Efficient Protocol for Synthesis of β‐Hydroxy(alkoxy)selenides via Electrochemical Iodide‐Catalyzed Oxyselenation of Styrene Derivatives with Dialkyl(aryl)diselenides

Abstract

An efficient protocol for the synthesis of β‐hydroxy(alkoxy)selenides was developed through the electrochemical iodide‐catalyzed oxyselenation of styrene derivatives with dialkyl(aryl)diselenides under mild reaction conditions. Mechanistic studies showed that the cation I+ is involved during the whole process, and accelerates the formation of seleniranium ion via substitution and addition reaction with dialkyl(aryl)diselenides and styrene derivatives. The corresponding products are formed in good to excellent yields. This electrochemical oxyselenation provides an efficient strategy for difunctionalization of alkenes.

The Renaissance of Electro‐Organic Synthesis for the Difunctionalization of Alkenes and Alkynes: A Sustainable Approach

“…The electrochemical oxyselenation of substituted styrenes with diorganoselenides were achieved in an undivided cell consisting of platinum cathode and graphite anode catalyzed by potassium iodide using water/alcohol to yied the β hydroxy or β ‐alkoxy product (Scheme 13). [63] The reaction was successful in gram scale synthesis of the product. The oxyselenation is initiated by anodic oxidation of iodide to form iodinium ion which on reaction with diorganoselenide to give phenyl hypoiodoselenoite.…”

“…The reactions employing highly advantageous aqueous conditions by the use of surfactants, greener ionic liquids and bi-phasic electrolysis is yet to be explored. The electrochemical difunctinalization could thus, be used as a foundation to synthesize functionalized unsaturated compounds with Pt(+)/Pt-(À ) [62] 3.0 V Styrenes and diorganoselenides Oxy selenation product Catalyst: KI, Reagent: Alcohol/water Solvent: acetonitrile, Cell: Undivided Pt(+)/C-(À ) [63] 6 mA Olefinic acids/ olefinic alcohols and diorganoselenide Selenomethyl-substituted cyclic lactones or ethers Catalyst and Electrolyte: NH 4 I Solvent: acetonitrile Cell: Undivided Pt(+)/RVC (À ) [64] 10 mA Alkynes, sulfonyl hydrazines and diphenylselenides…”

Recent progress in the electrochemical selenofunctionalization of alkenes and alkynes

“…Chen et al recently extended the scope of alkenes and diselenides by following the same reaction sequence in electrocatalytic conditions, employing KI as the electrolyte and catalyst, in which the highly active intermediate PhSeI accelerates the formation of seleniranium ions. 28 Despite the advantages of organic electrochemistry shown thus far, there are some limitations in batch reaction processes. One limitation is the necessity of using organic salts as electrolytes, as organic solvents generally have low conductivity; however, these salts can lead to undesired products.…”

Branching out: redox strategies towards the synthesis of acyclic α-tertiary ethers

“…211,212 More recently, this approach has been expanded by Chen & Shi via the use of KI as a substoichiometric electrolyte, implicated in generating iodine cations to effect the oxidation of the diselenide (Scheme 48). 213 Despite mainly focussing on the hydroxyselenation of alkenes, a single example was reported employing t-BuOH as the co-solvent and therefore the nucleophilic component.…”