Towards Iron‐Catalyzed Sonogashira Cross‐Coupling Reactions

Abstract Herein we report on the selective iron‐catalyzed cross‐coupling reaction of terminal phenylacetylenes with iodo‐aryl derivatives to afford the respective coupling products in the presence of 10 mol% FeCl 2 (bdmd) and 10 mol% [Cu(CH 3 CN) 4 ]BF 4 (bdmd=bis((diphenylphosphanyl)methyl)diphenylsilane). The yields are moderate to good in 1,4‐dioxane or DMF. This is the first example of a well‐defined and fully analysed ferrous complex acting as a precatalyst in Sonogashira cross‐coupling reactions. Notably, FeCl 2 (bdmd) is compatible with reactive substituents such as carbonyl‐, carboxyl‐, hydroxy‐, and amino‐groups, which allows for an effective cross‐coupling reaction in the presence of such functional groups.