Synthesis and Characterization of New Diazocine Derivatives for Application in Photopharmacology and Material Science

The incorporation of photoswitchable molecules into biological or technical systems is a promising approach for the selective control of such processes at the molecular level. The diazocine exhibits excellent switching efficiency and very high quantum yields. However, the initial diazocine has some weaknesses. By systematic improvement a promising “second generation” was developed with the diindanodiazocines (DIDs) and the N-acetyl diazocines (N‑Ac diazocines), whose further investigation and derivatization were the focus of this work.
By eliminating unproductive degrees of freedom, the switching properties were improved during the development of the DIDs. During the synthesis two diastereomers are formed, of which the racemate is chiral. The racemate was separated into its two enantiomers and their chiroptical switching behaviour was investigated. Irradiation with circular polarized light lead to the selective enrichment of the corresponding enantiomer and the enantiomeric excess could be determined. In order to make the DID-system accessible for further functionalization, synthesis strategies for the preparation of di- and tetrahalogenated DID‑diastereomers were developed.
In contrast to the original diazocine, the N-Ac diazocine is water-soluble. This makes the N‑Ac diazocines perfectly suitable for use as a photopharmacophore in the aqueous environments. Using of transition metal-catalyzed cross-couplings, new derivatives were synthesized from the monohalogenated N‑Ac diazocines. The new derivatives have been photochemically characterized both in organic solvents and in an aqueous environment. Some derivatives showed a strong inhibition of the endogenous 17βHSD3 enzyme catalyzing testosterone formation. However, a difference in efficacy between the Z ‑ and E ‑configurations of the derivatives could not be observed. 

Rechte

Nutzung und Vervielfältigung:

Keine Lizenz. Es gelten die Bestimmungen des deutschen Urheberrechts (UrhG).

Bitte beachten Sie, dass einzelne Bestandteile der Publikation anderweitigen Lizenz- bzw. urheberrechtlichen Bedingungen unterliegen können.

Zitieren

Zitierform:
Zitierform konnte nicht geladen werden.