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Twisted Allenyl-Pyridocyclophanes by Templated Cyclooligomerization: Chiral Cavities for Precision Molecular
Jonathan Álvarez-García1, María Magdalena Cid1
1Departamento de Química Orgánica. Ciencias Experimentais, Universidade de Vigo, Vigo 36310, Spain.
Abstract:
We report the palladium-catalyzed one-pot synthesis of enantiopure 20-, 30-, and 40-membered cyclophanes shaped by axially twisted allene units. Under Cs+-template, the two smaller macrocycles (2 and 3) are favored over the largest (4). X-ray studies reveal that rac-2 assembles into homochiral helices that pack to form channels, while rac-3 forms racemic dimers. These shape-persistent hosts, with unique chiral 3D cavities, undergo guest-induced conformational switching and (enantio)-selectively bind diols and ammonium cations, including hydroxycarboxylic acids and α-hydroxyammoniums, as evidenced by diagnostic ECD shifts.
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