Elucidating the origin of diastereoselectivity in a self-replicating system: selfishness versus altruism.
Chemistry
; 17(2): 468-80, 2011 Jan 10.
Article
em En
| MEDLINE
| ID: mdl-21207563
ABSTRACT
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 161. We applied 1D and 2Dâ
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.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Espectroscopia de Ressonância Magnética
/
Modelos Moleculares
/
Ciclopentanos
/
Maleimidas
Idioma:
En
Revista:
Chemistry
Ano de publicação:
2011
Tipo de documento:
Article