Synthesis of 2-methyl-D-erythritol via epoxy ester-orthoester rearrangement.
The biomimetic epoxy ester[bond]orthoester rearrangement has been applied to a new synthesis of 2-methyl-D-erythritol, a branched five-carbon sugar of importance to the deoxyxylulose pathway of isoprenoid biosynthesis. The intermediate orthoacetate is one of the few [2.2.1]-orthoesters to have been reported. Labeling studies with O-18 indicated that this reaction proceeds exclusively via a 5-exo cyclization. NMR analysis of chiral esters indicated an ee of 87% for the starting epoxide and an ee of 86% for the product. This route represents a rapid and convenient method for the synthesis of 2-methyl-D-erythritol and is expected to be useful for generating isotopically labeled intermediates for biochemical studies.
Giner
José-Luis
JL
Department of Chemistry, State University of New York-ESF, Syracuse, New York 13210, USA. jlginer@syr.edu
Ferris
William V
WV
Mullins
Joseph J
JJ
D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods; D003500:Cyclization; D004852:Epoxy Compounds / Q000737:chemistry*; D004896:Erythritol / Q000031:analogs & derivatives* / Q000138:chemical synthesis*; D004952:Esters / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013237:Stereoisomerism
D004852:Epoxy Compounds; D004952:Esters; C043904:3-C-methylerythritol; D004896:Erythritol