Regioselective methylation of methyl glycopyranosides with diazomethane in the presence of transition-metal chlorides and of boric acid

Abstract Partial methylation of the methyl pyranosides of a number of pentoses, hexoses, 6-deoxyhexoses, methyl uronates and their methyl ethers with diazomethane in the presence of transition-metal chlorides and boric acid was studied. It was found for methyl glycosides of pentoses and 6-deoxyhexoses that tin(II), antimony(III), and titanium(IV) chlorides as well as boric acid promoted substitution mainly of OH-3, but with cerium(III) and zinc(II) salts mainly substitution of OH-2 was observed. Methylation of methyl β- l -rhamnopyranoside demonstrated higher reactivity of OH-2 in all cases. The methylation of methyl glycosides of hexoses in the presence of tin(II), antimony(III) and cerium(III) chlorides gave mainly 3-methyl ethers. The 3-methyl ethers, which are not involved in further complexation, accumulated up to 50–80% of the reaction mixture (95–100% of monomethyl ether fraction). Convenient preparative syntheses of methyl ethers for a number of sugars are suggested.