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Oscillatory Symmetry Breaking in the Soai Reaction
A kinetic model of spontaneous amplification of enantiomeric excess in the autocatalytic addition of diisopropylzinc to prochiral pyrimidine carbaldehydes is extended by a negative feedback process. Simulations based on the extended model result in large-amplitude oscillations both in a continuous-f...
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| Published in: | The journal of physical chemistry. B 2008-07, Vol.112 (30), p.9196-9200 |
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| Main Authors: | , , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
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| Summary: | A kinetic model of spontaneous amplification of enantiomeric excess in the autocatalytic addition of diisopropylzinc to prochiral pyrimidine carbaldehydes is extended by a negative feedback process. Simulations based on the extended model result in large-amplitude oscillations both in a continuous-flow stirred tank reactor (CSTR) and in a semibatch configuration under optimized initial conditions. When sustained oscillations are maintained in a CSTR, no enantiomeric product distribution could be observed in the calculated series; the system keeps its initial enantiomeric ratio endlessly. During damped oscillations, or steady-state conditions, however, chiral amplification from a very small initial enantiomeric excess to more than 99% occurs in a semibatch configuration. Calculations indicated spontaneous enantiomeric product enrichment (i.e., accumulation of one of the enantiomers at the cost of the other one) from strictly achiral starting conditions in a semibatch configuration due to the inherent numerical error of the integrator method, which can be regarded as a model of the statistical fluctuation in the numbers of enantiomeric molecules. |
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| ISSN: | 1520-6106 1520-5207 |
| DOI: | 10.1021/jp803334b |