Interaction mechanisms enantioselectivity

Interactive mechanism for enantioselective organocatalytic Friedel-Crafts alkylation... 

Interactive mechanism for the proline-catalysed enantioselective aldol reaction... 

Interactive mechanism for catalytic enantioselective additions controlled by chiral anions... 

The principal mechanism for separation of enantiomers in CE is enantioselective selector-analyte interactions. The enantioselectivity might be reflected in the binding constants, in the mobilities of diastereomeric associates, or in both simultaneously. 

Absorption, metaboHsm, and biological activities of organic compounds are influenced by molecular interactions with asymmetric biomolecules. These interactions, which involve hydrophobic, electrostatic, inductive, dipole—dipole, hydrogen bonding, van der Waals forces, steric hindrance, and inclusion complex formation give rise to enantioselective differentiation (1,2). Within a series of similar stmctures, substantial differences in biological effects, molecular mechanism of action, distribution, or metaboHc events may be observed. Eor example, (R)-carvone [6485-40-1] (1) has the odor of spearrnint whereas (5)-carvone [2244-16-8] (2) has the odor of caraway (3,4). 

There can be significant differences in the detailed structure and mechanism of these catalysts. For example, the geometry of the phosphine ligands may affect the reactivity at the metal ion, but the basic elements of the mechanism of enantioselection are similar. The phosphine ligands establish a chiral environment and provide an appropriate balance of reactivity and stability for the metal center. The reactants bind to the metal through the double bond and at least one other functional group, and mutual interaction with the chiral environment is the basis for enantioselectivity. The new stereocenters are established under the influence of the chiral environment. 

A number of specialised stationary phases have been developed for the separation of chiral compounds. They are known as chiral stationary phases (CSPs) and consist of chiral molecules, usually bonded to microparticulate silica. The mechanism by which such CSPs discriminate between enantiomers (their chiral recognition, or enantioselectivity) is a matter of some debate, but it is known that a number of competing interactions can be involved. Columns packed with CSPs have recently become available commercially. They are some three to five times more expensive than conventional hplc columns, and some types can be used only with a restricted range of mobile phases. Some examples of CSPs are given below ... 

The enhanced synthetic potential of rhodium-complex-catalyzed enantioselective hydrogenation provided by these advances in ligand design has led to renewed interest in the reaction mechanism, and here we highlight four recent topics (i) the extended base of reactive intermediates (ii) an improved quadrant model for ligand-substrate interactions (iii) computational approaches to mechanism and (iv) (bis)-monophosphine rhodium complexes in enantioselective hydrogenation. These are discussed in turn. 

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