Helical chirality induction of expanded porphyrin analogues

Journal of Chemical Sciences

Jun-Ichiro Setsune1¹ 

[1] Department of Chemistry, Graduate School of Science, Kobe University, Nada-ku, Kobe 657 8501, Japan$$

关键词: Porphyrin analogues;    metal complexes;    helical chirality;    chirality sensing.;   

DOI  :  

来源: Indian Academy of Sciences

【 摘 要 】

Expanded porphyrin analogues with unique figure-eight conformation were prepared by way of useful pyrrole intermediates such as bis(azafulvene)s and 2-borylpyrrole. Supramolecular chirogenesis of cyclooctapyrrole O1 with 32𝜋-cycloconjugation was successfully applied to determine absolute configuration of chiral carboxylic acids. Dinuclear CuII complex of cyclooctapyrrole O2 with interrupted 𝜋-conjugation was resolved by HPLC into enantiomers and their helical handedness was determined by theoretical simulation of their CD spectral pattern. Enantioselective induction of helicity in the metal helicate formation in the presence of a chiral promoter was demonstrated by using (𝑅)-(+)-1-(1-phenyl)ethylamine that favoured 𝑃, 𝑃 helicity. Dinuclear CoII complexes of cyclotetrapyrroletetrapyridine O3 were found to be substitution labile and pick up amino acid anions in water. Those amino acid complexes of O3Co2 were rendered to adopt a particular unidirectional helical conformation preferentially depending on the ligated amino acid anion.

【 授权许可】

Unknown