Construction of an Axially Chiral 1,1′‐Bianthryl Framework via Scholl‐Type Oxidative Cyclization: Formation of an Eight‐Membered [1,4]Diazocine and Asymmetric Induction by a Chiral Brønsted Acid

An o ‐phenylene‐bridged di(2‐anthracenyl)diamine ( 2 ) bearing two 2‐anthryl units was synthesized through a two‐step Buchwald–Hartwig cross‐coupling strategy. Subsequent Scholl‐type oxidative cyclization with FeCl 3 or p ‐chloranil under acidic conditions proceeded with high regioselectivity, yielding a cyclic 1,1′‐bianthryl derivative ( 1B ) that incorporates an eight‐membered [1,4]diazocine framework generated concurrently with intramolecular biaryl bond formation. The photophysical properties of 2 and 1B were examined using UV–vis absorption and fluorescence spectroscopy, which revealed fluorescence bands and a marked reduction in fluorescence quantum yield upon cyclization. Enantiomeric resolution of racemic 1B was accomplished by chiral high‐performance liquid chromatography (HPLC), and the absolute configurations were determined through circular dichroism (CD) spectroscopy combined with time‐dependent density functional theory (TD‐DFT) calculations. Notably, when chiral camphorsulfonic acid served as the Brønsted acid additive in the p ‐chloranil‐mediated Scholl reaction, asymmetric induction was observed, affording an enantiomeric excess (ee) of up to 10%. Although the enantioselectivity remains modest, this finding provides experimental evidence that an external chiral acid can impart stereochemical information during oxidative intramolecular biaryl bond formation. This study establishes a proof of concept for asymmetric control in Scholl‐type reactions and underscores the potential of medium‐sized N ‐bridged frameworks for constructing chiral π‐conjugated architectures.