Dey Purusattam, Rai Pramod, Maji Biplab
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, 741246, India.
ACS Org Inorg Au. 2021 Dec 3;2(2):99-125. doi: 10.1021/acsorginorgau.1c00032. eCollection 2022 Apr 6.
The field of asymmetric catalysis has been developing to access synthetically efficacious chiral molecules from the last century. Although there are many sustainable ways to produce nonracemic molecules, simplified and unique methodologies are always appreciated. In the recent developments of asymmetric catalysis, chiral-at-metal Lewis acid catalysis has been recognized as an attractive strategy. The catalysts coordinatively activate a substrate while serving the sole source of chirality by virtue of its helical environment. These configurationally stable complexes were utilized in a large number of asymmetric transformations, ranging from asymmetric Lewis acid catalysis to photoredox and electrocatalysis. Here we provide a comprehensive review of the current advancements in asymmetric catalysis utilizing iridium and rhodium-based chiral-at-metal complexes as catalysts. First, the asymmetric transformations via LUMO and HOMO activation assisted by a chiral Lewis acid catalyst are reviewed. In the second part, visible-light-induced asymmetric catalysis is summarized. The asymmetric transformation via the electricity-driven method is discussed in the final section.
自上个世纪以来，不对称催化领域一直在不断发展，以获取具有合成效用的手性分子。尽管有许多可持续的方法来制备非外消旋分子，但简化且独特的方法始终受到青睐。在不对称催化的最新进展中，金属手性路易斯酸催化已被视为一种有吸引力的策略。这类催化剂通过配位作用活化底物，同时凭借其螺旋环境作为手性的唯一来源。这些构型稳定的配合物已被广泛应用于大量的不对称转化反应中，从不对称路易斯酸催化到光氧化还原和电催化。在此，我们全面综述了以铱和铑基金属手性配合物作为催化剂在不对称催化方面的当前进展。首先，综述了在手性路易斯酸催化剂辅助下通过LUMO和HOMO活化实现的不对称转化。第二部分总结了可见光诱导的不对称催化。最后一部分讨论了通过电驱动方法实现的不对称转化。
