2,3,6,7-Tetrasubstituted Decalins: Biconformational Transducers for Molecular Signal Transduction

• Published in: European journal of organic chemistry Vol. 2001; no. 3; pp. 575 - 586
• Main Authors: Koert, Ulrich, Krauss, Rolf, Weinig, Hans-Georg, Heumann, Carola, Ziemer, Burkhard, Mügge, Clemens, Seydack, Matthias, Bendig, Jürgen
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag GmbH 01.02.2001; WILEY‐VCH Verlag GmbH; Wiley
• Subjects: Biconformational double ring flip; Chemistry; Chemistry, Organic; Conformation analysis; Decalin; Physical Sciences; Science & Technology; Signal transduction; Synthesis design; conformation analysis; decalin; signal transduction; synthesis design; biconformational double ring flip
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/1099-0690(200102)2001:3<575::AID-EJOC575>3.0.CO;2-7

2,3,6,7‐Tetrasubstituted decalins of relative configuration (2β,3α,4aα,6α,7β,8aα) have been synthesized. If substituents as in 6 are chosen, the equilibrium of the biconformational system 2/3 is shifted towards conformer 2. Conversion into the bis(acetal) 16 resulted in a covalently induced double ring flip 17 → 18. A chelation‐induced double ring flip (21 → 22) was achieved when 2,2′‐bipyridyl substituents were attached by ether linkages at the receptor positions 6 and 7 of the decalin system. Effector groups were introduced by adding pyrene groups, through an (E)‐olefin linker, in positions 2 and 3. The resulting compound 25 proved to be an effective device for molecular signal transduction over a signal distance of 1.5 nm. A zinc signal caused a conformational axial‐to‐equatorial change at the receptor site, which was transduced by a double ring flip of the decalin moiety (28 → 29) to the pyrene effector site, where the induced equatorial‐to‐axial flip induced a characteristic fluorescence peak.