Synthesis and structure of a carbohydrate-fused [15]-macrodilactone

Abstract

The design, synthesis and structural characterization of a new α-d-glucose fused [15]-macrodilactone is reported. The macrolide was synthesized by a route involving sequential acylations of glucose at the C4' and C6' hydroxyl groups followed by an intramolecular Stille reaction previously established for other [15]-macrodilactones. Analysis of the X-ray crystallographic structure of the macrolide revealed a unique conformation of this macrocycle that differs from earlier models for [13]- and [15]-macrodilactones. Organizing the three planar units and the pyranose moiety into a macrocyclic ring resulted in a cup-shaped structure with planar chirality. Further, the gt conformation of the exocyclic hydroxymethyl group in the glucose unit was found to be crucial for controlling the planar chirality and, hence, governing the molecular shape and overall topology of the compound.

Keywords: Asymmetric center; Carbohydrate; Macrocycle; Macrodilactone; Planar chirality; Topology.