Stereoselective (2-naphthyl)methylation of sugar hydroxyls by the hydrogenolysis of diastereoisomeric dioxolane-type (2-naphthyl)methylene acetals

Abstract

The cis axial/equatorial OH groups of methyl alpha-L- and ethyl 1-thio-alpha-L-rhamnopyranoside, 1,6-anhydro-beta-D-mannopyranose, and 1,6-anhydro-beta-D-galactopyranose were reacted with 2-naphthaldehyde dimethyl acetal to diastereomeric dioxolane-type 2,3-O-(2-naphthyl)methylene or 3,4-O-(2-naphthyl)methylene acetals. The glycosides yielded the exo- and endo-isomers in nearly 1:1 ratio, 1,6-anhydro-beta-D-mannopyranose gave predominantly the endo-, and 1,6-anhydro-beta-D-galactopyranose exclusively endo-isomer. The acetals and some of their fully protected derivatives bearing benzyl or tert-butyldimethylsilyl groups were hydrogenolised with AlH(3) (3LiAlH(4)-AlCl(3)) or with Me(3)N.BH(3)-AlCl(3) reagents. The endo-isomers were cleaved by both reagents to give axial NAP ethers, the exo-isomers of pyranosides furnished equatorial NAP ethers. However, the exo-isomers of pyranoses gave irregular axial ethers with a > 30-fold enhancement of the reaction rates with respect to the endo-isomer.