Enantiodifferentiating Photodimerization of a 2, 6‐Disubstituted Anthracene Assisted by Supramolecular Double‐Helix Formation with Chiral Amines. (17th April 2020)

• Record Type: Journal Article
• Authors: Urushima, Akio; Taura, Daisuke; Tanaka, Makoto; Horimoto, Naomichi; Tanabe, Junki; Ousaka, Naoki; Mori, Tadashi; Yashima, Eiji
• Is Part Of: Angewandte Chemie. Volume 132:Number 19(2020)
• Page Start: 7548
• Page End: 7556
• Publication Date: 2020-04-17
• Subjects: diastereoselectivity -- double-helix -- enantioselectivity -- helicity induction -- photodimerization reaction; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201916103
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A novel 2, 6‐anthrylene‐linked bis( m ‐terphenylcarboxylic acid) strand (1 ) self‐associates into a racemic double‐helix. In the presence of chiral mono‐ and diamines, either a right‐ or left‐handed double‐helix was predominantly induced by chiral amines sandwiched between the carboxylic acid strands with accompanying stacking of the two prochiral anthracene linker units in an enantiotopic face‐selective way, as revealed by circular dichroism and NMR spectral analyses. The photoirradiation of the optically active double helices complexed with chiral amines proceeded in a diastereo‐ ( anti or syn ) and enantiodifferentiating way to afford the chiral anti ‐photodimer with up to 98 % enantiomeric excess when ( R )‐phenylethylamine was used as a chiral double‐helix inducer. The resulting optically active anti ‐photodimer can recognize the chirality of amines and diastereoselectively complex with chiral amines. Abstract : A 2, 6‐anthrylene‐linked bis( m ‐terphenylcarboxylic acid) strand forms a one‐handed homo double helix induced by chiral amines, thereby producing the chiral anti ‐photodimer with up to 98 % enantiomeric excess upon photoirradiation. The chirality of the anti ‐photodimer can be readily controlled by the chirality of the chiral amines.