Diverse Chiral Scaffolds from Diethynylspiranes: All-Carbon Double Helices and Flexible Shape-Persistent Macrocycles.

ABSTRACT

State-of-the-art chiroptical spectroscopies are valuable tools for structural elucidation. However, the potential of these spectroscopies for everyday applications has not been exploited to date partially due to the lack of sufficiently stable and efficient chiroptical systems. To this end, the development of suitable chiroptical structures is essential. Herein, we present the synthesis of spiro-compounds (P2 )-1 and (P4 )-2 as well as (M2 )-1 and (M4 )-2 exhibiting remarkable chiroptical responses. Theoretical simulations show that (P2 )-1, constituted by two (P)-configured spiranic chiral axes, presents an all-carbon double helix structure with (M)-helicity. On the other hand, molecular dynamic simulations reveal (P4 )-2 to have a single path for geometry-modification along its flat conformational space, certifying it as a chiral flexible shape-persistent macrocycle. Geometric quantification of chirality has been used to compare the spiranic derivatives presented herein.