Open-chain acetonides of D-galactono-l,4-lactone as starting materials for pyrrolidines, azepanes and 5-azidomethyltetrahydrofuran-2-carboxylates: Monomers for polyhydroxylated nylon and for tetrahydrofuran carbopeptoids

Article abstract of DOI:10.1039/a809807g

Treatment of D-gaIactono-l,4-lactone with dimethoxypropane in acetone in the presence of tosic acid forms methyl 2,3:5,6-di-0-isopropylidene-D-galactonate 6 (with only the secondary hydroxy group at C-4 unprotected) and methyl 2,3:4,5-di-O-isopropyIidene-D-galactonate 5 (with only the primary hydroxy group at C-6 unprotected) in yields of 20% and 78%, respectively. The value of such easily accessible intermediates is illustrated by the synthesis of l,4-dideoxy-l,4-imino-D-glucitol 16 (a pyrrolidine), and for the efficient preparation of 6-azido-6-deoxy-D-galactono1,4-lactone 22. The conversion of 22 to a seven-rhembered galactonolactam 21 (a tetrahydroxycaprolactam) may provide access to hydroxylated nylon polymers. The galactonolactam 21 has no significant inhibitory effect on a number of glycosidases. Reaction of 22 with triflic anhydride gives two epimeric 5-(azidomethyl)tetrahydrofuran-2carboxylates which provide starting materials for two series of carbopeptoids, one of which probably has a helical structure and the other a structure reminiscent of a β-turn.