Facile and Economical Electrochemical Dehalogenative Deuteration of (Hetero)Aryl Halides

Abstract

Deuterated compounds are valuable in synthetic, pharmaceutical and analytical chemistry. The deuteration of halides is a widespread method for its good site-selectivity. However, the facile, efficient and economical deuterium incorporation still remains a big challenge. In this work, we introduced a practical deuteration of (hetero)arylhalides through electrochemical reduction method. This transformation proceeded smoothly under room temperature without metal catalysts, external-reductants, toxic or dangerous reagents. Remarkably, low-cost and chemical equivalent D 2 O was the sole deuterium source in this reaction. The professional electrosynthesis equipment was not essential, but common batteries and electrodes were enough.

Electrochemical Oxidation Dearomatization of Anisol Derivatives toward Spiropyrrolidines and Spirolactones

“…In recent years, electrochemical synthesis has been widely recognized as an efficient and environmentally benign synthetic tool in synthetic chemistry. [24][25][26][27][28][29][30][31][32][33][34] With sufficient potential bias, organic substrates can lose electrons at the anode to generate highly reactive intermediates, which is superior than the classical reactions involving chemical oxidants. Compared with the well-versed chemical dearomative procedures, few sustainable electrochemical versions have been validated.…”

Current electrochemical approaches to selective deuteration

“…In the year prior to the investigations by Su into Pd catalysed deutero-dehalogenation discussed in Section 2, two convincing examples of single-electron reductive deutero-dehalogenation of aryl halides by electrochemistry emerged in close succession from Zhang and co-workers, 45 followed by Lei and co-workers. 46 In the former, Zhang demonstrated that a copper nanowire array cathode material could be used to affect selective reduction of mostly aryl carbon-halogen bonds over alkenes, alkynes, nitriles, imines, and carbonyl compounds (Scheme 10). 45 This cathode material, having a weak adsorption for H (and accordingly D ), is in contrast to a number of those discussed previously which employ a palladium cathode.…”

“…In the latter of these two works, Lei also demonstrated a simple alternative electrochemical setup, using a platinum anode and lead cathode in an undivided cell (Scheme 11). 46 Similarly, D 2 O was used as the source of D /D 2 for a coupling with the electrogenerated aryl radical derived from the corresponding chlorides, bromides or iodides, supported again by EPR radical trapping studies. The reaction conditions showed good tolerance for some functional groups susceptible to reduction including nitriles and esters.…”

Electrochemical Oxidative [4+2] Annulation of Different Styrenes toward the Synthesis of 1,2-Dihydronaphthalenes

“…[25][26][27][28] Recently, electrochemical synthesis attracted more and more attentions due to its simple and mild reaction conditions. [29][30][31][32][33][34] In 2019, Ye and his colleagues reported an electrochemical [4+2] annulation of styrenes to access naphthalene derivatives under mild conditions. 35 The transformation of styrenes, such as difunctionalization, 36-…”