Schmauck J, Breugst M
Universität zu Köln, Department für Chemie, Greinstraße 4, 50939 Köln, Germany.
Org Biomol Chem. 2017 Oct 4;15(38):8037-8045. doi: 10.1039/c7ob01599b.
Pnicogen bonding is a noncovalent interaction between the electrophilic region of a phosphorus atom and a Lewis base. Although this interaction can be comparable in strength to other noncovalent interactions, no systematic application in organic synthesis or catalysis is known so far. To identify the potential of this interaction for organocatalysis, we have now analysed different pnicogen-bond donors as catalysts for the activation of three different model reactions employing density functional theory. Our calculations suggest rate accelerations of several orders of magnitude for all cases indicating that synthetic applications should be feasible. Furthermore, our results indicate that pnicogen-bond donors can be comparable to halogen-bond-based catalysts in these reactions.
磷键是磷原子的亲电区域与路易斯碱之间的一种非共价相互作用。尽管这种相互作用在强度上可与其他非共价相互作用相媲美，但迄今为止，在有机合成或催化中尚无系统的应用。为了确定这种相互作用在有机催化中的潜力，我们现在利用密度泛函理论分析了不同的磷键供体作为催化剂用于三种不同模型反应的活化情况。我们的计算表明，在所有情况下反应速率都加快了几个数量级，这表明合成应用应该是可行的。此外，我们的结果表明，在这些反应中磷键供体可与基于卤键的催化剂相媲美。
