On the N‐Arylation of Acetamide Using 2‐, 3‐ and 1'‐Substituted Iodoferrocenes. Issue 4 (22nd December 2020)

• Record Type: Journal Article
• Authors: Kadari, Lingaswamy; Erb, William; Halauko, Yury S.; Ivashkevich, Oleg A.; Matulis, Vadim E.; Lyakhov, Dmitry; Roisnel, Thierry; Radha Krishna, Palakodety; Mongin, Florence
• Is Part Of: European journal of inorganic chemistry. Issue 4(2021)
• Page Start: 377
• Page End: 391
• Publication Date: 2020-12-22
• Subjects: Ferrocene -- Amides -- Copper -- Coupling -- Substituent effect; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202000904
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Various 2‐, 3‐ and 1'‐substituted iodoferrocenes were reacted with acetamide in the presence of copper(I) iodide (1 equiv), N, N' ‐dimethylethylenediamine (1 equiv), tripotassium phosphate (2 equiv) in dioxane at 90 °C for 14 h, and allowed a large range of original 1, 2‐, 1, 3‐ and 1, 1'‐disubstituted ferrocenes to be obtained. The results were compared as a function of the substituent and its position on the ring. DFT calculations revealed higher activation barrier for the oxidative addition in the ferrocene series when compared with classical planar aromatics. Structure‐property relationships were applied to rationalize the reactivity of the different iodoferrocenes. Abstract : Original 1, 2‐, 1, 3‐ and 1, 1'‐disubstituted ferrocenes were obtained from 2‐, 3‐ and 1'‐substituted iodoferrocenes by copper‐mediated reaction with acetamide. Compared with the corresponding planar aromatics, the activation barriers calculated for oxidative addition in the ferrocene series proved higher. However, the attempts to establish relationships between the yields and the substituents and their position evidenced the lack of tools to predict ferrocenyl iodide activation.