title: Elucidating the origin of diastereoselectivity in a self-replicating system: selfishness versus altruism.
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 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.
authors.affiliation: Lehrstuhl für Organische Chemie I, Bioorganische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany. arne.dieckmann@rub.de
authors.forename: Arne
authors.initials: A
authors.lastname: Dieckmann
authors.forename: Sabrina
authors.initials: S
authors.lastname: Beniken
authors.forename: Christian D
authors.initials: CD
authors.lastname: Lorenz
authors.forename: Nikos L
authors.initials: NL
authors.lastname: Doltsinis
authors.forename: Günter
authors.initials: G
authors.lastname: von Kiedrowski
mesh_terms: D003198:Computer Simulation; D003517:Cyclopentanes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008301:Maleimides / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D003517:Cyclopentanes; D008301:Maleimides; C017332:fulvene; C043592:maleimide