Regioselective ring opening of benzylidene acetal protecting group(s) of hexopyranoside derivatives by DIBAL-H

The reductive ring-opening reaction of benzylidene-protected glucosides and mannosides such as methyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-d-glucoside (1) and methyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-d-mannoside (4) by using a toluene stock solution of DIBAL-H and a dichloromethane stock solution of DIBAL-H gives mainly or selectively the corresponding 2,3,4-tri-O-benzyl derivatives (2, 5) and 2,3,6-tri-O-benzyl derivatives (3, 6), respectively, although that of methyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-d-galactoside (7) gives methyl 2,3,6-tri-O-benzyl-α-d-galactoside (9) selectively irrespective of the solvent of the stock solution of DIBAL-H. Similarly, the reaction of the exo-isomer of methyl 2,3:4,6-di-O-benzylidene-α-d-mannopyranosides (exo-10) with a toluene stock solution and dichloromethane stock solutions of DIBAL-H selectively gives methyl 3-O-benzyl-4,6-O-benzylidene-α-d-mannoside (12) and methyl 2-O-benzyl-4,6-O-benzylidene-α-d-mannoside (11), respectively, although that of endo-10 selectively affords 11, irrespective of the solvent of the stock solution of DIBAL-H.

Figure optionsDownload as PowerPoint slide