Asymmetric Strecker reaction at the solid/solid interface. Issue 3 (21st November 2022)

• Record Type: Journal Article
• Authors: Yoshimura, Yuki; Tanaka, Yudai; Kobayashi, Ryota; Niikura, Kohei; Kawasaki, Tsuneomi
• Is Part Of: Organic & biomolecular chemistry. Volume 21:Issue 3(2023)
• Page Start: 520
• Page End: 524
• Publication Date: 2022-11-21
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/d2ob01802k
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : Asymmetric solid-state Strecker reaction arising from crystal chirality of a racemic cyanohydrin has been demonstrated to afford highly enantioenriched α-aminonitrile. Abstract : Related to absolute asymmetric synthesis, a stereospecific reaction at the solid/solid interface arising from crystal chirality of the achiral or racemic substrates has not yet been reported. Here, we demonstrate the asymmetric Strecker-type solid/solid reaction between the chiral crystal of a racemic cyanohydrin (kryptoracemate) and the achiral crystal of an ammonium salt to afford highly enantioenriched α-aminonitrile in combination with amplification of chirality. rac -Cyanohydrin provides its chiral surface as a reactive site and the reaction proceeds with dissociation of cyanohydrin; thus, an asymmetric Strecker-type reaction takes place at the interface of the substrate crystals. Strecker synthesis coupled with cyanohydrin synthesis offers a credible abiotic synthesis mechanism of α-amino acids and α-hydroxy acids. For the first time, stereochemical relationship has been found between the two chiral intermediates, aminonitrile and cyanohydrin, which are in equilibrium in the synthesis mechanism.