Journal
HELVETICA CHIMICA ACTA
Volume 102, Issue 4, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/hlca.201900047
Keywords
chirality; cyclophanes; hydrogen bonds; self-assembly; supramolecular chemistry
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Funding
- American Chemical Society Petroleum Research Fund [56665-ND4]
- National Science Foundation REU program [CHE-1156907]
- National Science Foundation
- University of Florida
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A series of [2.2]paracyclophane-bisamide regioisomers and alkylated comparators were designed, synthesized, and characterized in order to better understand the transannular hydrogen bonding of [2.2]paracyclophane-based molecular recognition units. X-Ray crystallography shows that transannular hydrogen bonding is maintained in the solid-state, but no stereospecific self-recognition is observed. The assignment of both transannularly and intermolecularly hydrogen bonded N-H stretches could be made by infrared spectroscopy, and the effect of transannular hydrogen bonding on amide bond rotation dynamics is observed by H-1-NMR in nonpolar solvents. The consequences of transannular hydrogen bonding on the optical properties of [2.2]paracyclophane is observed by comparing alkylated and non-alkylated pseudo-ortho 4,12-[2.2]paracyclophane-bisamides. Finally, optical resolution of 4-mono-[2.2]paracyclophane and pseudo-ortho 4,12-[2.2]paracyclophane-bisamides was achieved through the corresponding sulfinyl diastereoisomers for circular dichroism studies. Transannular hydrogen bonding in [2.2]paracyclophane-amides allows preorganization for self-complementary intermolecular assembly, but is weak enough to allow rapid rotation of the amides even in nonpolar solvents.
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