Structures of three disubstituted [13]-macro-di-lac-tones reveal effects of substitution on macrocycle conformation.

The synthesis and crystal structures of three new disubstituted [13]-macro-di-lactones, namely, -4,8-dimethyl-1,10-dioxa-cyclo-tridec-5-ene-2,9-dione, CHO, , -4-(4-bromo-phen-yl)-13-methyl-1,10-dioxa-cyclo-tridec-5-ene-2,9-dione CHBrO, , and -11-methyl-4-phenyl-1,10-dioxa-cyclo-tridec-5-ene-2,9-dione, CHO, , are reported and their conformations are put in the context of other [13]-macrodilactone structures reported previously. Together, they show that the number, location, and relative disposition of groups attached at the termini of planar units of the [13]-macrodilactones subtly influence their aspect ratios.

Macrocycles All Aflutter: Substitution at an Allylic Center Reveals the Conformational Dynamics of [13]-Macrodilactones.

The shapes adopted by large-ring macrocyclic compounds play a role in their reactivity and their ability to be bound by biomolecules. We investigated the synthesis, conformational analysis, and properties of a specific family of [13]-macrodilactones as models of natural-product macrocycles. The features of our macrodilactones enabled us to study the relationship between stereogenic centers and planar chirality through the modular synthesis of new members of this family of macrocycles.