Real‐Time Control of the Enantioselectivity of a Supramolecular Catalyst Allows Selecting the Configuration of Consecutively Formed Stereogenic Centers

作者：Jérémy M. Zimbron, Xavier Caumes, Yan Li, C.M. Thomas, Matthieu Raynal, Laurent Bouteiller · 发表于：Angewandte Chemie International Edition · 年份：2017 · DOI：10.1002/anie.201706757 · 被引用次数：55 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Synthesis and Properties of Aromatic Compounds、Supramolecular Self-Assembly in Materials

Abstract The enantiomeric state of a supramolecular copper catalyst can be switched in situ in ca. five seconds. The dynamic property of the catalyst is provided by the non‐covalent nature of the helical assemblies supporting the copper centers. These assemblies are formed by mixing an achiral benzene‐1,3,5‐tricarboxamide (BTA) phosphine ligand (for copper coordination) and both enantiomers of a chiral phosphine‐free BTA co‐monomer (for chirality amplification). The enantioselectivity of the hydrosilylation reaction is fixed by the BTA enantiomer in excess, which can be altered by simple BTA addition. As a result of the complete and fast stereochemical switch, any combination of the enantiomers was obtained during the conversion of a mixture of two substrates.