Metal- and Reagent-Free Intramolecular Oxidative Amination of Tri- and Tetrasubstituted Alkenes

Abstract

A metal- and reagent-free, electrochemical intramolecular oxidative amination reaction of tri- and tetrasubstituted alkenes has been developed. The electrosynthetic method proceeds through radical cyclization to form the key C-N bond, allowing a variety of hindered tri- and tetrasubstituted olefins to participate in the amination reaction. The result is the efficient synthesis of a host of alkene-bearing cyclic carbamates and ureas and lactams.

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

“…88 Amides, carbamates, and ureas substituted with electron-rich aryl groups can be used as the radical precursor under galvanostatic conditions. In the absence of an alcoholic solvent, the cyclized radical intermediate can be oxidized further to provide an olefin.…”

External oxidant-free cross-coupling: electrochemically induced aromatic C–H phosphonation of azoles with dialkyl-H-phosphonates under silver catalysis

“…Thus, new electrochemical reactions of the C(sp 2 )-H phosphorylation [20][21][22][23][24][25][26][27] have been proposed in recent years. The progress of electroorganic synthesis in this field is described in numerous reviews 22,23,[28][29][30][31][32] and papers concerning some recent advances in C-H functionalization, such as fluoroalkylation, [33][34][35][36][37][38] amination, [39][40][41][42] aziridination, 43 oxygenation, [44][45][46] arylation, 47 alkylation, 48 amino-oxygenation, 49 etc. The first electrochemical oxidative phosphorylation of benzoxazoles in the presence of a 3d metal catalyst was reported in 2016.…”

Formal Aza‐Wacker Cyclization by Tandem Electrochemical Oxidation and Copper Catalysis

“…[11] To probe the role of the Cu catalyst, reactions of representative substrates were conducted with and without the Cu(OAc) 2 catalyst. [9] Cyclic voltammetry (CV) was used to probe the oxidation process at the electrode.T he direct oxidation of 1a started only at potentials higher than 1.0 Vversus the Fc + /Fc couple ( Figure 2). In the absence of Cu, however, 2a was obtained only in 28 %y ield, and the reaction gave 12 %of4a [Eq.…”

“…[9] It was proposed that electrochemical oxidation generated an amidyl radical, which underwent intramolecular cyclization to give an alkyl radical. [9] Thus,the scope of the method was limited. [9] Thus,the scope of the method was limited.…”