Regio- and stereoisomeric control of the aggregation of zinc-chlorins possessing inverted interactive hydroxyl and carbonyl groups.
As models for a self-aggregative, naturally occurring magnesium-chlorin bacteriochlorophyll-d possessing 3(1)-secondary alcoholic hydroxyl and 13(1)-oxo groups, zinc-chlorins were synthesized with 3(1)-oxo and 13(1)-secondary (1) or tertiary hydroxyl groups (2). Compared to the monomers in a tetrahydrofuran solution, diastereomers 13(1)R-1R and 13(1)S-1S gave red-shifted absorption maxima (643 --> 674 nm in 1R and 708 nm in 1S) in 1 v/v% CH(2)Cl(2)-hexane solution, indicating their self-aggregation. Therefore, the positioning of the two groups at 3(1)/13(1) or 13(1)/3(1) on the N21-N23 molecular (Q(y)) axis is not necessarily important for the self-aggregation. The (1)H NMR and CD spectroscopic studies showed that the 674 nm absorbing species of 1R was characterized as a face-to-face "closed" dimer, while the 708 nm absorbing species of 1S was a large oligomer constructed with aggregation of head-to-tail "open" dimers. This diastereomeric control over the aggregation of 1R and 1S is more pronounced than that observed in the regioisomerically 3(1)-secondary alcoholic R/S-diastereomers 3R and 3S. The difference is ascribable to the conformational fixation of the 13(1)-hydroxyl group of the exo five-membered ring in 1. In contrast to self-aggregative 3(1)-tertiary alcoholic 4, both 13(1)-epimers of 13(1)-tertiary alcoholic 2 were monomeric even in nonpolar organic media: the additional 13(1)-methyl group (1 --> 2) drastically suppressed the self-aggregation due to the interference of the methyl group in intermolecular pi-pi interaction.
Yagai
Shiki
S
Department of Bioscience and Biotechnology, Faculty of Science and Engineering, Ritsumeikan University, Kusatsu, Shiga 525-8577, Japan.
Miyatake
Tomohiro
T
Tamiaki
Hitoshi
H
D002942:Circular Dichroism; D019281:Dimerization; D008665:Metalloporphyrins / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D011166:Porphyrins / Q000138:chemical synthesis / Q000737:chemistry; D013057:Spectrum Analysis; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry
D008665:Metalloporphyrins; D011166:Porphyrins; C006969:chlorin; D015032:Zinc