Recent Advances in Asymmetric Organometallic Electrochemical Synthesis (AOES).

Abstract

ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with asymmetric transition metal catalysis. On one hand, we have rationalized that organometallic compounds can serve as molecular electrocatalysts (mediators) to reduce overpotentials and enhance both the reactivity and selectivity of reactions. On the other hand, the conditions for asymmetric transition metal catalysis can be substantially improved through electrochemistry, enabling precise modulation of the transition metal's oxidation state by controlling electrochemical potentials and regulating the electron transfer rate via current adjustments. This synergistic approach addresses key challenges inherent in traditional asymmetric transition metal catalysis, particularly those related to the use of redox-active chemical reagents. Furthermore, the redox potentials of molecular electrocatalysts can be conveniently tuned by modifying their ligands, thereby governing the reaction regioselectivity and stereoselectivity. As a result, the AOES has emerged as a powerful and promising tool for the synthesis of chiral compounds.In this Account, we summarize and contextualize our recent efforts in the field of AOES. Our primary strategy involves leveraging the controllability of electrochemical potential and current to regulate the oxidation state of organometallics, thereby facilitating the desired reactions. An efficient asymmetric synthesis platform was established under mild conditions, significantly reducing the reliance on chemical redox reagents. Our research has been systematically categorized into three sections based on distinct electrolysis modes: asymmetric transition metal catalysis combined with anodic oxidation, cathodic reduction, and paired electrolysis. In each section, we highlight our innovative discoveries tailored to the unique characteristics of the respective electrolysis modes.In many transformations, transition metal-catalyzed reactions involving traditional chemical redox reagents and those utilizing electrochemistry exhibit similar reactivities. However, we also observed notable differences in certain cases. These findings include the following: (1) Enhanced efficiency in asymmetric electrochemical synthesis: for instance, the Rh-catalyzed enantioselective electrochemical functionalization of C-H bonds demonstrates superior efficiency. (2) Expanded scope of transformations: certain transformations, previously challenging in traditional transition metal catalysis, can be achieved through electrochemistry due to the tunability of redox potentials. A notable example is the enantioselective reductive coupling of aryl chlorides, which significantly expands the range of accessible transformations. Additionally, our mechanistic studies explore unique techniques intrinsic to electrochemistry, such as controlled potential electrolysis experiments, the impact of electrode materials on catalyst performance, and cyclic voltammetry studies. These investigations provide a more intuitive understanding of the behavior of metal catalysts through the study of electrochemical mechanisms, which can also guide the design of new catalytic systems.The advancements in this field offer a robust platform for environmentally friendly and sustainable selective asymmetric transformations. By integrating electrochemistry with transition metal catalysis, we have developed a versatile approach for organic synthesis that not only enhances the efficiency and selectivity of reactions but also reduces the environmental impact. We anticipate that this Account will stimulate further research and innovation in the realm of AOES, leading to the discovery of new catalytic systems and the development of more sustainable synthetic methodologies.