Deracemization of Chiral-at-Ruthenium Catalyst by Diastereoselective Dynamic Resolution,Organometallics

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Deracemization of Chiral-at-Ruthenium Catalyst by Diastereoselective Dynamic Resolution
Organometallics ( IF 2.5 ) Pub Date : 2021-12-19 , DOI: 10.1021/acs.organomet.1c00602
Dominik Baran ₁ , Sergei I. Ivlev ₁ , Eric Meggers ₁

Affiliation

In this work, we introduce an auxiliary-mediated deracemization protocol in the synthesis of a non-C₂-symmetric chiral-at-ruthenium catalyst bearing two cyclometalated 7-methyl-1,7-phenanthrolinium heterocycles, a CO ligand, and an additional labile MeCN ligand. Upon coordination of a monodentate chiral oxazoline ligand as chiral auxiliary, the racemic complex mixture is transformed into a single diastereomer in quantitative yield via a diastereoselective dynamic resolution process. After removal of the oxazoline ligand under acidic conditions, enantiomerically pure complexes (>20:1 er) with a Δ- and Λ-configuration were obtained. An application of the chiral-at-ruthenium catalyst to an enantioselective ring-closing C(sp³)-H amidation of a 1,2,4-dioxazol-5-one to the corresponding chiral γ-lactam is demonstrated.

中文翻译：

非对映选择性动态拆分手性钌催化剂的去外消旋化

在这项工作中，我们在非合成引入的辅助介导的去外消旋协议Ç ₂ -对称手性在钌催化剂轴承2环金属化7-甲基-1,7-菲咯啉的杂环，在CO配体，和一个附加不稳定的 MeCN 配体。在将单齿手性恶唑啉配体作为手性助剂配位后，外消旋络合物混合物通过非对映选择性动态拆分过程转化为定量产率的单一非对映异构体。在酸性条件下去除恶唑啉配体后，获得了具有 Δ- 和 Λ- 构型的对映体纯复合物 (>20:1 er)。手性钌催化剂在对映选择性闭环 C(sp ^{3) 中的应用})-H 酰胺化 1,2,4-dioxazol-5-one 为相应的手性 γ-内酰胺。

更新日期：2022-01-10

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