Alkylating ability of carbohydrate oxetanes: Practical synthesis of bolaform skeleton derivatives

Abstract

The alkylating ability of the oxetane ring in the carbohydrate structure was investigated and a flexible method for the construction of a bolaform amphiplile skeleton with xylose as the polar head is proposed. The method is based on oxetane ring opening in the easily accessible 3,5-anhydro-1,2-O-cyclohexylidenexylofuranose (1). One-step nitrogen alkylation in terminal diamines with 1 gave the basic cationic bolaform skeleton with xylose as potential polar head and a deliberately chosen length of the non-polar spacer. Under similar experimental conditions, but with an appropriate mole ratio of the alkylating agent, the alkylation reaction provide for selective monoalkylation of the diamines. Successful alkylation in the xanthine series (theophylline) was also achieved with 1, giving a new 5-deoxy-5-(1,2,3,6-tetrahydro-1,3-dimethyl- 2,6-dioxo-7H-purin-7-yl)-alpha-D-xylofuranose derivative.