Chirality Exchange from sp~3 Central Chirality to Axial Chirality: Benzannulation of Optically Active Diaryl-2,2-dichlorocyclopropylmethanols to Axially Chiral α-Arylnaphthalenes

摘要

Axially chiral biaryls are well recognized as a characteristic chemical class in organic synthesis due to their utility as efficient chiral ligands and key intermediates of biologically active compounds.1 Various synthetic methods have been exploited to produce chiral biaryls.2 Chirality transfer protocols from stereogenic axes to the sp3 centers have also attracted much attention for studies of asymmetric reactions.3 In addition, opposite methodologies for chirality transfer from a stereogenic sp3 center to axial chirality have moved into the spotlight.2c-h,4,5 This transformation requires more than two steps to obtain atropenantiomers: the initial chirality transfer to construct chiral atropdiastereomers, followed by removal of the sp3 central chirality to produce atropenantiomers. Recently, Shair and co-workers achieved an elegant biomimetic synthesis of (-)-longithorone A using a chirality transfer as the key step.