Photoredox-catalyzed C(sp2)–N coupling reactions

Intermolecular radical carboamination of alkenes

“…Generation of the N-radicals has to proceed under mild conditions that are compatible with the subsequent C-C bond formation. Along these lines, various N-X reagents and oxime derivatives have been exploited for amidyl radical generation [35][36][37][38][39] and the azidyl radical can be mildly accessed through SET oxidation of commercial TMSN 3 . 44,45…”

“…Considering the first class and an alkene as a C-radical acceptor, the reactivity of two different alkenes has to be controlled and the alkene carboamination selectivity is governed by polar effects. 34 Since N-radicals are electrophilic species, [35][36][37][38][39][40][41] initial C-N bond formation occurs highly chemoselective with an electron-rich alkene such as an aliphatic alkene, a vinyl ether or an enamide to give the corresponding nucleophilic C-radical adduct that gets trapped either via reaction with a p-acceptor or via oxidation and subsequent nucleophilic trapping. Transition metal mediated C-C bond formation is also possible.…”

Reaction of Nitrogen‐Radicals with Organometallics Under Ni‐Catalysis: N‐Arylations and Amino‐Functionalization Cascades

“…Finally,w eq uestioned if the presented cyclization-functionalization strategy could be extended to alkyl organometallic reagents (Scheme 3D). [28] Mechanistically,w ew ere intrigued by the possibility of accessing dialkyl-Ni III intermediate S,w hich would ultimately lead to aN -cyclizationalkylation process.T his strategy would deliver the concomitant formation of vicinal sp 3 CÀNa nd sp 3 -sp 3 CÀCb onds, at ransformation that, to the best of our knowledge,h as not been possible by either ionic, transition metal-mediated, or radical pathways.…”

“…The N-cyclization-alkylation cascade introduces an ovel retrosynthetic disconnection for the assembly of substituted lactams and pyrrolidines with its potential demonstrated in the short total synthesis of four venom alkaloids.Nitrogen-radicals are versatile synthetic intermediates that can engage in ab road range of chemical reactions. [1] In general, they are used in intramolecular cyclizations, [1] intramolecular 1,5-H-atom abstractions (HATs), [2] and intermolecular additions to p-systems [3] (Scheme 1A). Aconsiderably underdeveloped reactivity stream is their engagement in transition metal-based processes,a ni nterplay heavily exploited with C-radicals (Scheme 1B).…”

Reaction of Nitrogen‐Radicals with Organometallics Under Ni‐Catalysis: N‐Arylations and Amino‐Functionalization Cascades

“…[1] In general, they are used in intramolecular cyclizations, [1] intramolecular 1,5-H-atom abstractions (HATs), [2] and intermolecular additions to p-systems [3] (Scheme 1A). [1] In general, they are used in intramolecular cyclizations, [1] intramolecular 1,5-H-atom abstractions (HATs), [2] and intermolecular additions to p-systems [3] (Scheme 1A).…”