Regioselective Synthesis of Unsymmetrical Vicinal Diamines via Azidoimination of Alkenes with TMSN₃ and Ketimines

Photocatalytic Unsymmetrical Diamination of Styrenes, Indoles, and Benzofurans Facilitated by Benzotriazolyl and Iminyl Radicals

“…Recently, Shin , and Cho reported that N -enoxybenzotriazoles serve as precursors for the generation of benzotriazoly and α-carbonyl radicals via energy transfer photolysis (Scheme B), successfully achieving the double functionalization of electron-rich olefins. The field of difunctionalization of unsaturated compounds has recently witnessed significant advancements in photochemical and electrochemical radical chemistry …”

Cobalt-Promoted Photoredox 1,2-Amidoamination of Alkenes with N-Sulfonamidopyridin-1-ium Salts and Free Amines

“…Mild and selective diamination of olefins is an important and longstanding goal in synthetic chemistry because it can simultaneously install two amino groups on the CC bond for the elaboration of privileged vicinal diamines, which are essential structural motifs widely existing in bioactive natural products, pharmaceuticals, molecular catalysts, and functional materials . Conventional methods are centered on transition-metal-catalyzed 1,2-diamination of olefins with various amino reagents, such as azides, diaziridines, N , N ′-disubstituted ureas and their derivatives, N -fluorobenzenesulfonimides, O -acylhydroxylamines, diamines, amides, and free amines, in an intramolecular or an intermolecular mode, allowing for the direct construction of vicinal diamine architectures. While these transition-metal-catalyzed intramolecular alkene 1,2-diamination methods can inlay two same or different amino groups across the CC bond by devising substrates to prepare the N -heterocyclic vicinal diamines, such intermolecular approaches are largely limited to the introduction of two same amino groups for the installation of symmetrical vicinal diamines.…”

Photocatalytic Sulfonyl Peroxidation of Alkenes via Deamination of N-Sulfonyl Ketimines

“…Radical-based photocatalytic methods with N -sulfonyl imines have emerged as a complementary tool to introduce the sulfonylation group into the alkene feedstocks. − For example, using N -sulfonyl imines as the bifunctional reagents, Glorius et al and Du et al, respectively, realized the imino-sulfonylation of alkenes upon a visible-light-induced energy transfer (EnT) process (Scheme b). Furthermore, when a thiol- or silyl-based hydrogen atom donor was added in the reaction, the reactivity of N -sulfonyl imines could be tuned toward hydrosulfonylation via the synergistic EnT and hydrogen atom transfer (HAT) pathways, as reported independently by Glorius’s group and Willis’s group …”

“…In this context, the prefunctionalization of sulfonamides into various derivatives, including N -sulfonyl imines, N -acylsulfonamides, sulfonyl pyrylium salts, and sulfonyl pyrroles, etc., has facilitated the efficient N–S bond cleavage and further manipulations. Among them, N -sulfonyl imines serve as a bench-stable and readily available radical-type sulfonylation reagent (BDE of N–S bond ≈ 70 kcal/mol) under light-mediated reaction conditions.…”