Manganese-Catalyzed N–F Bond Activation for Hydroamination and Carboamination of Alkenes

Abstract

A visible-light-promoted method for generating amidyl radicals from N-fluorosulfonamides via a manganesecatalyzed N−F bond activation strategy is reported. This protocol employs a simple manganese complex, Mn 2 (CO) 10 , as the precatalyst and a cheap silane, (MeO) 3 SiH, as both the hydrogen-atom donor and the F-atom acceptor, enabling intramolecular/intermolecular hydroaminations of alkenes, two-component carboamination of alkenes, and even three-component carboamination of alkenes. A wide range of valuable aliphatic sulfonamides can be readily prepared using these practical reactions.

Earth-Abundant 3d Transition Metal Catalysts for Hydroalkoxylation and Hydroamination of Unactivated Alkenes

“…Despite the interesting features of being of low toxicity and eco-friendly, manganese remains unexploited for the development of catalytic hydroamination and hydroalkoxylation methodologies of unactivated alkenes [40]. To our knowledge, there is only one report of manganese-catalyzed hydroamination of unactivated alkenes [41,42]. This year, the group of Qu and Zhang reported an elegant visible-light-induced manganese-promoted N-F bond activation strategy to generate amidyl radicals from N-fluorinated sulfonamides (Figure 1).…”

“…Indeed, due to electronic matching problems, low reactivity is observed for alkyl-substituted alkenes. This protocol can also be applied to a two-and three-component carboamination of alkenes [41]. The authors proposed that a light-induced homolysis of the Mn-Mn bond in Mn 2 (CO) 10 generates a metalloradical Mn(CO) 5 having the ability to abstract the F atom from the substrate and leading to the formation of the reactive amidyl radicals [43].…”

Visible‐Light‐Catalyzed N‐Radical‐Enabled Cyclization of Alkenes for the Synthesis of Five‐Membered N‐Heterocycles

“…[23] In 2021, Zhang and co-workers proposed a Mn-catalyzed strategy for generating amidyl radicals from N-fluorinated sulfonamides using visible light (Scheme 4). [24] In this work, aliphatic sulfonamides were generated after intramolecular hydroaminations of alkenes with Mn 2 (CO) 10 as the precatalyst and (MeO) 3 SiH as both the Hatom donor and the F-atom acceptor. More importantly, the scope and limitations of this transformation were investigated using a series of substrates featuring various substituents.…”

Catalytic Intramolecular Aminoarylation of Unactivated Alkenes with Aryl Sulfonamides

“…22,23 We expected our N-centered radical approach to circumvent this limitation as well, based on strong literature precedent describing anti-Markovnikov sulfonamidyl radical additions to unactivated alkenes. [24][25][26][27][28][29][30] However, no examples of Smiles-Truce rearrangements have been demonstrated in these systems.…”