Bucky‐Bowl‐Derived Unnatural Amino Acids and Peptides: Synthesis and Substituent Effect on Bowl Inversion Dynamics and Electronic Structure

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AbstractA new kind of bucky‐bowl‐derived unnatural amino acids and their peptides have been designed and synthesized. The substituent effect on bowl inversion dynamics and the electronic structure of corannulene‐derived amino acids has been examined. The data of the inversion barrier revealed that all amino acid‐linked corannulene cognates exhibit a slightly lower inversion barrier in comparison with the pristine corannulene; perhaps due to the repulsion energy between the peri‐hydrogen of the corannulene moiety with the amino acid linker, it flattens the bowl and hence lowers the inversion barrier. The temperature of coalescence (TC) and free energy barrier of unsubstituted corannulene and their corresponding amino acid derivatives were significantly different from the parent corannulene. Electrochemical measurement indicated that amino acid‐based bucky‐bowl than that of unsubstituted bucky‐bowl confirmed the electron‐rich character of the group, which is incorporated in the bowl skeleton.