Kinetic Modeling of Chiral Amplification and Enantioselectivity Reversal in Asymmetric Reactions
Keywords:
Asymmetric synthesis, chiral amplification, non linear effects, organozinc additions, catalysisAbstract
Abstract. Nonlinear effects in asymmetric synthesis and the occasionally observed reversal of the enantioselectivity of the employed catalyst are evaluated by a generalized kinetic approach. A non-autocatalytic and an autocatalytic reaction system are considered as two different prototype scenarios. It is predicted that during the course of enantioselectivity reversal in the non-autocatalytic system a gradual transition between both optically active states under loss of chiral amplification occurs while in the autocatalytic system a sharp transition under retention of chiral amplification is observed.
Resumen. Los efectos no lineales en síntesis asimétrica y la inversión de la enantioselectividad del catalizador empleado son evaluados a través de un modelado cinético generalizado. Un sistema reactivo autocatalítico y otro no autocatalítico son considerados como dos escenarios prototipos diferentes. Se predice que durante el curso de la inversión de la enantioselectividad en el sistema no autocatalítico ocurre una transición gradual entre los dos estados óptimamente activos donde la amplificación quiral decae mientras en el sistema autocatalítico ocurre una transición abrupta observándose la retención de la amplificación quiral.
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