Asymmetric synthesis plays a critical role in the production of pharmaceuticals, agrochemicals, and a wide array of functional materials. Recent years have witnessed remarkable successes in asymmetric synthesis including Friedel-Crafts (F-C) alkylation, Diels-Alder (D-A) cycloaddition, Michael addition and sulfoxidation reactions. In these reactions, copper-based organic catalysts and enzymes have emerged as extraordinary and powerful catalysts to offer precise control over the stereochemistry. However, organic catalysis faces the challenges of harsh reaction environment as well as poor specificity, and enzymes catalyze a narrow range of substrates. In this regard, artificial copper enzymes, incorporating chemically synthetic copper centers into protein scaffolds/nucleic acid strands, mimic the selectivity and mild condition of biocatalysis and meanwhile keep the intrinsic catalytic reactivity of chemical catalysis. This review outlines the progresses on artificial copper enzymes catalyzed asymmetric synthesis and illustrates their design principles and synthesis strategies. It is believed that artificial copper enzymes are promising to reshape the landscape of asymmetric synthesis and facilitate a diverse range of chemical transformations.

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人工铜生物催化剂的不对称合成

不对称合成在药物、农用化学品和各种功能材料的生产中发挥着关键作用。近年来，在不对称合成方面取得了显着的成功，包括弗里德尔-克拉夫茨（FC）烷基化、狄尔斯-阿尔德（DA）环加成、迈克尔加成和磺化氧化反应。在这些反应中，铜基有机催化剂和酶已成为非凡而强大的催化剂，可以精确控制立体化学。然而，有机催化面临着反应环境恶劣、特异性差、酶催化底物范围窄等挑战。在这方面，人工铜酶将化学合成的铜中心掺入蛋白质支架/核酸链中，模拟了生物催化的选择性和温和条件，同时保留了化学催化的固有催化反应活性。该综述概述了人工铜酶催化不对称合成的进展，并阐述了其设计原理和合成策略。人们相信，人工铜酶有望重塑不对称合成的格局并促进多种化学转化。