Kinetic resolution of racemic alcohols catalyzed by minimal artificial acylases derived from l-histidine

• Published in: Tetrahedron Vol. 63; no. 27; pp. 6191 - 6203
• Main Authors: Kosugi, Yuji, Akakura, Matsujiro, Ishihara, Kazuaki
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 02.07.2007; Elsevier
• Subjects: Asymmetric acylation; Chemistry; Chemistry, Organic; Histidine; Kinetic resolution; Nucleophilic catalyst; Organocatalyst; Physical Sciences; Science & Technology; Asymmetric acylation; Nucleophilic catalyst; Histidine; Kinetic resolution; Organocatalyst; ASYMMETRIC CATALYSIS; 4-(DIMETHYLAMINO)PYRIDINE; ACYLATION; ANALOGS; asymmetric acylation; nucleophilic catalyst; SECONDARY ALCOHOLS; M-TERPHENYLS; PEPTIDE-BASED CATALYSTS; kinetic resolution; organocatalyst; DERIVATIVES; histidine
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2007.02.020

The artificial acylases, tert-butyldiphenylsilyl ether and tris(trimethylsilyl)silyl ether of N(π)-methyl- N(α)-(2,4,6-triisopropylbenzenesulfonyl)- l-histidinol, are simple and small molecules, which contain only one chiral carbon center that originates from natural l-histidine. Asymmetric acylation of racemic secondary alcohols with isobutyric anhydride induced by these artificial acylases gave optically active isobutyrates and optically active alcohols with an S( k fast-reacting enantiomer/ k slow-reacting enantiomer) value of up to 132. One hydrogen bonding interaction between a sulfonamidyl group of the catalysts and a substrate should be essential for inducing the high level of kinetic resolution through catalytic asymmetric acylation. Furthermore, a reusable polystyrene-bound artificial acylase was developed to examine its practicality. [Display omitted]