Functionalization of 3‐Iodo‐ N , N ‐diisopropylferrocenecarboxamide, a Pivotal Substrate to Open the Chemical Space to 1,3‐Disubstituted Ferrocenes

From 2-iodo-N,N-diisopropylferrocenecarboxamide, the halogen 'dance' reaction was applied to deliver gram quantities of the 3-iodo isomer. The latter was successfully functionalized by Ullmann-type and Suzuki-Miyaura cross-couplings to build C-O and C-C bonds, respectively. Lithium/iodine exchange-electro-philic trapping sequences were also implemented to provide ferrocenes bearing valuable functional groups. Borane-mediated carboxamide reduction was next studied on selected substrates to deliver the corresponding amino derivatives in moderate to excellent yields. One of them, 1-(N,N-diisopropylaminomethyl)-3-iodoferrocene, was used as a substrate to access various iodoferrocene derivatives. Not only this work constitutes a general entry into the world of 1,3-disubstituted ferrocenes, but it also extends the chemical space available around this original scaffold.