Supramolecular Chirogenesis in Zinc Porphyrins:  Mechanism, Role of Guest Structure, and Application for the Absolute Configuration Determination

• Published in: Journal of the American Chemical Society Vol. 123; no. 13; pp. 2979 - 2989
• Main Authors: Borovkov, Victor V, Lintuluoto, Juha M, Inoue, Yoshihisa
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04.04.2001
• Subjects: Circular Dichroism; Ligands; Metalloporphyrins - chemistry; Metalloporphyrins - physiology; Molecular Conformation; Nuclear Magnetic Resonance, Biomolecular; Spectrophotometry, Ultraviolet; Stereoisomerism; Structure-Activity Relationship; Zinc - chemistry; Zinc - physiology
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0032982

The achiral syn folded (face-to-face conformation) host molecule of the ethane-bridged bis(zinc porphyrin) transforms into the corresponding chiral extended anti bis-ligated species in the presence of enantiopure amine guests. The mechanism of the supramolecular chirogenesis is based upon the screw formation in bis(zinc porphyrin), arising from steric interactions between the largest substituent at the ligand's asymmetric carbon and peripheral alkyl groups of the neighboring porphyrin ring pointing toward the covalent bridge. The screw direction is determined by the guest's (amines) absolute configuration resulting in a positive chirality induced by (S)-enantiomers due to formation of the right-handed screw, and a negative chirality produced by the left-handed screw of (R)-enantiomers. The screw magnitude is strongly dependent upon the structure of the chiral guests. The amines with bulkier substituents result in stronger CD signals and larger 1H NMR resonance splittings of enantiotopic protons. This system possesses a high degree of chiroptical activity, which allows the differentiation of one of the smallest homologous elements of organic chemistry, that is, the methyl and ethyl groups attached to the asymmetric carbon, and additionally, which senses a remote chiral center at a position β to the amine binding group.