The direct C–H amination of arenes is an important strategy to streamline the discovery and preparation of functional molecules. Herein, we report an operationally simple arene C–H amination reaction that, in contrast to most literature precedent, affords directly the synthetically versatile primary aniline products without relying on protecting group manipulations. Inexpensive Fe(II)-sulfate serves as a convenient catalyst for the transformation. The reaction tolerates a wide scope of arenes, including structurally complex drugs. Importantly, the arene substrates are used as limiting reagents in the transformation. This operationally simple transformation should considerably accelerate the discovery of medicines and functional molecules
A new transfer hydrofunctionalization strategy to turnover H-M -X complexes has enabled both intra- and intermolecular Mizoroki-Heck (MH)-type reactions of aryl cyanides that are challenging to realize under traditional, basic conditions. Initially, a cascade carbonickelation/MH reaction of 2-cyanostyrenes was achieved using a key alkyne transfer hydrocyanation step. Mechanistic experiments supported the proposed catalytic cycle, including the turnover-enabling transfer hydrocyanation step. The reactivity was then extended to the intermolecular MH reaction of benzonitriles and styrenes.
We demonstrate that a simple cobalt complex can regioselectively couple epoxides and aziridines with alkenes to generate valuable homoallylic alcohols and amines. The intramolecular reaction exhibits complete atom economy and, in contrast to traditional Mizoroki-Heck reactions, does not require stoichiometric amounts of base. An indole derivative was also shown to be a suitable coupling partner. Finally, promising results regarding the development of an intermolecular process using both epoxides and aziridines are reported, as well as preliminary mechanistic studies suggesting a radical mechanism.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.