Kinetic Chiral Resolutions of 1,2-Diols and Desymmetrization of Glycerol Catalyzed by Glycerol Kinase

• Published in: Journal of organic chemistry Vol. 63; no. 12; pp. 4039 - 4045
• Main Authors: Chenault, H. Keith, Chafin, Laura F, Liehr, Sebastian
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 12.06.1998; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; ORGANIC-SYNTHESIS; ACID; ANALOGS; ESTERIFICATION; HYDROLYSIS; 3-BUTENE-1,2-DIOL; LIPASE; GENERATION; DERIVATIVES; (R)-GLYCEROL
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo980122y

Enantioselective phosphorylation catalyzed by glycerol kinase (EC 2.7.1.30) facilitated the kinetic chiral resolution of 3-chloro-1,2-propanediol, 3-fluoro-1,2-propanediol, 3-butene-1,2-diol, and 1,2,4-butanetriol. Both enantiomers of each compound were isolated in free diol or triol form, in excellent enantiomeric purity (91 to >99.5% ee) and in moderate to good yield (60−94% of theoretical). The enantioselectivities of glycerol kinase from different sources were compared, using 1,2,4-butanetriol as the substrate. The effect of elevated temperatures on enzymatic activity, stability, and enantioselectivity were studied, and procedures for the isolation of diol and triol products were optimized. Glycerol kinase-catalyzed phosphorylation facilitated the three-step chemoenzymatic conversion of glycerol to (S)-1,2-O-isopropylideneglycerol in 83% yield and >99.5% ee).