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

Abstract

Keywords: Biconformational double ring flip / Conformation analysis / Decalin / Signal transduction / Synthesis design 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 Ǟ 18. A chelation-induced double ring flip (21 Ǟ 22) was achieved when 2,2Ј-bipyridyl substituents were attached by ether linkages at the receptor positions 6 and 7 of the decalin system. Effector groups were introduced by

Cyclohexane-Based Conformationally Controlled Crowns and Podands

“…A conformational impulse can be transmitted over a larger distance if the cyclohexane transmitting unit is extended by additional units as in cis-decalin or cis-anti-cisperhydroanthracene [31][32][33][34][35][36]. Similar to cyclohexane, these structures have two low energy chair conformations that can switch when the attached binding groups interact with a guest.…”

“…In these structures, a substituent plays a role of 'conformational lever', and the cyclohexane moiety is a mechanical transmitter. These ideas were successfully explored also by Costero et al [26][27][28][29][30], and were expanded by Koert et al [31][32][33][34][35][36] to decaline and perhydroanthracene derivatives. These ideas were successfully explored also by Costero et al [26][27][28][29][30], and were expanded by Koert et al [31][32][33][34][35][36] to decaline and perhydroanthracene derivatives.…”

Trans-2-aminocyclohexanols as pH-triggered molecular switches

“…By affecting these interactions one can control the position of conformational equilibrium of the type 1A 1B, thus controlling the shape and the complexing ability of the macrocycle or podand. These ideas were successfully explored also by Costero et al, [28][29][30][31][32] and were expanded by Koert et al [33][34][35][36][37][38] to cis-decaline and perhydroanthracene derivatives.…”

Molecular Signal Transduction by Conformational Transmission: Use of Tetrasubstituted Perhydroanthracenes as Transducers

“…The corresponding binding energy required to induce the double ring flip in the decalin series has been determined as DG 6.8 kcal mol À1 . [11] Both values exceed the limit for the switching energy of 6 kcal mol À1 estimated as the requirement for shifting the equilibrium 5 > 6 towards 6. The triple ring flip (18 3 19) could be monitored by an 1 H NMR titration experiment on the reaction of 15 with Zn(OTf) 2 ( Figure 6b).…”