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用于对映选择性钴电催化C-H活化的κ-恶唑啉前配体的参数化

Parametrization of κ-,-Oxazoline Preligands for Enantioselective Cobaltaelectro-Catalyzed C-H Activations.

作者信息

Dana Suman, Pandit Neeraj Kumar, Boos Philipp, von Münchow Tristan, Peters Sven Erik, Trienes Sven, Haberstock Laura, Herbst-Irmer Regine, Stalke Dietmar, Ackermann Lutz

机构信息

WISCh (Wöhler-Research Institute for Sustainable Chemistry), Georg-August-Universität Göttingen, 37077 Göttingen, Germany.

出版信息

ACS Catal. 2025 Feb 28;15(6):4450-4459. doi: 10.1021/acscatal.5c00250. eCollection 2025 Mar 21.

Abstract

Enantioselective electrocatalyzed C-H activations have emerged as a transformative platform for the assembly of value-added chiral organic molecules. Despite the recent progress, the construction of multiple C(sp)-stereogenic centers via a C(sp)-C(sp) bond formation has thus far proven to be elusive. In contrast, we herein report an annulative C-H activation strategy, generating chiral Fsp-rich molecules with high levels of diastereo- and enantioselectivity. κ-,-oxazoline preligands were effectively employed in enantioselective cobalt(III)-catalyzed C-H activation reactions. Using DFT-derived descriptors and regression statistical modeling, we performed a parametrization study on the modularity of chiral κ-,-oxazoline preligands. The study resulted in a model describing ligands' selectivity characterized by key steric, electronic, and interaction behaviors.

摘要

对映选择性电催化C-H活化已成为用于组装高附加值手性有机分子的变革性平台。尽管最近取得了进展,但迄今为止,通过形成C(sp)-C(sp)键来构建多个C(sp) - 立体ogenic中心已被证明是难以实现的。相比之下,我们在此报告了一种环化C-H活化策略,可生成具有高非对映选择性和对映选择性的富含Fsp的手性分子。κ-,-恶唑啉前配体有效地用于对映选择性钴(III)催化的C-H活化反应。使用DFT衍生的描述符和回归统计建模,我们对手性κ-,-恶唑啉前配体的模块化进行了参数化研究。该研究得出了一个描述配体选择性的模型,其特征在于关键的空间、电子和相互作用行为。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fab9/11934137/47d6283a71e7/cs5c00250_0001.jpg

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