Control of functional group proximity and direction by conformational networks: synthesis and stereodynamics of persubstituted arenes

Kilway, Kathleen V.; Siegel, Jay S.

doi:10.1016/s0040-4020(01)00248-4

Cited by 54 publications

(42 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is well documented that the three substituents at alternating positions of a hexasubstituted benzene point in the same direction, either above or below the benzene plane. [15,16] Hence, the three aldehyde substituents upon imine formation will present three arms protruding from the same side of the benzene ring, thus providing convergent recognition elements for the binding of the target. [17] The synthetic strategies used to synthesize the two platforms are shown in Scheme 1.…”

Section: Resultsmentioning

confidence: 99%

The Advantage of Covalent Capture in the Combinatorial Screening of a Dynamic Library for the Detection of Weak Interactions

et al. 2010

View full text Add to dashboard Cite

In this paper we address the advantage of screening a dynamic library by covalent capture in comparison with an approach in which the target is not covalently bound to the molecular receptor. The aim is the selection of recognition units for the binding of an anion (or polyanion) by relatively weak binding interactions, a situation typically found in supramolecular chemistry. To compare the two approaches, two model systems have been studied both based on the functionalization of a molecular platform by reversible imine formation. In the case of the noncovalently bound substrate, the platform PI is a trisubstituted benzene unit, 2,4,6-trimethylbenzene-1,3,5-tricarbaldehyde, to select three recognition arms for the binding of the trisodium salt of benzene-1,3,5-tricarboxylate. For the covalent-capture-based approach the platforms P2 and P4 are benzene derivatives with a tethered phosphonate target (tetrabutylammonium 2-formylphenyl ethylphosphonate) for the selection of a single recognition unit. The library of recognition elements comprises phenyl- and ammonium-functionalized amines. We show that the selection of recognition units for the binding of the substrate with weak to medium binding constants may encounter, by using a noncovalently bound substrate, serious problems. This is because the best conditions for the amplification of the library, that is, a large excess of variable recognition elements and target, lead also to competitive binding of the elements not bound to the platform with the target. This may result in negligible amplification of the best-fit members of the library. In contrast, upon tethering the target to the platform and using the covalent-capture strategy for the selection of the recognition elements, significant amplification is observed, even for systems with much lower binding constants. Although competition with excess recognition units may also become an issue in the case of the tethered target, there is a way to overcome the problem by working at low concentrations

show abstract

Section: Resultsmentioning

confidence: 99%

The Advantage of Covalent Capture in the Combinatorial Screening of a Dynamic Library for the Detection of Weak Interactions

et al. 2010

View full text Add to dashboard Cite

show abstract

“…The alternating 1,3,5‐up‐2,4,6‐down structure of HEB also prompted Kilway and Siegel to prepare a series of derivatives in which functional groups were introduced either in meta positions (and thus arranged convergently) or ortho / para , in which case they were oriented divergently, as exemplified in Figure . Moreover, it was shown that the dynamic stereochemistry of these molecules was influenced mainly by the steric bulk of the substituents …”

Section: Dynamic Behaviour Of Hexaethylbenzene Complexesmentioning

confidence: 99%

Hexaethylbenzene: A Sterically Crowded Arene and Conformationally Versatile Ligand

McGlinchey

2018

ChemPlusChem

View full text Add to dashboard Cite

show abstract

“…By the appropriate modification of the basic skeleton of 1, other ligand topologies are available. [8] For example, introduction of two binding groups in the 1-and 4-positions of 1, would result in a derivative with divergent binding groups pointing to opposite faces of the aryl ring. [8] Scheme 2…”

Section: Conformation Of Hexaethylbenzenementioning

confidence: 99%

Stereochemistry of Polyethylated Aromatic Systems

2003

View full text Add to dashboard Cite

Hexaethylbenzene adopts a conformation with the ethyl groups perpendicular to the aromatic ring and oriented in a fully alternated up‐down arrangement. The synthesis, stereochemistry and rotational barriers of systems possessing two polyethylaryl rings in spatial proximity (e.g., decaethylbiphenyl, octaethylbiphenylene) are reviewed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

show abstract

Control of functional group proximity and direction by conformational networks: synthesis and stereodynamics of persubstituted arenes

Cited by 54 publications

References 57 publications

The Advantage of Covalent Capture in the Combinatorial Screening of a Dynamic Library for the Detection of Weak Interactions

The Advantage of Covalent Capture in the Combinatorial Screening of a Dynamic Library for the Detection of Weak Interactions

Hexaethylbenzene: A Sterically Crowded Arene and Conformationally Versatile Ligand

Stereochemistry of Polyethylated Aromatic Systems

Contact Info

Product

Resources

About