Preparation of 12‐ and 16‐Membered Macrolactones (Oligolides) from (S)‐Malic Acid – Low Molecular‐Mass Analogs of the Biopolymer Poly[(S)‐Malic Acid] (PMA)

As model compounds of uniform composition for the biopolymer PMA, 12‐ and 16‐membered oligolides derived from malic acid by esterification between the carboxylic acid and the β‐hydroxy groups were prepared (Schemes 1 and 2). A reduced form of the triolide derivatives 2, 4, the tris(hydroxymethyl) triolide 10, was also synthesized (Scheme 3). The macrocyclic compounds were isolated in up to 60% yield and fully characterized. The water‐soluble tri‐ and tetracarboxylic acids of this type, thus available for the first time, will be studied as potential binders to polycationic biomolecules.