Enantioselective Preparation of Planar‐Chiral Transition Metal Complexes by Asymmetric Olefin‐Metathesis Reactions in Metal Coordination Spheres
Enantioselective Preparation of Planar‐Chiral Transition Metal Complexes by Asymmetric Olefin‐Metathesis Reactions in Metal Coordination Spheres
复制标题
金属配位球中不对称烯烃复分解反应对映选择性制备平面手性过渡金属配合物
DOI：
10.1002/tcr.202100102
复制
发表时间：
2021
期刊：
影响因子：
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通讯作者：
Ogasawara Masamichi
中科院分区：
文献类型：
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作者：
石垣侑祐;水野真一;菅原一真;鈴木修一;鈴木孝紀;網井秀樹;Ogasawara Masamichi
平面手性过渡金属配合物是有机化学和有机金属化学中有用的手性助剂，它们被用作手性配体、手性催化剂或手性结构单元等。尽管此类平面手性物种在不对称合成中非常重要，但其光学活性形式的制备仍然是一个具有挑战性的问题。事实上，报道的平面手性配合物的催化对映选择性合成的例子很少，这一直是该领域的一个发展领域。在这个个人账户中，总结了我们研究小组在催化不对称合成各种平面手性过渡金属配合物方面的最新成果。由明确定义的钼-烷叉物种催化的不对称闭环复分解反应是控制二茂铁、二茂茂、（η6-芳烃）铬络合物和（η5-芳烃）锰（I）络合物的平面手性的有力方法。并介绍了用我们的方法得到的对映体富集配合物的应用。
Planar‐chiral transition metal complexes are useful chiral auxiliaries in organic and organometallic chemistry, and they have been utilized as chiral ligands, chiral catalysts, or chiral building blocks, etc. Despite the importance of such planar‐chiral species in asymmetric synthesis, their preparation in optically active forms is still a challenging problem. Indeed, reported examples of catalytic enantioselective synthesis of planar‐chiral complexes have been rare, and this has been a developing area in this field. In this personal account, recent results from our research group on the catalytic asymmetric synthesis of various planar‐chiral transition metal complexes are summarized. The asymmetric ring‐closing metathesis reactions catalyzed by the well‐defined molybdenum‐alkylidene species are powerful methods to control the planar chirality in ferrocenes, ruthenocenes, (η6‐arene)chromium complexes, and (η5‐cyclopentadienyl)manganese(I) complexes. Application of the enantiomerically enriched complexes obtained by our methods is described as well.