Bifunctional Chiral Electrocatalysts Enable Enantioselective α‐Alkylation of Aldehydes

• Published in: Angewandte Chemie International Edition Vol. 63; no. 39; pp. e202401355 - n/a
• Main Authors: He, Jin‐Yu, Zhu, Cuiju, Duan, Wen‐Xi, Kong, Ling‐Xuan, Wang, Na‐Na, Wang, Yan‐Zhao, Fan, Zhi‐Yong, Qiao, Xin‐Ying, Xu, Hao
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 23.09.2024
• Edition: International ed. in English
• Subjects: Aldehydes; Alkylation; Asymmetry; bifunctional chiral electrocatalyst; bifunctional electrolysis; Catalysts; Catalytic activity; Electrocatalysts; Electrochemistry; electrosynthesis; Enantiomers; enantioselectivity; Phenols; redox mediator; Stereoselectivity; bifunctional electrolysis bifunctional chiral electrocatalyst electrosynthesis redox mediator enantioselectivity
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202401355

Herein, we describe an innovative approach to the asymmetric electrochemical α‐alkylation of aldehydes facilitated by a newly designed bifunctional chiral electrocatalyst. The highly efficient bifunctional chiral electrocatalyst combines a chiral aminocatalyst with a redox mediator. It plays a dual role as a redox mediator for electrooxidation, while simultaneously providing remarkable asymmetric induction for the stereoselective α‐alkylation of aldehydes. Additionally, this novel catalyst exhibits enhanced catalytic activity and excellent stereoselective control comparable to conventional catalytic systems. As a result, this strategy provides a new avenue for versatile asymmetric electrochemistry. The electrooxidation of diverse phenols enables the C−H/C−H oxidative α‐alkylation of aldehydes in a highly chemo‐ and stereoselective fashion. Detailed mechanistic studies by control experiments and cyclic voltammetry analysis demonstrate possible reaction pathways and the origin of enantio‐induction. The novel designed bifunctional chiral electrocatalyst has been presented for the asymmetric electrochemical α‐alkylation of aldehydes. The new bifunctional catalyst, which combines a chiral aminocatalyst with a redox mediator, significantly enhances efficiencies and stereoselectivities compared to conventional catalysts. It plays a dual role as a redox mediator for electrooxidation while simultaneously providing remarkable asymmetric induction for the stereoselective α‐alkylation of aldehydes.