Herein we report the successful synthesis of an electronically-dissymmetric macrocycle. This macrocycle has the following key features: (a) clearly defined electron-rich and electron-deficient segments, which enable it to bind two electronically distinct small molecules simultaneously; (b) flexible methylene linkers that will enable it to be used as a supramolecular catalyst; (c) an all-organic backbone that may have reduced toxicity relative to heavy-metal macrocycles; and (d) straightforward, highyielding synthesis that enables the synthesis of a variety of analogues.The macrocycle can form ternary complexes with a variety of small-molecule guests, which will in turn dictate the relevant applications. In particular, two applications are currently being investigated: (a) making one guest an electron-rich diene and one guest an electron-deficient dienophile, to determine whether the macrocycle can catalyze challenging Diels-Alder cycloadditon reactions; and (b) making one guest a polycyclic aromatic hydrocarbon (PAH) and one guest a small-molecule fluorophore, and investigating the energy transfer from the PAH to the fluorophore as a method for PAH detection.Computational studies using semi-empirical PM3 level calculations have shown that the newly synthesized macrocycle has a cavity of approximately the same dimensions as gamma-cyclodextrin, which is known to bind two small-molecule guests simultaneously.

Synthesis of an electronically dissymmetric macrocycle

245th National Meeting (2013)

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