Synthesis and study of C(3)-symmetric hydropyran cyclooligolides with oriented aryl and alcohol appendages at 10 A spacing.
Modular syntheses of C(3)-symmetric macrocycles with pendant aryl and hydroxymethyl groups are described. These functional groups, amenable to further elaboration, were installed early in each synthesis and carried through an iterative sequence of module coupling and macrolactonization. Association constants for macrolides 1a-c with alkali metal cation guests were determined, and sandwich-type complexes with Ba(2+) were confirmed for these macrocycles based on (1)H NMR studies, including Job plots. X-ray crystallographic data for macrolides 1a and 1c were obtained and are discussed in detail. These data provide support that the macrolides are structurally well-defined and preorganized for binding the potassium cation. Preparation of the tris(bromoacetylated) macrotriolide 43 exemplifies a functionalized platform suitable for elaboration with peptide or carbohydrate residues.
Burke
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SD
Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706-1396, USA. burke@chem.wisc.edu
Zhao
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D000438:Alcohols / Q000737:chemistry* / Q000378:metabolism; D001464:Barium / Q000378:metabolism; D018360:Crystallography, X-Ray; D018942:Macrolides / Q000138:chemical synthesis* / Q000737:chemistry* / Q000378:metabolism; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D011188:Potassium / Q000378:metabolism; D011714:Pyrans / Q000138:chemical synthesis* / Q000737:chemistry* / Q000378:metabolism; D013816:Thermodynamics
D000438:Alcohols; D018942:Macrolides; D011714:Pyrans; D001464:Barium; D011188:Potassium