Practical Synthesis of Chiral Ferrocenenylphosphino-Gold(I) Catalysts and NEST Analysis of the Enantioinduction

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-01-24 DOI:10.1021/acscatal.4c07495

Pablo Mora, Imma Escofet, Maria Besora, Federica Cester Bonati, Antonio M. Echavarren

引用次数: 0

Abstract

The concise modular synthesis of a family of monodentate 1,2-disubstituted ferrocene ligands containing a diaryl phosphine and a 2-aryl indole is described. Their gold(I) complexes were applied to the enantioselective gold(I)-catalyzed formal [4 + 2] cycloaddition of 1,6-arylenynes, the enyne cyclization/nucleophile addition of N-tethered 1,6-enynes, and the methoxycyclization of 1,6-arylenynes with high levels of enantioselectivity in all cases. Crystallographic and computational studies highlighted the relevant role of noncovalent interactions within the ligand scaffold and between the ligand and substrate in the modes of enantioinduction in the cyclization of unsaturated substrates. Our recently developed open-source tool NEST was applied to analyze the chiral pockets of the catalysts, which in combination with RDKit allowed us to understand the enantioselectivity in these reactions, paving the way for a predictive-based approach toward the rational development of chiral ligands for enantioselective Au(I) catalysis.

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手性二茂铁基磷酸金(I)催化剂的实际合成及对映体诱导的NEST分析

描述了一组含有二芳基膦和2芳基吲哚的单齿1,2-二取代二茂铁配体的简洁模块化合成。他们的金(I)配合物被应用于金(I)催化的1,6-芳炔的形式[4 + 2]环加成，n -拴链1,6-芳炔的炔环化/亲核加成，以及1,6-芳炔的甲氧基环化，在所有情况下都具有高水平的对映选择性。晶体学和计算研究强调了配体支架内部和配体与底物之间的非共价相互作用在不饱和底物环化的对映体诱导模式中的相关作用。我们最近开发的开源工具NEST用于分析催化剂的手性口袋，该工具与RDKit相结合，使我们能够了解这些反应的对映选择性，为基于预测的方法合理开发用于对映选择性Au(I)催化的手性配体铺平了道路。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.