氮氧自由基TEMPO在合成化学中的应用进展
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摘要
氧化反应及硝化反应是化学合成中的基础反应类型,传统合成方法污染性大且选择性差,绿色环保的实验方法更加受到青睐。2,2,6,6-四甲基哌啶-1-氧自由基(TEMPO)是一种稳定的自由基,自发现以来被广泛地应用在化学合成的各个领域中。因其具有高活性、高选择性和高稳定性,因此在醇的氧化反应和烯烃的硝化反应上得到广泛应用。以TEMPO在醇氧化反应及烯烃的硝化反应上的应用为方向,描述了TEMPO在各种不同助氧化剂及硝化剂下参与的氧化反应及硝化反应,并综述了最新的研究进展。
Oxidation and nitration are the primary reactions types in chemical synthesis,but the traditional methods have the disadvantages of severe pollution and poor selectivity.The green environmental experiment method is more favored.2,2,6,6-tetramethylpiperidine-1-oxyl radical( TEMPO) as green and stable free radical,has been widely used in various fields of chemical synthesis.It has been employed in the oxidation of alcohols and high stability.Based on the application of TEMPO in alcohol oxidation and olefin nitration,the latest research progress with regards to the oxidation and nitration reactions of TEMPO under the presence of varying oxidants and nitrating agents was reviewed.
Oxidation and nitration are the primary reactions types in chemical synthesis,but the traditional methods have the disadvantages of severe pollution and poor selectivity.The green environmental experiment method is more favored.2,2,6,6-tetramethylpiperidine-1-oxyl radical( TEMPO) as green and stable free radical,has been widely used in various fields of chemical synthesis.It has been employed in the oxidation of alcohols and high stability.Based on the application of TEMPO in alcohol oxidation and olefin nitration,the latest research progress with regards to the oxidation and nitration reactions of TEMPO under the presence of varying oxidants and nitrating agents was reviewed.
引文
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[30]ZHANG J,JIANG Z J.Transition-metal-free TEMPO catalyzed aerobic oxidation of alcohols to carbonyls using an efficient Br2,equivalent under mild conditions[J].Chinese J.Chem.,2013,31(6):794-798.
[31]LAEINI M S,SHAABANI A. A transition-metal-free homogeneous TEMPO-based catalyst:aerobic oxidation of alcohols in aqueous media[J].Chemistry Select,2017,2(28):9 084-9 087.
[32]FIORAVANTI S,PELLACANI L,TARDELLA P A,et al.Facile and highly stereoselective one-pot synthesis of either(E)-or(Z)-nitro alkenes[J]. Org. Lett.,2008,10(7):1 449-1 451.
[33]MAITY S,MANNA S,RANA S,et al.Efficient and stereoselective nitration of mono-and disubstituted olefins with Ag NO2and TEMPO[J]. J. Am. Chem. Soc.,2013,135(9):3 355-3 358.
[34]MANNA S,MAITY S,RANA S,et al. Ipso-nitration of arylboronic acids with bismuth nitrate and perdisulfate[J].Org.Lett.,2012,14(7):1 736-1 739.
[35]MAITY S,NAVEEN T,SHARMA U,et al.Efficient and stereoselective nitration of olefins with Ag NO2and TEMPO[J].Synlett,2014,25(5):603-607.
[36]LI Y,STUDER A. Transition-metal-free trifluoromethylaminoxylation of alkenes[J]. Angew. Chem. Int. Edit.,2012,51(33):8 221-8 224.
[37]NAVEEN T,MAITY S,SHARMA U,et al.A predictably selective nitration of olefin with Fe(NO3)3and TEMPO[J].J.Org.Chem.,2013,78(12):5 949-5 954.
[38]MAITY S,NAVEEN T,SHARMA U,et al. Stereoselective nitration of olefins with(t)Bu ONO and TEMPO:direct access to nitroolefins under metal-free conditions[J].Org.Lett.,2013,15(13):3 384-3 387.
[39]BACHMAN G,BIERMANN T. Nitration studies.ⅩⅦ.conversion of carboxylic acid derivatives to nitroalkanes[J].J.Org.Chem.,1970,35(12):4 229-4 231.
[40]DAS J P,SINHA P,ROY S. A nitro-hunsdiecker reaction:from unsaturated carboxylic acids to nitrostyrenes and nitroarenes[J]. Org. Lett.,2002,4(18):3 055-3 058.
[41]WU X F,SCHRANCK J,NEUMANN H,et al.Convenient and mild synthesis of nitroarenes by metal-free nitration of arylboronic acids[J]. Chem. Commun.,2012,43(11):12 462-12 463.
[42]MANNA S,JANA S,SABOO T,et al.Synthesis of(E)-nitroolefins via decarboxylative nitration using t-butylnitrite(t-Bu ONO)and TEMPO[J]. Chem. Commun.,2013,49(46):5 286-5 288.
[43]ZHAO A,JIANG Q,JIA J,et al.K2S2O8-mediated nitration of alkenes with Na NO2and 2,2,6,6-tetramethylpiperidine-1-oxyl:stereoselective synthesis of(E)-nitroalkenes[J].Tetrahedron Lett.,2016,57(1):80-84.
[2]YAMAGO S,NAKAMURA Y.Recent progress in the use of photoirradiation in living radical polymerization[J].Polymer,2013,54(3):981-994.
[3]WERTZ S,STUDER A. Nitroxide-catalyzed transitionmetal-free aerobic oxidation processes[J]. Green Chem.,2013,15(11):3 116-3 134.
[4]TEBBEN L,STUDER A. Nitroxides:applications in synthesis and in polymer chemistry[J].Angew.Chem.Int.Edit.,2011,50(22):5 034-5 068.
[5]CHU T,LIN R Y,LEE C,et al.Ionic liquid with a dualredox couple for efficient dye-sensitized solar cells[J].Chem Sus Chem,2014,7(1):146-153.
[6]BERGNER B J,HOFMANN C,SCHURMANN A,et al.Understanding the fundamentals of redox mediators in Li-O2batteries:a case study on nitroxides[J]. Phys.Chem.Chem.Phys.,2015,17(47):31 769-31 779.
[7]JANOSCHKA T,MARTIN N,MARTIN U,et al.An aqueous,polymer-based redox-flow battery using non-corrosive,safe,and low-cost materials[J]. Nature,2015,527(7 576):78-81.
[8]ANELLI P L,BIFFI C,MONTANARI F.Oxidation of diols with alkali hypochlorites catalyzed by oxammoniun salts under two-phase conditions[J].J.Org.Chem.,1989,54(12):2 970-2 972.
[9]GOLUBEY V A,ROZANTSEYG,NEIMAN M B.Some reactions of free iminoxyl radicals with the participation of the unpaired electron[J].Bull.Acad.Sci.USSR,Div.Chem.Sci.,1965,14(11):1 898-1 904.
[10]ROGER A,SHELDON R.Organocatalytic oxidations mediated by nitroxyl radicals[J]. Adv. Synth. Catal.,2004,346(9/10):1 051-1 071.
[11]SEMMELHACK M F,CHOU C S,CORTES D A.Nitroxyl-mediated electrooxidation of alcohols to aldehydes and ketones[J]. J. Am. Chem. Soc.,1983,105(13):4 492-4 494.
[12]SEMMELHACK M F,SCHMID C R,CORTS D A.Mechanism of the oxidation of alcohols by 2,2,6,6-tetramethylpiperidine nitrosonium cation[J]. Tetrahedron Lett.,1986,27(10):1 119-1 122.
[13]BAILRY W F,BOBBITT J M,WIBERG K B.Mechanism of the oxidation of alcohols by oxoammonium cations[J].J.Org.Chem.,2007,72(12):4 504-4 509.
[14]TOMOHIDE O,TOMOTAKE A,YUKIHIRO S,et al.Sodium hypochlorite pentahydrate(Na OCl·5H2O)crystals; an effective re-oxidant for TEMPO oxidation[J].Tetrahedron,2016,72(22):2 818-2 827.
[15]BRACKMAN W,GAASBEEK C. Homogeneous catalysis.:Radicals of the R2NO type as catalysts for the oxidation of methanol by cupric complexes and as promoters for various oxidations catalysed by copper[J]. Rec.Trav.Chim.,1966,85(2):221-241.
[16]BRACKMAN W,GAASBEEK C. Homogeneous catalysis.:Di-tert-butylnitroxide as promoter of the copper-catalyzed oxidation of methanol by oxygen[J]. Rec. Trav.Chim.,1966,85(2):257-267.
[17]SEMMELHACK M F,SCHMID C R,CORTES D A,et al. Oxidation of alcohols to aldehydes with oxygen and cuppic ion,mediated by nitrosonium ion[J]. J. Am.Chem.Soc.,1984,106(11):3 374-3 376.
[18]GAMEZ P,ARENDS I,SHELDON R,et al.Room temperature aerobic copper-catalysed selective oxidation of primary alcohols to aldehydes[J]. Adv. Synth. Catal.,2004,346(7):805-811.
[19]KUMPULAINEN E T,KOSKINEN A M.Catalytic activity dependency on catalyst components in aerobic copperTEMPO oxidation[J]. Chem. Eur. J.,2010,15(41):10 901-10 911.
[20]HOOVER J M,STAHL S S. Highly practical copper(Ⅰ)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols[J]. J. Am. Chem. Soc.,2011,133(42):16 901-16 910.
[21]WANG L Y,SHANG S S,LI G S,et al.Iron/ABNO-catalyzed aerobic oxidation of alcohols to aldehydes and ketones under ambient atmosphere[J]. J. Org. Chem.,2016,47(28):2 189-2 193.
[22]MA S M,LIU J X,LI S H,et al.Development of a general and practical Iron nitrate/TEMPO-catalyzed aerobic oxidation of alcohols to aldehydes/ketones:catalysis with table salt[J]. Adv. Synth. Catal.,2011,353(6):1 005-1 017.
[23]LAGERBLOM K,LAGERSPETS E,KESKIVALI J,et al. Practical aerobic oxidation of alcohols:ligand enhanced TEMPO/Mn(NO3)2catalyst system[J]. ChemCat Chem,2017,9(20):3 880-3 887.
[24]HANSON S K,WU R,SILKS L A.Mild and selective vanadium-catalyzed oxidation of benzylic,allylic,and propargylic alcohols using air[J]. Org. Lett.,2011,13(8):1 908-1 911.
[25]LIU R H,LING X M,DONG C Y,et al.Transition-metal-free:a highly efficient catalytic aerobic alcohol oxidation process[J]. J. Am. Chem. Soc.,2004,126(13):4 112-4 113.
[26]LIU R H,DONG C Y,LIANG X M,et al. Highly efficient catalytic aerobic oxidations of benzylic alcohols in water[J].J.Org.Chem.,2005,70(2):729-731.
[27]XIE Y,MO W M,XU D,et al.Efficient NO equivalent for activation of molecular oxygen and its applications in transition-metal-free catalytic aerobic alcohol oxidation[J].J.Org.Chem.,2007,72(11):4 288-4 291.
[28]WANG X L,LIU R H,JIN Y,et al. TEMPO/HCl/Na NO2catalyst:a transition-metal-free approach to efficient aerobic oxidation of alcohols to aldehydes and ketones under mild conditions[J]. Chem. Eur. J.,2010,14(9):2 679-2 685.
[29]YANG G Y,WANG W,ZHU W M,et al.In situ formation of NOx,and Br anion for aerobic oxidation of benzylic alcohols without transition metal[J]. Synlett,2010,41(3):437-440.
[30]ZHANG J,JIANG Z J.Transition-metal-free TEMPO catalyzed aerobic oxidation of alcohols to carbonyls using an efficient Br2,equivalent under mild conditions[J].Chinese J.Chem.,2013,31(6):794-798.
[31]LAEINI M S,SHAABANI A. A transition-metal-free homogeneous TEMPO-based catalyst:aerobic oxidation of alcohols in aqueous media[J].Chemistry Select,2017,2(28):9 084-9 087.
[32]FIORAVANTI S,PELLACANI L,TARDELLA P A,et al.Facile and highly stereoselective one-pot synthesis of either(E)-or(Z)-nitro alkenes[J]. Org. Lett.,2008,10(7):1 449-1 451.
[33]MAITY S,MANNA S,RANA S,et al.Efficient and stereoselective nitration of mono-and disubstituted olefins with Ag NO2and TEMPO[J]. J. Am. Chem. Soc.,2013,135(9):3 355-3 358.
[34]MANNA S,MAITY S,RANA S,et al. Ipso-nitration of arylboronic acids with bismuth nitrate and perdisulfate[J].Org.Lett.,2012,14(7):1 736-1 739.
[35]MAITY S,NAVEEN T,SHARMA U,et al.Efficient and stereoselective nitration of olefins with Ag NO2and TEMPO[J].Synlett,2014,25(5):603-607.
[36]LI Y,STUDER A. Transition-metal-free trifluoromethylaminoxylation of alkenes[J]. Angew. Chem. Int. Edit.,2012,51(33):8 221-8 224.
[37]NAVEEN T,MAITY S,SHARMA U,et al.A predictably selective nitration of olefin with Fe(NO3)3and TEMPO[J].J.Org.Chem.,2013,78(12):5 949-5 954.
[38]MAITY S,NAVEEN T,SHARMA U,et al. Stereoselective nitration of olefins with(t)Bu ONO and TEMPO:direct access to nitroolefins under metal-free conditions[J].Org.Lett.,2013,15(13):3 384-3 387.
[39]BACHMAN G,BIERMANN T. Nitration studies.ⅩⅦ.conversion of carboxylic acid derivatives to nitroalkanes[J].J.Org.Chem.,1970,35(12):4 229-4 231.
[40]DAS J P,SINHA P,ROY S. A nitro-hunsdiecker reaction:from unsaturated carboxylic acids to nitrostyrenes and nitroarenes[J]. Org. Lett.,2002,4(18):3 055-3 058.
[41]WU X F,SCHRANCK J,NEUMANN H,et al.Convenient and mild synthesis of nitroarenes by metal-free nitration of arylboronic acids[J]. Chem. Commun.,2012,43(11):12 462-12 463.
[42]MANNA S,JANA S,SABOO T,et al.Synthesis of(E)-nitroolefins via decarboxylative nitration using t-butylnitrite(t-Bu ONO)and TEMPO[J]. Chem. Commun.,2013,49(46):5 286-5 288.
[43]ZHAO A,JIANG Q,JIA J,et al.K2S2O8-mediated nitration of alkenes with Na NO2and 2,2,6,6-tetramethylpiperidine-1-oxyl:stereoselective synthesis of(E)-nitroalkenes[J].Tetrahedron Lett.,2016,57(1):80-84.