Enantioselectivity reversal by achiral additives in the soai reaction: A kinetic understanding

Numerical kinetic simulations have been employed to understand the origin of enantioselectivity reversal of chiral beta-amino alcohol catalysts occurring in the presence of their achiral analogs in the autocatalytic addition of diisopropylzinc to pyrimidine carbaldehydes (Soai reaction). In a preceding work (Rivera Islas, J.; Lavabre, D.; Grevy, J. M.; Hernandez Lamoneda, R.; Rojas Cabrera, H.; Micheau, J. C.; Buhse, T. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 13743-13748), we provided a possible explanation for the phenomenon of spontaneous mirror-symmetry breaking observed in this reaction. The effect of enantioselectivity reversal, giving rise to steep and abrupt transitions between opposed optically active states, has been identified by our current approach as another manifestation of such mirror-symmetry breaking capability. In the present case, we considered the involvement of the chiral catalyst and its achiral analog in the reaction network. Our modeling indicates that the enantioselectivity reversal can be either caused (i) by an interaction between the chiral and achiral additives or (ii) by an interaction of the customary products of the Soai reaction with the additives. The second option, which stands for the reversible inhibition of the chirally selective autocatalysts by the additives, could also explain a number of further additive effects in the Soai reaction reflecting the extraordinary sensitivity of this system toward the initial addition of almost any, even catalytically inactive, chiral substance.