The development of robust and reactive chiral catalysts is a fundamental aim in asymmetric catalysis, and crucial for providing efficient methods for synthesizing chiral molecules. Chiral paddle-wheel bimetallic complexes provide a highly tunable chiral environment in rhodium-catalysed asymmetric carbene/nitrene transfer reactions and Lewis acid-catalysed reactions. Chiral paddle-wheel complexes having other transition metals as the reactive metal centre, however, have not yet been identified in asymmetric catalysis. Here, we report the synthesis, structures and high catalytic performances of chiral paddle-wheel diruthenium complexes. The cationic chiral diruthenium complex [Ru₂((S)-BPTPI)₄]⁺ exhibited remarkable reactivity as a Lewis acid catalyst for asymmetric hetero-Diels–Alder reactions, achieving a turnover number of up to 1,880,000 with high enantioselectivity (>90% e.e.). The chiral diruthenium complexes also exhibited good reactivity and high enantioselectivity in C–H amination and cyclopropanation reactions under oxidizing conditions, indicating their high tolerance towards oxidation. Our results reveal the chiral paddle-wheel diruthenium scaffold as a promising platform for asymmetric catalysis.

鲁棒性和反应性手性催化剂的开发是不对称催化的基本目标，对于提供合成手性分子的有效方法至关重要。手性桨轮双金属配合物在铑催化的不对称卡宾/硝烯转移反应和路易斯酸催化的反应中提供了高度可调的手性环境。然而，尚未在不对称催化中鉴定出具有其他过渡金属作为反应性金属中心的手性桨轮络合物。在这里，我们报告手性桨轮二钌配合物的合成，结构和高催化性能。阳离子手性二钌络合物[Ru ₂（（S）-BPTPI）₄ ] ⁺表现出出色的反应性，可作为路易斯酸催化剂用于不对称杂Diels-Alder反应，实现高达1,880,000的周转数和高对映选择性（> 90％ee）。在氧化条件下，CH-H胺化和环丙烷化反应中，手性二钌配合物也表现出良好的反应性和高对映选择性，表明它们对氧化的高耐受性。我们的研究结果表明手性桨轮钌支架是不对称催化的有前途的平台。