Chiral paddle-wheel diruthenium complexes for asymmetric catalysis
Chiral paddle-wheel diruthenium complexes for asymmetric catalysis
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DOI：
10.1038/s41929-020-00513-w
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发表时间：
2020-10-05
期刊：
影响因子：
37.8
通讯作者：
Matsunaga, Shigeki
中科院分区：
文献类型：
--
作者：
Miyazawa, Taku;Suzuki, Takuro;Matsunaga, Shigeki
手性催化剂的开发是不对称催化的一个基本目标，也是提供高效合成手性分子方法的关键。手性桨轮络合物在铑催化的不对称碳烯/氮烯转移反应和刘易斯酸催化的反应中提供了高度可调的手性环境。然而，具有其他过渡金属作为活性金属中心的手性桨轮络合物在不对称催化中尚未被确定。本文报道了手性桨轮型双钌配合物的合成、结构和高催化性能。阳离子手性双钌配合物[Ru-2（（S）-BPTPI）（4）]（+）作为刘易斯酸催化剂催化不对称杂Diels-桤木反应，表现出显著的活性，转化数高达1，880，000，对映体选择性> 90% e.e.手性双钌配合物在氧化条件下的C-H胺化和环丙烷化反应中也表现出良好的反应活性和高的对映选择性，表明它们对氧化具有很高的耐受性。我们的结果表明，手性桨轮二钌支架是一个有前途的不对称催化平台。
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 [Ru-2((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.