Frank model and spontaneous emergence of chirality in closed systems.
In a closed system an irreversible enantioselective autocatalysis coupled to a mutual inhibition reaction, corresponding to a fast and low exergonic formation of the heterochiral dimer which reverts to the monomers in the final reaction work-up, yields absolute asymmetric synthesis even in the absence of chiral polarizations. This is due to the very high chiral amplifications of the initial small statistical deviations from the ideal racemic composition. Moreover, this system is sensitive to very small chiral polarizations (energy differences between transition states below the mJ mol(-1) range). This behaviour can also be observed in reversible exergonic reactions, because the racemization time scale is substantially longer than that of the transformation of the initial reagents. The effect of the presence of other reactions likely to occur (i.e. non-catalytic transformations, non-enantioselective catalysis and homodimer formation) is discussed. Even if these decrease the sensitivity of the network in several chemical scenarios, the emergence of kinetically controlled spontaneous symmetry breaking is not hindered. These features, together with the response of the system to a sequential reaction procedure, suggest that a similar type of network is at the heart of the Soai reaction.
Crusats
Joaquim
J
Departament de Química Orgànica, Universitat de Barcelona, C. Martí I Franquès 1, 08028-Barcelona, Catalonia, Spain.
Hochberg
David
D
Moyano
Albert
A
Ribó
Josep M
JM
D002384:Catalysis; D007700:Kinetics; D009930:Organic Chemicals / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
D009930:Organic Chemicals