New gold catalysts for enantioselective cyclization reactions

高效、立体选择性地构建复杂分子支架是合成复杂天然产物和药物分子的一大挑战。事实证明，金催化剂特别适合于这项任务。到目前为止，许多手性配体已经被开发出来，它们提供了各种不对映选择性碳环化反应的产物，具有良好的对映体选择性。然而，能够获得高光学纯度的底物范围往往是有限的，这限制了其在目标分子合成中的应用。本项目的目标是设计基于联芳基膦骨架的新型手性配体。这种结构解释了Au(I)络合物中独特的线性配位几何结构，因为它允许将手性信息定位在远离金属结合膦而靠近反应中心的位置。此外，立体和电子性质可以通过手性配体上的几个可变残基来调节。相应的金络合物将在环化反应中进行评估，并最终用于组装有价值的支架。

The efficient and stereoselective construction of complex molecular scaffolds is a major challenge for the synthesis of complex natural products and drug molecules. Gold catalysis proved to be especially suited for this task. Numerous chiral ligands have been developed to date that deliver the products of various enantioselective carbocyclization reactions with excellent enantioselectivity. Nevertheless, the substrate scope for which high optical purities can be achieved is often limited which restricts the application to the synthesis of target molecules.The objective of this project is the design of novel chiral ligands based on a biaryl phosphine framework. This architecture accounts for the unique linear coordination geometry in Au(I) complexes as it allows to position the chiral information distant from the metal binding phosphine but in close proximity to the site of reaction. In addition, the steric and electronic properties can be adjusted by several variable residues at the chiral ligand. The corresponding gold complexes will be evaluated in cyclization reactions and ultimately be used for the assembly of valuable scaffolds.