Electrochemical Desaturative β‐Acylation of Cyclic N‐Aryl Amines. (20th December 2021)

• Record Type: Journal Article
• Authors: Feng, Tian; Wang, Siyi; Liu, Yin; Liu, Shouzhuo; Qiu, Youai
• Is Part Of: Angewandte Chemie. Volume 134:Number 6(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-12-20
• Subjects: β-Acylation -- Desaturation -- Electrochemistry -- Ferrocene mediator -- Selectivity; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202115178
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Herein, we disclose a straightforward, robust, and simple route to access β‐substituted desaturated cyclic amines via an electrochemically driven desaturative β‐functionalization of cyclic amines. This transformation is based on multiple single‐electron oxidation processes using catalytic amounts of ferrocene. The reaction proceeds in the absence of stoichiometric amounts of electrolyte under mild conditions, affording the desired products with high chemo‐ and regioselectivity. The reaction was tolerant of a broad range of substrates and also enables late‐stage β‐C(sp 3 )−H acylation of potentially valuable products. Preliminary mechanistic studies using cyclic voltammetry reveal the key role of ferrocene as a redox mediator in the reaction. Abstract : A straightforward and simple method of electrochemical desaturative β‐C(sp 3 )−H acylation of cyclic N ‐aryl amines has been developed to access the desired β‐substituted enamines with excellent levels of chemo‐ and regioselectivity under mild conditions. This procedure proved to be a powerful route to the late‐stage modification of natural products and derivatives.