Electrochemical Mn-Promoted Radical Selenylation of Boronic Acids with Diselenide Reagents

Abstract

A powerful and environmentally friendly electrochemical manganese-promoted free radical selenylation reaction between boronic acids and diselenide reagents was established. This electrochemical protocol provides a practically applicable way to a series of valuable organoselenium compounds with the use of easy available materials. Mechanistic experiments implied that the seleno-radical formed via direct or indirect electrochemical oxidation of diselenide may be involved as a key species in this transformation.

Mn(III)-Mediated Radical Addition/Cyclization of Isocyanides with Aryl Boronic Acids/Diarylphosphine Oxides: Access to 11-Functionalized Dibenzodiazepines

“…On the basis of the above control experiments and previous studies, − a possible mechanism is shown in Scheme . First, phosphonyl or aryl radical is formed from corresponding radical precursors diphenylphosphine oxide 4a and phenyl boronic acid 2a under Mn 3+ oxidant.…”

“…In 2012, Chatani reported a Mn 3+ -mediated oxidative radical cyclization of 2-isocyanobiphenyls with boronic acid, since then, Mn­(III)-promoted radical reactions of organoboron reagents have received great attention. ,− Among them, Wang, Ji, and co-workers reported corresponding radical cyclization reactions for the synthesis of pyrrolopyridine and pyrroloisoquinoline derivatives via Mn­(III)-mediated cascade reactions of isocyanides with boronic acids. , Luo, Zhu, and co-workers reported the Mn­(III)-mediated cascade reaction of functionalized isocyanides with aryl boronic acid to construct indole-fused scaffolds . Furthermore, Lei’s group recently also reported Mn-catalyzed electrochemical radical reactions of boronic acids…”

Electrochemical synthesis and transformation of organoboron compounds

“…Almost spontaneously, Lei and co-workers reported an electrochemical manganese-promoted selenylation of organic boronic acids with diselenide reagents (Scheme 22d). 57 Aryl, alkyl and alkenyl boronic acids were all suitable substrates to provide a series of valuable selenoether compounds. Very recently, the electrochemical sulfonylation of organoboronic acids with sodium arylsulfinate salts has been reported by Ma and co-workers (Scheme 22e).…”

A Palladium-Catalyzed Borylation/Silica Gel Promoted Hydrolysis Sequence for the Synthesis of Hydroquinine-6′-Boric Acid and Its Applications

“…Arylboronic acids are highly active molecules that serve as the most essential building blocks in organic synthesis . In the past decades, arylboronic acids participated in several significant types of coupling reaction, such as Suzuki–Miyaura cross-coupling reaction, Chan–Lam reaction, Liebeskind–Srogl reaction, Petasis reaction, P -arylation, and selenylation, leading to the construction of numerous valuable compoundsmedicines, catalysts, natural products, and pesticides …”