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Three-component Reactions Of Ketones,amines And Carbon Dioxide Under Electrochemical Conditions

Posted on:2021-01-05Degree:MasterType:Thesis
Country:ChinaCandidate:J W WangFull Text:PDF
GTID:2381330602499084Subject:Organic Chemistry
Abstract/Summary:PDF Full Text Request
organic electrochemical synthesis is an interdisciplinary subject which uses electrochemical techniques to synthesize organic compound.It is the core mechanisation that chemicals exchange electrons on the surface of the electrode to attain the effect of redox,thus the use of chemical redox reagents is reduced or even avoided.In addition,the magnitude of current or voltage can be controled to improve the efficiency and selectivity of the reaction in the electrochemistry.Now,organic electrochemical synthesis can be simply divided into electrochemical oxidation reaction and electrochemical reduction reaction.It can be realized both by the electron gain or loss of the reaction substrate on the electrode surface directly and by the electron transfer through an electrochemical medium.Generally,the redox potential of electrochemical medium is lower than that of the reaction substrate,which means a lower reaction voltage,making the reaction more mild and selective.Anyway,electrochemical techniques provide a new choice for organic synthesis to construct C-C bonds,C-N bonds and other C-X bonds and X-X bonds.Carbon dioxide is a ubiquitous,renewable C1 resource.Meanwhile,carbon dioxide is also a serious greenhouse gas.The earth releases the energy,absorbed from the sun,into space in the form of long waves of radiation.However,some of the energy will be absorbed again by carbon dioxide and then remain in the atmosphere,causing the earth to warm up.Therefore,carbon dioxide fixation can not only increase resource utilization,but also improve greenhouse effect.Since its high thermodynamic stability and kinetic inertia,the conditions of carbon dioxide fixation in organic synthesis are generally harsh.In the present study,organic chemists mainly fix carbon dioxide to synthesize carboxylic acid,carbamate and other organic compounds.The synthesis of carboxylic acids by catalyzing carbon dioxide to format C-C bonds is mainly confined to typical ? systems or organometallic species formed by halides and metals.And,the main method of synthesizing carbamate and other organic compounds is to use high energy substrates or reaction intermediates to react with carbon dioxide,such as amines and electrophilic phenylacetylene generated in situ.This paper are mainly divided into two parts.The first part reviews the representative work of organic electrochemical synthesis and carbon dioxide fixation.The application of organic electrochemical synthesis in carbon dioxide fixation is studied in the second part.Carbamate derivatives are synthesized from ketones,amines and carbon dioxide in one pot under the condition of atmospheric pressure carbon dioxide,no metal and no chemical oxidant.Specifically,carbamate derivatives are synthesized from ketones,amines and carbon dioxide in one pot under the condition of atmospheric pressure carbon dioxide,metal-and chemical oxidant-free.Carbamate structure is widely found in natural products,agricultural products and pharmaceutical molecules.The traditional synthesis of carbamate depends on highly toxic phosgene and its derivatives,or on the prefunctionalization of substrates.Gratifyingly,Safe and non-toxic carbon dioxide is used instead of phosgene and its derivatives in our method.Meanwhile,we choose the strategy of C(sp3)-H functionalization to synthesize carbamate in one pot.Therefore,environment-friendly and high atomic economy is the superiority of our method.
Keywords/Search Tags:Organo-electrosynthesis, carbon dioxide fixation, carbamate
PDF Full Text Request
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