Transition‐Metal‐Catalyzed 1,2‐Diaminations of Olefins: Synthetic Methodologies and Mechanistic Studies

Abstract

1,2‐Diamines are synthetically important motifs in organo‐catalysis, natural products, and drug research. Continuous utilization of transition‐metal based catalyst in direct 1,2‐diamination of olefines, in contrast to metal‐free transformations, with numerous impressive advances made in recent years (2015‐2023). This review summarized contemporary research on the transition‐metal catalyzed/mediated [e.g., Cu(II), Pd(II), Fe(II), Rh(III), Ir(III), and Co(II)] 1,2‐diamination (asymmetric and non‐asymmetric) especially emphasizing the recent synthetic methodologies and mechanistic understandings. Moreover, up‐to‐date discussion on (i) paramount role of oxidant and catalyst (ii) key achievements (iii) generality and uniqueness, (iv) synthetic limitations or future challenges, and (v) future opportunities are summarized related to this potential area.

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

“…The possible mechanism for this photoredox alkene 1,2-amidoamination protocol is outlined in Scheme b on the basis of the current results and precedent literatures. ,− Direct single electron transfer (SET) between the excited state Ir III * and N -(sulfonamido)­pyridin-1-ium salt 2 can occur to afford the N -(sulfonamido)­pyridine radical intermediate A . , Meanwhile, CoCl 2 is reduced by the excited state Ir III * to form a Co radical anion, which sequentially undergoes electron transfer (ET) with 2 to deliver the N -(sulfonamido)­pyridine radical intermediate A (supported by the CV analysis of a mixture of 2a and CoCl 2 and the Stern–Volmer fluorescence quenching experiments). The N–N bond cleavage of the intermediate A generates the amidyl radical B and pyridine .…”

“…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.…”