原位生成的水溶性Salen-Cu配合物催化水中H_2O_2氧化醇的研究
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摘要
本文报道一种水溶性Salen与Cu(Ⅱ)离子在水溶液中原位生成铜配合物后,催化双氧水氧化醇生成相应的醛和酮的反应。以苯甲醇为底物,通过对不同的铜盐和反应温度的考察,发现以硫酸铜为配合物的铜源,在40℃下反应3 h,就有93%的苯甲醇氧化成苯甲醛。在同一条件下,考察了该催化体系对苯甲醇衍生物、杂环芳香醇、烯丙醇衍生物以及饱和脂肪醇的氧化性能研究,该体系能很好地氧化苯甲醇衍生物和烯丙醇衍生物,对含O和S杂原子的芳香醇的氧化可获得中等的转化率,对芳香仲醇和脂肪族伯醇氧化效果很差。
A water soluble Salen and Cu( Ⅱ) formed a water soluble Cu-complex in situ.The complex was used as catalyst for the oxidation of alcohols to correspond aldehydes and ketones.The influences of different copper salt and reaction temperature on the oxidation of benzyl alcohol were investigated.It was found that copper sulfate as copper source of complex,under 40℃,the oxidation was last for 3 h,93%of benzyl alcohol was converted to benzaldehyde. Under the same reaction condition,the performances of the catalytic system for the oxidation of benzylic alcohols,heterocyclic aryl alcohols,allylic alcohols and aliphatic alcohol were examined.The catalytic system expressed excellent activity for the oxidation of benzylic alcohols and allylic alcohol,the moderate conversion for the oxidation of containing O and S heterocyclic aryl alcohols.The catalytic system was not suitable for the oxidation of aryl secondary alcohols and aliphatic alcohols.
A water soluble Salen and Cu( Ⅱ) formed a water soluble Cu-complex in situ.The complex was used as catalyst for the oxidation of alcohols to correspond aldehydes and ketones.The influences of different copper salt and reaction temperature on the oxidation of benzyl alcohol were investigated.It was found that copper sulfate as copper source of complex,under 40℃,the oxidation was last for 3 h,93%of benzyl alcohol was converted to benzaldehyde. Under the same reaction condition,the performances of the catalytic system for the oxidation of benzylic alcohols,heterocyclic aryl alcohols,allylic alcohols and aliphatic alcohol were examined.The catalytic system expressed excellent activity for the oxidation of benzylic alcohols and allylic alcohol,the moderate conversion for the oxidation of containing O and S heterocyclic aryl alcohols.The catalytic system was not suitable for the oxidation of aryl secondary alcohols and aliphatic alcohols.
引文
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[33]Ahmad J U,Raisanen M T,LeskelaM,et al.Copper catalyzed oxidation of benzylic alcohols in water with H2O2[J].Appl Catal A:General,2012,411-412:180-187.
[2]Sheldon R A,Kochi J K.Metal catalyzed oxidation of organic compounds[M]. New York:Academic Press,1984,204,359-367.
[3]March J. Advanced organic chemistry:reactions,mechanisms,and structure,fourth ed[M]. New York:Wiley,1992:425-933.
[4]Dess D B,Martin J C.Readily accessible 12-I-5 oxidant for the conversion of primary and secondary alcohols to aldehydes and ketones[J].J Org Chem,1983,48(22):4 155-4 156.
[5]Dess D B,Martin J C. A useful 12-I-5 triacetoxyperiodinane(the Dess-Martin periodinane)for the selective oxidation of primary or secondary alcohols and a variety of related 12-I-5 species[J]. J Am Chem Soc,1991,113(19):7277-7 287.
[6]Alvarez R,Iglesias B,López S,et al.Stereocontrolled synthesis of all-(E)and(8Z)–anhydroretinol[J].Tetrahedron Lett,1998,39(31):5 659-5 662.
[7]Paterson I,Delgado O,Florence G J,et al.1,6-Asymmetric induction in boron-mediated aldol reactions:application to a practical total synthesis of(+)-discodermolide[J]. Org Lett,2002,5(1):35-38.
[8]Muzart J. Palladium-catalysed oxidation of primary and secondary alcohols[J].Tetrahedron,2003,59(31):5 789-5 816.
[9]Willis M C,McNally S J,Beswick P J.Chelation-controlled intermolecular hydroacylation:direct addition of alkyl aldehydes to functionalized alkenes[J]. Angew Chem Int Ed,2004,43(3):340-343.
[10]Jiang,Feng Y,Ison E A.Mechanistic investigations of the iridium(III)-catalyzed aerobic oxidation of primary and secondary alcohols[J].J Am Chem Soc 2008,30(44):14462-14 464.
[11]Sheldon R A,Arends I W C E,Dijksman A.New developments in catalytic alcohol oxidations for fine chemicals synthesis[J].Catal Today,2000,57(1/2):157-166.
[12]Parmeggiani C,Cardona F. Transition metal based catalysts in the aerobic oxidation of alcohols[J].Green Chem,2012,4(3):547-564.
[13]Dewan A,Sarma T,Bora U,et al.Rapid and selective oxidation of benzyl alcohols to aldehydes and ketones with novel vanadium polyoxometalate under solvent-free conditions[J]. Tetrahedron Lett,2011,52(20):25 632-25635.
[14]Song T,Park JE,Chung YK.Rhodium-catalyzed synthesis of imines and esters from benzyl alcohols and nitroarenes:change in catalyst reactivity depending on the presence or absence of the phosphine ligand[J]. J Org Chem,2018,83:4 197-4 203.
[15]Semmelhack M F,Schmid C R,Cortes D A,et al.Oxiadation of alcohols to aldehydes with oxygen and cupric ion,mediated by mitrosonium ion[J].J Am Chem Soc,1984,106:3 374-3 376.
[16]MarkóI E,Giles R R,Tsukazaki M,et al.Efficient,ecologically benign,aerobic oxidation of alcohols[J]. J Org Chem,1999,64:2 433-2 439.
[17]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,2011,133:16901-16 910.
[18]Greene J F,Hoover J M,Mannel D S,et al.Continuousflow aerobic oxidation of primary alcohols with a copper(I)/TEMPO catalyst[J].Org Process Res Dev,2013,17:1 247-1 251.
[19]Steves J E,Stahl S S.Copper(I)/ABNO-catalyzed aerobic alcohol oxidation:alleviating steric and electronic constraints of Cu/TEMPO catalyst systems[J]. J Am Chem Soc,2013,135:15 742-15 745.
[20]Hoover J M,Ryland B L,Stahl S S.Copper/TEMPO-catalyzed aerobic alcohol oxidation:mechanistic assessment of different catalyst systems[J].ACS Catal,2013,3:2 599-2605.
[21]Hoover J M,Ryland B L,Stahl S S.Mechanism of copper(I)/TEMPO-catalyzed aerobic alcohol oxidation[J]. J Am Chem Soc,2013,135:2 357-2 367.
[22]Mannam S,Alamsetti S K,Sekar G.Aerobic,chemoselective oxidation of alcohols to carbonyl compounds catalyzed by a DABCO-copper complex under mild conditions[J].Adv Synth Catal,2007,349:2 253-2 258.
[23]Jiang N,Ragauskas A J.Copper-catalyzed highly efficient aerobic oxidation of alcohols under ambient conditions[J].Chem SUSChem,2008,1:823-825.
[24]孙斌,李忆雪.酰胺型非卟啉类N4配体的合成及其促进溴化铜催化的苄醇氧化性能研究[J].化学研究与应用,2017,29:1 845-1 850.
[25]张淑芳,苗成霞,徐大乾,等,基于四氮配体的铜配合物/TEMPO催化的苄醇与烯丙醇的氧化反应[J].催化学报,2014,35:1 864-1 873.
[26]Chen H,Li Y Z,Chen J R,et al. Synergistic effect of TPPTS and TPPDS on the regioselectivity of olefin hydroformylation in two-phase catalytic system[J]. Catal Today,2002,74:131-135.
[27]Ahmad J U,Raisanen M T,Kemell M,et al.Facile open air oxidation of benzylic alcohols in distilled water by in situ made copper(II)complexes[J].Appl Catal A:General,2012,449:153-162.
[28]Patil M R,Kapdi A R,Kumar A V.Recyclable supramolecular ruthenium catalyst for the selective aerobic oxidation of alcohols on water:application to total synthesis of brittonin A[J]. ACS Sustainable Chem Eng,2018,6:3264-3 278.
[29]Fu H,Li M,Chen H.Higher olefin hydroformylation in organic/aqueous biphasic system accelerated by double long-chain cationic surfactants[J].J Mol Catal A:Chem,2006,259:156-160.
[30]Ang W J,Lam Y.Allylic and benzylic sp3C-H oxidation in water[J].Org Biomol Chem,2015,13:1 048-1 052.
[31]No3l S,Perez F,Pedersen J T. A new water-soluble Cu(II)chelator that retrieves Cu from Cu(amyloid-β)species,stops associated ROS production and prevents Cu(II)-induced Aβaggregation[J].J Inorg Biochem,2012,117:322-325.
[32]Hu Z,Kerton F M.Room temperature aerobic oxidation of alcohols using Cu Br2with TEMPO and a tetradentate polymer based pyridyl-imine ligand[J].Appl Catal A:General,2012,413-414:332-339.
[33]Ahmad J U,Raisanen M T,LeskelaM,et al.Copper catalyzed oxidation of benzylic alcohols in water with H2O2[J].Appl Catal A:General,2012,411-412:180-187.