有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
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Chiral-at-Metal錯体の精密設計:四面体型キラル亜鉛錯体の合成と触媒機能
遠藤 健一Yuanfei Liu宇部 仁士長田 浩一塩谷 光彦
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2022 年 80 巻 5 号 p. 498-505

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Chiral metal complexes have been widely used as enantioselective catalysts and chiroptical materials. In recent years, “chiral-at-metal” complexes, in which the ligand is achiral but the coordination geometry is chiral, have appeared, expanding the variety of chiral metal complexes. However, functional chiral-at-metal complexes are so far limited to those with octahedral or half-sandwich geometry. Since tetrahedral chiral-at-metal complexes usually racemize instantaneously, optically pure complexes were not available, especially in solution. Here, we present the first example of a tetrahedral chiral-at-metal complex with high configurational stability and enantioselective catalytic function. In this complex, an elaborately designed tridentate ligand imparted stability against stereoinversion while leaving a labile coordination site. We have also developed a method for the asymmetric synthesis of this chiral-at-metal complex using an acidic chiral auxiliary. The emergence of tetrahedral chiral-at-metal complexes is expected to make a significant contribution to catalytic chemistry and materials science.

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