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

八面体手性金属络合物作为惰性支架用于不对称催化剂的设计

• 批准号: 259002125
• 负责人: Professor Dr. Eric Leif Meggers
• 金额: --
• 依托单位: Fachgebiet Chemische Biologie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/259002125?language=en
• 关键词: Octahedral; Chiral; Metal; Complexes; Inert

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.

在不对称催化中，手性来源是催化剂功能的关键方面，并且通常源自一个或多个四面体立体中心、轴向手性、平面手性或其组合。本论文的主要目的是研究利用手性金属八面体金属配合物作为模板分子设计不对称催化剂。在这个概念中，金属实现了纯粹的结构作用，而催化作用是通过在惰性金属络合物的三维配体球中适当排列的官能团介导的。特别地，手性金属环化铱（III）配合物将用于设计不对称烯胺催化剂、不对称布朗斯台德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型的不对称催化剂，这些催化剂基于含金属的支架，但将不对称有机催化的概念应用于其催化机制。

项目成果

Exploiting Octahedral Stereocenters: From Enzyme Inhibition to Asymmetric Photoredox Catalysis.

• DOI: 10.1002/anie.201612516
• 发表时间: 2017-05
• 期刊: Angewandte Chemie
• 作者: E. Meggers

Stereogenic-Only-at-Metal Asymmetric Catalysts.

• DOI: 10.1002/asia.201700739
• 发表时间: 2017-09
• 期刊: Chemistry, an Asian journal
• 作者: Lilu Zhang;E. Meggers

Asymmetric Nazarov Cyclizations Catalyzed by Chiral-at-Metal Complexes

• DOI: 10.1002/adsc.201701546
• 发表时间: 2018-06-05
• 期刊: ADVANCED SYNTHESIS & CATALYSIS
• 影响因子: 5.4
• 作者: Mietke，Thomas;Cruchter，Thomas;Meggers，Eric
• 通讯作者: Meggers，Eric

Asymmetric Nucleophilic Catalysis with an Octahedral Chiral-at-Metal Iridium(III) Complex

• DOI: 10.1021/acscatal.7b01296
• 发表时间: 2017-08-01
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Cruchter, Thomas;Medvedev, Michael G.;Meggers, Eric
• 通讯作者: Meggers, Eric