Octahedral Chiral-at-Metal Complexes as Inert Scaffolds for the Design of Asymmetric Catalysts

在不对称催化中，手性的来源是催化剂功能的一个关键方面，通常来自一个或多个四面体立体中心、轴向手性、平面手性或它们的组合。本文的主要目的是研究用惰性手性金属八面体金属配合物作为模板设计不对称催化剂。在这个概念中，金属发挥了纯粹的结构作用，而催化作用是通过在惰性金属配合物的三维配体球体中适当排列的官能团来介导的。特别是手性金属环金属化铱（III）配合物将用于设计不对称烯胺催化剂、不对称Brønsted酸催化剂和不对称酰基转移催化剂。这项研究可能有助于开发一类新的不对称催化剂，这些催化剂以含金属支架为基础，但应用不对称有机催化的概念来研究其催化机制。

In asymmetric catalysis, the source of chirality is a crucial aspect for the catalysts function and is typically derived from one or more tetrahedral stereogenic centers, axial chirality, planar chirality, or a combination thereof. This proposal has the main objective to investigate the use inert chiral-at-metal octahedral metal complexes as templates for the design of asymmetric catalysts. In this concept, the metal fulfills a purely structural role, whereas catalysis is mediated through functional groups properly arranged in the three-dimensional ligand sphere of the inert metal complexes. Particularly, chiral-at-metal cyclometalated iridium(III) complexes will be used for the design of asymmetric enamine catalysts, asymmetric Brønsted acid catalysts, and asymmetric acyl transfer catalysts. This proposed research may contribute to the development of a novel class of asymmetric catalysts which are based on metal-containing scaffolds but apply the concepts of asymmetric organocatalysis for their catalytic mechanisms.