Aromatische Ringe in chemischer und biologischer Erkennung: Energien und Strukturen

Abstract

Dieser Aufsatz beschreibt Phänomene der molekularen Erkennung von aromatischen Ringen in chemischen und biologischen Systemen in einem multidimensionalen Ansatz. Neue Ergebnisse aus der Wirt‐Gast‐Chemie, biologischen Affinitätsassays und Biostrukturanalysen, Datenbanksuchen in der Cambridge Structural Database (CSD) und der Protein Data Bank (PDB) und hochentwickelten Rechnungen, die seit dem Erscheinen eines früheren Aufsatzes in 2003 veröffentlicht wurden, sind hier zusammengefasst. Die Themen Aren‐Aren‐, Perfluoraren‐Aren‐, Schwefel‐Aren‐, Kation‐π‐ und Anion‐π‐Wechselwirkungen sowie Wasserstoffbrücken zu aromatischen Systemen werden behandelt. Das gewonnene Wissen kommt besonders der strukturbasierten Hit‐zur‐Leitstruktur‐Entwicklung und der Leitstrukturoptimierung sowohl in der pharmazeutischen als auch in der Pflanzenschutzindustrie zugute. Zudem erleichtert es die Entwicklung neuer Materialien und supramolekularer Systeme und soll zu weiteren Anwendungen von Wechselwirkungen mit aromatischen Ringen zur Kontrolle des stereochemischen Verlaufs chemischer Umsetzungen inspirieren.

A Quest for Ligand‐Unsupported Li+–π Interactions in Mono‐, Di‐, and Tritopic Lithium Arylborates

“…[2][3][4][5] Today, it is undisputed that Li + cation-π interactions are relevant for numerous applications, e.g. as a conformation-controlling tool in various regio-and stereoselective syntheses [6][7][8][9][10][11] and for the intercalation of lithium between graphite layers in lithium-ion batteries. [12] Experimental and theoretical gas-phase binding energies indicate that alkali metal ion-π interactions tend to follow a classical electrostatic trend (i.e.…”

Synthesis, crystal structures and photocatalytic properties of four silver(I) coordination polymers based on semirigid bis(pyrazole) and carboxylic acid co-ligands

“…This in turn results in a wide variety of sophisticated coordination architectures, including grids [6], helicates [7], cyclic helicates [8] and clusters [9]. In addition, Ag(I) coordination polymers (CPs) often show AgÁÁÁAg [10], AgÁÁÁp [11], AgÁÁÁN [12] and AgÁÁÁO [13] interactions, as well as noncovalent intermolecular interactions such as hydrogen bonding [14] and pÁÁÁp interactions [15], as well as exhibiting high-dimensional structures and interesting optoelectronic properties. However, it is still difficult to control the final supramolecular architectures because of various parameters such as the selection of metals with different coordination geometries [16], the nature of the ligands used [17], the metal-ligand ratio [18], solvent system [19], pH of the reaction [20] and temperature [21].…”

Catalysis with Anion–π Interactions

“…[4] Intriguing results with transport promised attractive applications to catalysis, because evidence for anion binding in the ground state implied that anionic transition states could be similarly stabilized. Anion-p interactions [5][6][7][8][9][10][11][12][13][14] were particularly interesting for this purpose because wonderful examples exist for catalysis with complementary cation-p interactions, [15] reaching from carbocation stabilization in terpenoid and steroid cyclization to surprisingly rare and recent use in organocatalysis. [16] Anion-p interactions, however, have essentially [5][6][7] not been used in catalysis.…”

“…[16] Anion-p interactions, however, have essentially [5][6][7] not been used in catalysis. [5][6][7][8][9][10][11][12][13][14] This is understandable, because experimental evidence for their functional relevance appeared only recently, [1] and discussions concerning their nature and significance continue. [5][6][7][8][9][10][11][12][13][14] The poor development of the field presumably originates from the limited occurrence, availability, and diversity of the required p-acids, that is aromatic rings with strong enough electron-withdrawing substituents to invert their usually negative quadrupole moments into positive ones.…”

“…This is a very reasonable value. [5][6][7][8][9][10][11][12][13][14] The DDG TS = 30.3 AE 0.4 kJ mol À1 corresponds to a transition-state recognition by the most p-acidic catalyst C2 with an apparent dissociation constant of K TS = 4.9 AE 0.8 mm. The catalytic proficiency more than doubled from (k cat /K m )/k non = 9.2 10 4 m À1 for C1 to (k cat /K m )/k non = 2.0 10 5 m À1 for C2.…”