铜催化手性硒基多功能合成物的对映选择性合成

摘要(中文译文)

对映体富集的有机硒化合物在有机合成、不对称催化和药物化学等领域有着广泛的应用，这推动了对高效催化方法的需求，以获取新型手性有机硒分子。然而，与氧基和硫基类似物相比，硒基手性化合物的催化不对称合成路线仍发展不足，且尚无催化方法被报道用于制备能够承担多重功能角色的手性硒基分子。在此，我们描述了一种温和且简单的铜(II)/二胺催化体系，可提供具有广泛下游用途的手性硒基多功能合成子，包括作为有价值的合成中间体、手性有机催化剂和生物活性剂的应用。计算研究探索了对映选择性决定因素的可能性以及硒配位四齿铜催化剂模型。广泛的底物范围实验支持了这一机理提议。我们预期这项工作将提供一个稳健的硒基合成工具箱，并拓展手性有机硒化学中可及的化学空间。

Abstract

Enantioenriched organoselenium compounds have found diverse applications across organic synthesis, asymmetric catalysis, and medicinal chemistry, driving a growing demand for efficient catalytic approaches to access novel chiral organoselenium molecules. However, in contrast to their oxygen- and sulfur-based counterparts, catalytic asymmetric routes to selenium-based chiral compounds remain underdeveloped, and no catalytic method has been reported for preparing chiral selenium-based molecules capable of serving multiple functional roles. Here, we describe a mild and simple Cu-(II)/diamine catalytic system that delivers chiral selenium-based versatile synthons with broad downstream utility, including applications as valuable synthetic intermediates, chiral organocatalysts, and bioactive agents. Computational studies explored the possibility of enantioselectivity-determining factors and a selenium-coordinating tetradentate copper catalyst model. A broad substrate scope was performed that supported this mechanistic proposal. We anticipate that this work will furnish a robust selenium-based synthetic toolbox and expand the accessible chemical space in chiral organoselenium chemistry.

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