A Class of Readily Tunable Planar-Chiral Cyclopentadienyl Rhodium(III) Catalyst for Asymmetric C-H Activation.
A Class of Readily Tunable Planar-Chiral Cyclopentadienyl Rhodium(III) Catalyst for Asymmetric C-H Activation.
复制标题
一类用于不对称 C-H 活化的易于调节的平面手性环戊二烯基铑 (III) 催化剂。
DOI：
10.1002/anie.202201522
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发表时间：
2022
影响因子：
--
通讯作者：
Jun Wang
中科院分区：
文献类型：
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作者：
Xiaoqian Yan;Jijun Jiang;Jun Wang
手性半夹心双金属铑（III）（CpRh III）配合物是促进不对称C-H活化反应的强催化剂。它们的制备通常涉及将Cp基序连接或嵌入到某个手性骨架上，以形成所谓的手性Cp配体。然而，制备带有非手性Cp配体的平面手性CpRh III催化剂仍然是一个艰巨的挑战，很少有报道。本文描述了一类不寻常的带有非手性Cp配体的平面手性铑催化剂。与现有的催化剂不同，这种催化剂易于调节。合成了12种手性CpRh Ⅲ催化剂，并成功地用于两个手性C-H活化反应。该催化剂具有合成方便、结构可调性好等优点，有望在不对称C-H催化反应中得到更广泛的应用。
Chiral half-sandwich cyclopentadienyl rhodium(III) (CpRh III ) complexes are powerful catalysts to promote asymmetric C-H activation reactions. Their preparation normally involved linking or embedding the Cp motif to or into a certain chiral backbone to forge the so-called chiral Cp ligand. However, preparation of planar-chiral CpRh III catalyst bearing a non-chiral Cp ligand remains a formidable challenge and rarely reported. We describe herein an unusual class of planar-chiral rhodium catalysts bearing non-chiral Cp ligands. Differed from existing ones, this catalyst is facile to tune. Twelve chiral CpRh III catalysts had been prepared with ease, and successfully used into two enantioselective C-H activation reactions. Given its convenient synthesis and high structural tunability, this catalyst is expected to find more utilities in asymmetric C-H activation.