2,3,6,7‐Tetrasubstituted Perhydroanthracenes: Stereoselective Synthesis and Biconformationality Studies

Abstract

2,3,6,7‐Tetrasubstituted perhydroanthracenes with the relative configuration 2β,3α,4aα,6β,7α,8aβ,9aα,10aβ have been synthesized stereoselectively. The biconformationality of these compounds has been investigated in solution by NMR and in the solid state by X‐ray crystallography. A triple‐ring flip 2 → 3 was realized for the first time by the covalently induced transition 29 → 30.

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.…”

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

“…The alcohol 10, which is accessible from a cyclohexenone precursor by means of a DielsϪAlder reaction with 1,3-butadiene, [6] was allowed to react with m-chloroperbenzoic acid (MCPBA). The two diasteromeric epoxides 11 and 12 were obtained as a 4.3:1 mixture in 80% yield, and could be separated by chromatography.…”

“…Figure 4, b summarizes the NOE contacts found for 16. Of particular importance are the contacts between the three axial protons H β -(4), H- (6), and H β -(8), as well as the contact between H β -(8) and CH 2 OH- (2). H β -(8) (δ ϭ 1.48), is the only signal with three large J coupling constants of 12 Hz [ 2 J and two 3 J (transdiaxial)].…”

“…[4] The associated motion is transmitted by the transducer to the effector site, where a second conformational change gives some kind of measurable effect, such as a new signal, a chemical reaction, or a mechanical change. [5] The two-state behavior of biconformational cis-anti-cis-perhydroanthracenes [6] is suited for this purpose. Here, a triple ring flip of one all-chair conformer to the other all-chair conformer has been used to bridge a signal distance of 2 nm.…”

(1R*,2R*)-1,2-(2,3-Dimethoxybutane-2,3-dioxy)cyclohexane

“…The title compound, (I), was synthesized as a model compound for substituted diequatorial ®xed vicinal transcyclohexanediols (Berninger et al, 1999). Following the method of Ley et al (1994) and Montchamp et al (1996), the reaction of trans-cyclohexane-1,2-diol with 2,2,3,3-tetramethoxybutane, trimethyl orthoformate and catalytic camphorsulfonic acid in methanol at 313 K for 3 h led to the title compound, (I), in 86% yield.…”