheme1.Our hypothesis for the synthesis of an axially chiral molecule.[a] Prof.Scheme3.Transformationo f8a to 10 a.Scheme2.Transformationo f2a to 8a.Scheme4.Two-pottransformation from 2a to 8a.

No abstract

A new pot‐economical and highly enantioselective synthesis of axially chiral biaryls was developed. The protocol features a domino reaction mediated by an organocatalyst, and a subsequent aromatization preceded by Nef reaction. The axial information of the precursor, which existed as a single axial conformer, was temporarily lost in the intermediate step, and it reemerges with a complete inversion in the final biaryls. The resulting absolute configuration on the chiral axis of the biaryl products was fixed at the aromatization step by a phenomenon of central to axial chirality transfer. More information can be found in the Full Paper by Y. Hayashi et al. on page 4524.

No abstract