科研之友
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摘要
Nonlinear effects in asymmetric synthesis are identified by a nonlinear relationship between the enantiomeric excess of the product versus that of the chiral catalyst. Such information is not always sufficient to reveal if the active catalyst acts in its monomeric or dimeric form. Numerical simulations of two kinetic models including monomer and dimer catalysis with a Michaelis-Menten-type reaction mechanism suggest that the nonlinear effects are mainly sensitive to an analogue of the Michaelis-Menten constant as well as to the diastereomeric energy difference between homochiral and heterochiral catalyst dimers. A practical monomer- dimer discrimination table is presented showing that the influence of the initial catalyst enantiomeric excess and the catalytic charge on the product enantiomeric excess and on the reaction half-time together with the assessment of the kinetic order of the prochiral substrate are sufficient to assess whether the active catalyst acts in its monomeric or dimeric form.
- 出版日期2016-5-20
