Iron-catalyzed C(sp³)–H functionalization ofN,N-dimethylanilines with isocyanides

Abstract

An efficient ligand-free Fe-catalyzed oxidative Ugi-type reaction toward the assembly of α-amino amides and short peptides is described. The reaction proceeds through the α-C(sp)-H oxidation of N,N-dimethylanilines and further nucleophilic attack of the resulting iminium species by isocyanides. Additive screening showed that judicious choice of the carboxylic acid could lead to the formation of α-amino imides via a 3-component reaction. The process occurs with operational simplicity and is compatible with a variety of sensitive functional groups.

Bond Forming Reactions Involving Isocyanides at Diiron Complexes

“…Considerable efforts have been made in order to expand the research field to other transition-metals, given the strong interest in replacing noble and rare metals with more abundant and sustainable transition metals, such as iron. Indeed, the number of Fe-catalyzed reactions is rapidly expanding, but those involving isocyanides are still limited [23][24][25].…”

“…given the strong interest in replacing noble and rare metals with more abundant and sustainable transition metals, such as iron. Indeed, the number of Fe-catalyzed reactions is rapidly expanding, but those involving isocyanides are still limited [23][24][25]. This mini-review focuses on reactions involving isocyanides and diiron complexes, aimed at the formation of C-C or C-heteroatom bonds for the construction of more complex molecular architectures.…”

Click-based conjugated microporous polymers as efficient heterogeneous photocatalysts for organic transformations

“…The C(sp 3 )-H α-carbamoylation of N,N-dimethylanilines, namely the Ugi multicomponent reaction, is a widely studied organic transformation and can give straightforward access to α-amino amides, [47][48][49][50] which are prevalent chemicals in organic synthesis. 51 However, most studies have focused on the reactions of alkyl isocyanides with N,N-dimethylanilines, while the research on the reactions of aryl isocyanides with N,N-dimethylanilines is rarely involved.…”

Transition Metal and Inner Transition Metal Catalyzed Amide Derivatives Formation through Isocyanide Chemistry

“…The use of Fe(OAc) 2 as an alternative catalyst for oxidative Ugi-type reaction of N,N-dimethylanilines was reported by Correa and co-workers. 56 The results were improved by Fe(II) compared to copper, albeit in some cases, high yields of -amino amides were obtained by the addition of acetic acid. Moreover, using picolinic acid preferentially led to picolinamides.…”