Facile and general electrochemical deuteration of unactivated alkyl halides

Abstract

Herein, a facile and general electroreductive deuteration of unactivated alkyl halides (X = Cl, Br, I) or pseudo-halides (X = OMs) using D2O as the economical deuterium source was reported. In addition to primary and secondary alkyl halides, sterically hindered tertiary chlorides also work very well, affording the target deuterodehalogenated products with excellent efficiency and deuterium incorporation. More than 60 examples are provided, including late-stage dehalogenative deuteration of natural products, pharmaceuticals, and their derivatives, all with excellent deuterium incorporation (up to 99% D), demonstrating the potential utility of the developed method in organic synthesis. Furthermore, the method does not require external catalysts and tolerates high current, showing possible use in industrial applications.

Electrochemical, Regioselective, and Stereoselective Synthesis of Allylic Thioethers and Selenoethers under Transition-Metal-Free and Oxidant-Free Conditions

“…On the basis of previous reports, , control experiments, and cyclic voltammetry data, a plausible reaction pathway is depicted in Figure for this interesting electrochemical C–S bond formation process by taking 1a and 2a as a model substrate. 2a initially gains an electron at the cathodic position and forms radical anionic species Int A , which later is transformed into PhS • and PhS – .…”

Site‐Selective Electrochemical C−H Carboxylation of Arenes with CO2

“…[11] Related to our work, Fuchs and co-workers reported several early examples of electrochemical carboxylation of quinolines, albeit with a limited substrate scope, low reactivity and selectivity (Figure 1a). [12] In sharp contrast, with our continuous interests in sustainable electrochemical CÀ H(X) functionalization [13,14] and CO 2 valorization, [15] herein we report the unprecedented, metal-free, and direct electrochemical CÀ H carboxylation of arenes through reductive activation with CO 2 with significant and unique regioselectivity. A wide range of structurally novel and useful aryl carboxylic acids that are otherwise not easily obtained using traditional methods were afforded smoothly from diverse arenes (Figure 1b).…”

Electroreductively Induced Radicals for Organic Synthesis

“…However, corresponding reports on unactivated alkyl halides have not been well elucidated [ 47 , 48 ]. Recently, the Qiu group showed electrochemically dehalogenative deuteration of un-activated alkyl halides (X = Cl, Br, I) or pseudo halides (X = OMs) using D 2 O as the economical deuterium source ( Figure 4 ) [ 49 ]. This strategy is a good complement to the electrochemical deuteration of aryl halides, which has recently been successfully developed [ 50 , 51 ].…”