Elucidating the Role of Isotopically Chiral Initiators in the Soai Asymmetric Autocatalytic Reaction

2018-06-18T16:57:35Z (GMT) by Neil Hawbaker Donna Blackmond
A mechanistic rationalization is given for how asymmetric amplification is induced with fidelity in the Soai autocatalytic reaction by chiral initiators that are enantiomeric only by virtue of an isotope, e.g. – CH3 vs.CD3. A transient <i>inhibition</i> of the autocatalytic pathway at the outset of the reaction implicates an interaction between initiator and product initially formed in the uncatalyzed background reaction. Selectivity in formation of the product-initiator complex ultimately induces a slight enantioenrichment in the active dimer catalysts that trigger and direct the autocatalytic pathway.<br>