Oximes of ketones and aldehydes are efficiently converted to the corresponding carbonyl compounds, using a combination of NaHSO4.H20 and paraformaldehyde in good to excellent yields under solid state conditions at roo...Oximes of ketones and aldehydes are efficiently converted to the corresponding carbonyl compounds, using a combination of NaHSO4.H20 and paraformaldehyde in good to excellent yields under solid state conditions at room temperature for 10 minutes.展开更多
Oximes were oxidized to the corresponding carbonyl compounds in good to high yields by environmentally friendly and green oxidant, H202 catalyzed by montmorillonite K-10 supported cobalt（Ⅱ） chloride.
Deoximation is an important transformation in synthetic industry.It can be employed in protection,characterization and purification of the carbonyls,and in the synthesis of ketones from non-carbonyl molecules.In the f...Deoximation is an important transformation in synthetic industry.It can be employed in protection,characterization and purification of the carbonyls,and in the synthesis of ketones from non-carbonyl molecules.In the field,oxidative deoximation reaction can utilize the driving force caused by the oxidation process so that the reaction can occur under relatively mild conditions.Recently,we designed and prepared polyaniline-supported molybdenum(Mo@PANI)just by immersing PANI into the EtOH/H_(2)O solution of MoCl_(5).The material was successfully applied as the efficient catalyst for oxidative deoximation reactions,which were performed in ethanol using H_(2)O_(2)as the clean oxidant.The substrate scope of the reaction was wide.It could be applied on heterocycle-containing substrates,making this protocol preferable for pharmaceutical intermediate synthesis.Since Mo is a necessary trace element for both animals and plants,this method is environment-friendly and is suitable for large-scale preparation.This work as the first example of Mo-catalyzed oxidative deoximation reaction may inspire novel ideas for both catalyst design and synthetic process development.展开更多
Polyaniline-supported tungsten(W@PANI)was easily prepared by immersing polyaniline(PANI)in the aqueous solution of Na2WO4.It was found to be an efficient catalyst for oxidative deoximation reaction,the very important ...Polyaniline-supported tungsten(W@PANI)was easily prepared by immersing polyaniline(PANI)in the aqueous solution of Na2WO4.It was found to be an efficient catalyst for oxidative deoximation reaction,the very important transformation for pharmaceutical industry.Besides the green features,the method employed very few of catalytic tungsten(0.048 mol%vs.oxime substrates),resulting in the high turnover numbers(TONs)of the catalyst(ca.103 mol/mol)and the low metal residues in product(<0.1 ppm).The reaction is applicable for a variety of substrates,including those containing heterocycles,which are key intermediates in medicine synthesis.It has also been successfully magnified to kilogram scale production to afford the desired carbonyl products smoothly.展开更多
Deoximation reaction is one of the most important transformations in organic synthesis and for fine chemical production.Since oximes are easily synthesized from carbonyl compounds and are stable compounds,this reactio...Deoximation reaction is one of the most important transformations in organic synthesis and for fine chemical production.Since oximes are easily synthesized from carbonyl compounds and are stable compounds,this reaction can be used for protection-deprotection,purification,and characterization of carbonyl compounds in organic synthesis,especially for the synthesis of medicines as well as the natural products.Moreover,because many oximes can be synthesized from non-carbonyl starting materials,the deoximation reaction is also widely used in the production of many carbonyl-contained fine chemicals.Deoximation methods by using stoichiometric reagents are mature and can produce the related carbonyl products in very high yield with broad substrate application scopes.But for environment-protection consideration as well as the production cost controlling purpose in fine chemical industry,developing catalytic deoximation methods is the trend of the field and there are a series of references on this topic in recent years.This short review summarized recent advances on the development of deoximation methods from stoichiometric reaction to catalytic reaction and the mechanisms of some important transformations were discussed in detail for reader reference.展开更多
Catalyzed by commercially available(PhTe)2, molecular oxygen could be utilized as the mild, cheap and safe oxidant for oxidative deoximation reactions under solvent-free conditions. As the first report on organotellur...Catalyzed by commercially available(PhTe)2, molecular oxygen could be utilized as the mild, cheap and safe oxidant for oxidative deoximation reactions under solvent-free conditions. As the first report on organotellurium-catalyzed deoximation reaction, this work not only provides an efficient deoximation method, but also discloses new features of tellurium catalyst different from those of the organoselenium catalysts.展开更多
Irradiated by visible light,the recyclable(PhTe)2-catalyzed oxidative deoximation reaction could occur under mild conditions.In comparison with the thermo reaction,the method employed reduced catalyst loading(1 mol%vs...Irradiated by visible light,the recyclable(PhTe)2-catalyzed oxidative deoximation reaction could occur under mild conditions.In comparison with the thermo reaction,the method employed reduced catalyst loading(1 mol%vs.2.5 mol%),but afforded elevated product yields with expanded substrate scope.This work demonstrated that for the organotellurium-catalyzed reactions,visible light might be an even mo re precise driving energy than heating because it could break the Te—Te bond accurately to generate the active free radical catalytic intermediates without damaging the fragile substituents(e.g.,heterocycles)of substrates.The use of O_(2) instead of explosive H_(2)O_(2) as oxidant affords safer reaction conditions from the large-scale application viewpoint.展开更多
An acceptor-free catalysis protocol for the deoximation of ketoximes and aldoximes using RuCl3 as the catalyst has been developed. Under the optimized conditions, various oximes were converted to ketones and nitriles ...An acceptor-free catalysis protocol for the deoximation of ketoximes and aldoximes using RuCl3 as the catalyst has been developed. Under the optimized conditions, various oximes were converted to ketones and nitriles with excellent isolated yields.展开更多
Deoximation in metal chloride ionic liquids based on 1-alkyl-3-methylimidazolium and triethylene ammonium cations, such as AmimBr（Cl）-MClx （A=ethyl, butyl, benzyl; M=Al, Fe, Cu, Sn and Zn; x=2, 3） and Et3NHCl-FeCl...Deoximation in metal chloride ionic liquids based on 1-alkyl-3-methylimidazolium and triethylene ammonium cations, such as AmimBr（Cl）-MClx （A=ethyl, butyl, benzyl; M=Al, Fe, Cu, Sn and Zn; x=2, 3） and Et3NHCl-FeCl3 were investigated under mild conditions. Ferrate chloride ionic liquid was proved to be an effective catalyst for deoximation of cyclohexanone oxime, exhibiting high conversion of oximes and selectivity to cyclo- hexanone. Good performance for the deoximation of other oximes such as salicylald oxime, acetone oxime, benzo- phenone oxime, 4-nitrobenzald oxime, acetophenone oxime, 2-chlorobenzaldehyde oxime, Acetald oxime, 2-butanone oxime and （1R）-camphor oxime was also achieved with bmimBr-FeCl3 as catalyst and solvent. The de- oximation was determined to carry out via acid-catalytic hydrolysis and the reaction mechanism was proposed.展开更多
A variety of aldoximes and ketoximes were oxidized to corresponding aldehydes and ketones by nitric oxide in the presence of oxygen. A presumed mechanism was suggested.
A wide variety of aldoximes and ketoximes were regenerated to corresponding carbonyl compounds with Al（NO3）3·9H2O in presence of catalytic amounts of NaBr in CH2Cl2 at room temperature.
文摘Oximes of ketones and aldehydes are efficiently converted to the corresponding carbonyl compounds, using a combination of NaHSO4.H20 and paraformaldehyde in good to excellent yields under solid state conditions at room temperature for 10 minutes.
文摘Oximes were oxidized to the corresponding carbonyl compounds in good to high yields by environmentally friendly and green oxidant, H202 catalyzed by montmorillonite K-10 supported cobalt（Ⅱ） chloride.
基金Priority Academic Program Development of Jiangsu Higher Education Institutions for supportfinancially supported by the fund of the joint-laboratory of Shanghai Dingya Pharmaceutical Chemical Technology Co.,Ltd.with Yangzhou University(No.2022-2027).
文摘Deoximation is an important transformation in synthetic industry.It can be employed in protection,characterization and purification of the carbonyls,and in the synthesis of ketones from non-carbonyl molecules.In the field,oxidative deoximation reaction can utilize the driving force caused by the oxidation process so that the reaction can occur under relatively mild conditions.Recently,we designed and prepared polyaniline-supported molybdenum(Mo@PANI)just by immersing PANI into the EtOH/H_(2)O solution of MoCl_(5).The material was successfully applied as the efficient catalyst for oxidative deoximation reactions,which were performed in ethanol using H_(2)O_(2)as the clean oxidant.The substrate scope of the reaction was wide.It could be applied on heterocycle-containing substrates,making this protocol preferable for pharmaceutical intermediate synthesis.Since Mo is a necessary trace element for both animals and plants,this method is environment-friendly and is suitable for large-scale preparation.This work as the first example of Mo-catalyzed oxidative deoximation reaction may inspire novel ideas for both catalyst design and synthetic process development.
基金Jiangsu Provincial Six Talent Peaks Project(No.XCL-090)Natural Science Foundation of Jiangsu Province(No.BK20181449)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)for support。
文摘Polyaniline-supported tungsten(W@PANI)was easily prepared by immersing polyaniline(PANI)in the aqueous solution of Na2WO4.It was found to be an efficient catalyst for oxidative deoximation reaction,the very important transformation for pharmaceutical industry.Besides the green features,the method employed very few of catalytic tungsten(0.048 mol%vs.oxime substrates),resulting in the high turnover numbers(TONs)of the catalyst(ca.103 mol/mol)and the low metal residues in product(<0.1 ppm).The reaction is applicable for a variety of substrates,including those containing heterocycles,which are key intermediates in medicine synthesis.It has also been successfully magnified to kilogram scale production to afford the desired carbonyl products smoothly.
基金supported by National Key Research and Development Program of China (No. 2018YFD0200100)Natural Science Foundation of Guangling College (Key Project: No. ZKZD17005+4 种基金 major special project: No. ZKZZ18001)Natural Science Foundation of Jiangsu Province (No. BK20181449)Jiangsu Provincial Six Talent Peaks Project (No. XCL-090)Opening Foundation of the Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University (No. 2016GDGP0104)Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
文摘Deoximation reaction is one of the most important transformations in organic synthesis and for fine chemical production.Since oximes are easily synthesized from carbonyl compounds and are stable compounds,this reaction can be used for protection-deprotection,purification,and characterization of carbonyl compounds in organic synthesis,especially for the synthesis of medicines as well as the natural products.Moreover,because many oximes can be synthesized from non-carbonyl starting materials,the deoximation reaction is also widely used in the production of many carbonyl-contained fine chemicals.Deoximation methods by using stoichiometric reagents are mature and can produce the related carbonyl products in very high yield with broad substrate application scopes.But for environment-protection consideration as well as the production cost controlling purpose in fine chemical industry,developing catalytic deoximation methods is the trend of the field and there are a series of references on this topic in recent years.This short review summarized recent advances on the development of deoximation methods from stoichiometric reaction to catalytic reaction and the mechanisms of some important transformations were discussed in detail for reader reference.
基金financially supported by the National Key Research and Development Program of China (2018YFD0200100)Natural Science Foundation of Jiangsu Province (BK20181449)+2 种基金Zhejiang Provincial Natural Science Foundation (LY19B020004)Jiangsu Provincial Six Talent Peaks Project (XCL-090)Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
文摘Catalyzed by commercially available(PhTe)2, molecular oxygen could be utilized as the mild, cheap and safe oxidant for oxidative deoximation reactions under solvent-free conditions. As the first report on organotellurium-catalyzed deoximation reaction, this work not only provides an efficient deoximation method, but also discloses new features of tellurium catalyst different from those of the organoselenium catalysts.
基金the Natural Science Foundation of Jiangsu Province(No.BK20181449)Natural Science Foundation of Zhejiang Province(No.LY19B020004)+1 种基金Jiangsu Provincial Six Talent Peaks Project(No.XCL-090)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)for financial support。
文摘Irradiated by visible light,the recyclable(PhTe)2-catalyzed oxidative deoximation reaction could occur under mild conditions.In comparison with the thermo reaction,the method employed reduced catalyst loading(1 mol%vs.2.5 mol%),but afforded elevated product yields with expanded substrate scope.This work demonstrated that for the organotellurium-catalyzed reactions,visible light might be an even mo re precise driving energy than heating because it could break the Te—Te bond accurately to generate the active free radical catalytic intermediates without damaging the fragile substituents(e.g.,heterocycles)of substrates.The use of O_(2) instead of explosive H_(2)O_(2) as oxidant affords safer reaction conditions from the large-scale application viewpoint.
基金Financial support from the National Natural Science Foundation of China （No. 21072055） and the National High Technology Research and Development Program of China （863 Program） （No. 2008AA06Z306）.
文摘An acceptor-free catalysis protocol for the deoximation of ketoximes and aldoximes using RuCl3 as the catalyst has been developed. Under the optimized conditions, various oximes were converted to ketones and nitriles with excellent isolated yields.
基金Project supported by the Natural Science Foundation of Heilongjiang Province, China （Nos. ZD200820-01 and B200814）.
文摘Deoximation in metal chloride ionic liquids based on 1-alkyl-3-methylimidazolium and triethylene ammonium cations, such as AmimBr（Cl）-MClx （A=ethyl, butyl, benzyl; M=Al, Fe, Cu, Sn and Zn; x=2, 3） and Et3NHCl-FeCl3 were investigated under mild conditions. Ferrate chloride ionic liquid was proved to be an effective catalyst for deoximation of cyclohexanone oxime, exhibiting high conversion of oximes and selectivity to cyclo- hexanone. Good performance for the deoximation of other oximes such as salicylald oxime, acetone oxime, benzo- phenone oxime, 4-nitrobenzald oxime, acetophenone oxime, 2-chlorobenzaldehyde oxime, Acetald oxime, 2-butanone oxime and （1R）-camphor oxime was also achieved with bmimBr-FeCl3 as catalyst and solvent. The de- oximation was determined to carry out via acid-catalytic hydrolysis and the reaction mechanism was proposed.
基金Project supported by the National Natural Science Foundation of China (No. 2967201)the Natural Science Foundation of Gansu Province
文摘A variety of aldoximes and ketoximes were oxidized to corresponding aldehydes and ketones by nitric oxide in the presence of oxygen. A presumed mechanism was suggested.
基金support for this work by the research facilities of Ilam University
文摘A wide variety of aldoximes and ketoximes were regenerated to corresponding carbonyl compounds with Al（NO3）3·9H2O in presence of catalytic amounts of NaBr in CH2Cl2 at room temperature.
