Lehrstuhl für Organische Chemie I, Bioorganische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany.
Chemistry. 2011 Jan 10;17(2):468-80. doi: 10.1002/chem.201002325.
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.
我们采用 NMR 光谱学与计算建模相结合的双管齐下方法，研究了基于富烯衍生物与马来酰亚胺环加成的非对映选择性自复制体系。在没有复制的情况下，两种非对映异构体以相同的速率形成。当启用复制时，一种非对映异构体作为“自私”的自催化剂接管资源，同时利用竞争对手作为较弱的“利他主义者”，从而导致非对映选择性为 16:1。我们应用了一维和二维 NMR 光谱技术，辅以从头算化学位移和从头算分子动力学模拟，来研究基础网络的结构和动态。这种强大的组合使我们能够破解观察到的行为背后的能量和结构原理，而目前该领域中使用的静态计算方法则无法做到这一点。
