Enantioselective preparation of mechanically planar chiral rotaxanes by kinetic resolution strategy

• Published in: Nature communications 2021-01, Vol.12 (1), p.404-7, Article 404
• Main Authors: Imayoshi, Ayumi, Lakshmi, Bhatraju Vasantha, Ueda, Yoshihiro, Yoshimura, Tomoyuki, Matayoshi, Aki, Furuta, Takumi, Kawabata, Takeo
• Format: Article
• Language: English
• Subjects: 140/131; 140/58; 639/638/403/933; 639/638/403/935; 639/638/541/964; Acylation; Alcohol; Asymmetric synthesis; Asymmetry; Catalysts; Chirality; Discrimination; Enantiomers; Humanities and Social Sciences; multidisciplinary; Pharmaceuticals; Rotaxanes; Science; Science (multidisciplinary); Selectivity; Yield
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-020-20372-0

Asymmetric synthesis of mechanically planar chiral rotaxanes and topologically chiral catenanes has been a long-standing challenge in organic synthesis. Recently, an excellent strategy was developed based on diastereomeric synthesis of rotaxanes and catenanes with mechanical chirality followed by removal of the chiral auxiliary. On the other hand, its enantioselective approach has been quite limited. Here, we report enantioselective preparation of mechanically planar chiral rotaxanes by kinetic resolution of the racemates via remote asymmetric acylation of a hydroxy group in the axis component, which provides an unreacted enantiomer in up to >99.9% ee in 29% yield (the theoretical maximum yield of kinetic resolution of racemate is 50%). While the rotaxane molecules are expected to have conformational complexity, our original catalysts enabled to discriminate the mechanical chirality of the rotaxanes efficiently with the selectivity factors in up to 16. Since the discovery of mechanically planar chiral rotaxanes and topologically chiral catenanes, their asymmetric synthesis has been a long-standing challenge. Here, the authors report enantioselective preparation of mechanically planar chiral rotaxanes with up to 99.9% ee in 29% yield.