Study On Green And Economical Electrochemical Difunctionalization Of Alkenes

Olefin difunctionalization is a simple and effective method for constructing complex molecules.This area of research has been of great interest to many researchers.Both traditional transition metal catalysis and the more recent development of organocatalysis have made significant contributions to the field of olefin difunctionalization.In recent years,there has been a rapid development of photochemical and electrochemical catalytic reactions.This has led to the emergence of new strategies for green and economical methodologies in the development of organic synthesis.In this paper,we combined the research progress of olefin difunctionalization in recent years and explored the construction of C-C bond,C-N bond and C-O bond during olefin difunctionalization reactions under electrochemical conditions,and the main results are as follows:1.Electrochemical trifluoromethyl-amination reaction of olefinsThe reaction does not require the participation of transition metals or the addition of oxidants.Sodium trifluorosulfinate,which is cheap and easily available,is used as the trifluoromethylation reagent,and imine is used as the nitrogen source.Trifluoromethylamination of alkenes is achieved under electrical drive for the first time.This strategy offers a new approach for constructing β-trifluoromethyl primary amines by hydrolyzing such products into free amines under hydrochloric acid conditions.2.Decarboxylative alkoxy-alkoxycarbonylation reaction of alkenes under electrochemistryThe reaction utilizes the potassium salt of oxalic acid monoester to be oxidized and decarboxylated at the anode to form an alkoxycarbonyl radical,which is adducted with the olefin to obtain a new carbon-centered radical,and the new radical is further oxidized by the anode to generate a carbon positive ion and is captured by the nucleophilic reagent,and synthesizes a series of β-alkoxy alkoxycarbonylation products;at the same time,hydrogen is precipitated by the cathode,which achieves the electronic equilibrium of the whole circuit.The reaction realized the highly regioselective oxidative addition of olefins by two types of nucleophilic reagents by using the oxidation effect of anode.The reaction not only has good substrate suitability but also good functional group compatibility,providing a new method for the synthesis of βalkoxycarboxylic acids or 1,3-dihydroxy derivatives.3.Electrochemical decarboxylative alkoxyl-alkylation reaction of olefinsThe system utilizes the carboxylic acid quaternary ammonium salt as both a precursor for alkyl radicals and an electrolyte for electrochemical reactions.This enables the oxidative decarboxylation of the salt to produce alkyl radicals,which can then undergo addition reactions with olefins without the need for metal-catalysts or extra oxidants.Additionally,it includes an extended study of the classical Kolbe electrolysis reaction and a new strategy for the alkylation of olefins with long carbon chains.