Elucidating the Origin of Diastereoselectivity in a Self-Replicating System: Selfishness versus Altruism

We have investigated a diastereoselective self‐replicating system based on a cycloaddition of a fulvene derivative and a maleimide using a two‐pronged approach of combining NMR spectroscopy with computational modelling. Two diastereomers are formed with identical rates in the absence of replication....

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Veröffentlicht in:Chemistry : a European journal 2011-01, Vol.17 (2), p.468-480
Hauptverfasser: Dieckmann, Arne, Beniken, Sabrina, Lorenz, Christian D., Doltsinis, Nikos L., von Kiedrowski, Günter
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Sprache:eng
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Zusammenfassung:We have investigated a diastereoselective self‐replicating system based on a cycloaddition of a fulvene derivative and a maleimide using a two‐pronged approach of combining NMR spectroscopy with computational modelling. Two diastereomers are formed with identical rates in the absence of replication. When replication is enabled, one diastereomer takes over the resources as a “selfish” autocatalyst, while exploiting the competitor as a weak “altruist”, resulting in a diastereoselectivity of 16:1. We applied 1D and 2D NMR spectroscopic techniques supported by ab initio chemical shifts as well as ab initio molecular dynamics simulations to study the structure and dynamics of the underlying network. This powerful combination allowed us to decipher the energetic and structural rationale behind the observed behaviour, while static computational methods currently used in the field did not. Modelled to perfection! A diastereoselective self‐replicating system based on the cycloaddition of a fulvene derivative and a maleimide was investigated by using a two‐pronged approach of combining NMR spectroscopy with computational modelling. One template takes over the resources as a “selfish” autocatalyst, while exploiting the competitor as a weak “altruist”, resulting in a diastereoselectivity of 16:1.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201002325