发展了非血红素类四氮配体的铜配合物和2,2,6,6-四甲基哌啶-氮-氧自由基(TEMPO)相结合的催化体系,应用于分子氧参与的伯醇氧化反应。该体系具有条件温和、高效、高选择性、无需任何助剂和底物(包括苄醇、烯丙基醇和含杂原子伯醇)使用性强等优点。此外,利用高分辨质谱和紫外-光谱等对反应活性中间体进行了初步探讨。
A new system consisting of a copper(I) complex generated in situ from a tetradentate nitrogen lig-and and CuI in combination with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) derivatives was successfully developed. The system was suitable for efficient and selective aerobic oxidation of primary benzyl and allyl alcohols with a wide range of functional groups to the corresponding al-dehydes at room temperature. The best result was obtained with N,N'-dimethyl-N,N'-bis(2-pyri-dylmethyl)ethane-1,2-diamine as the ligand and 4-OH-TEMPO as a cocatalyst in CH3CN. In addition, high-resolution mass spectrometry, ultraviolet-visible spectroscopy, and electrochemical experi-ments were used to provide evidence of intermediates.
参考文献
| [1] | de Montellano P R O.Cytochrome P450:Structure,Mechanism,and Biochemistry.2nd Ed[M].New York:Plenum Press,1995 |
| [2] | Turlington C R;White P S;Brookhat M;Templeton J L .[J].Journal of the American Chemical Society,2014,136:3981. |
| [3] | Jacobsen E N.[A].Oxford(UK):Pergamon,1995 |
| [4] | McDonald A R;Que L Jr .[J].Coordination Chemistry Review,2013,257:414. |
| [5] | White M C;Doyle A G;Jacobsen E N .[J].Journal of the American Chemical Society,2001,123:7194. |
| [6] | Prat I;Font D;Company A;Junge K Ribas X Beller M Costas M .[J].Adv Syn Catal,2013,355:947. |
| [7] | Chen M S;White M C .[J].SCIENCE,2007,318:783. |
| [8] | Wu, M;Wang, B;Wang, SF;Xia, CG;Sun, W .Asymmetric Epoxidation of Olefins with Chiral Bioinspired Manganese Complexes[J].Organic letters,2009(16):3622-3625. |
| [9] | Wang, B.;Miao, C.;Wang, S.;Xia, C.;Sun, W. .Manganese catalysts with C _1-symmetric N _4 ligand for enantioselective epoxidation of olefins[J].Chemistry: A European journal,2012(22):6750-6753. |
| [10] | Wang, B.;Wang, S.;Xia, C.;Sun, W. .Highly enantioselective epoxidation of multisubstituted enones catalyzed by non-heme iron catalysts[J].Chemistry: A European journal,2012(24):7332-7335. |
| [11] | Sheldon R A;Arends I W C E;ten Brink G J;Dijksman A .[J].Accounts of Chemical Research,2002,35:774. |
| [12] | 张华,付罗岭,钟红敏.吸附NOx的功能化硅胶用于催化温和条件下醇的选择性氧化[J].催化学报,2013(10):1848-1854. |
| [13] | Wang L Y;Li J;Lv Y;Zhao G D Gao S .[J].Applied Organometallic Chemistry,2012,26:37. |
| [14] | Fritz-Langhals E .[J].Organic Process Research and Development,2005,9:577. |
| [15] | Mu R Z;Liu Z Q;Yang Z J;Liu Z G Wu L M Liu Z L .[J].Advanced Synthesis and Catalysis,2005,347:1333. |
| [16] | 余依玲,高保娇,李艳飞.含环氧基团的聚合物微球固载2,2,6,6-四甲基哌啶氮氧自由基催化剂的制备及其催化分子氧氧化苯甲醇[J].催化学报,2013(09):1776-1786. |
| [17] | Vogler T;Studer A.[J].Synthesis,2008:1979. |
| [18] | Sasano Y;Nagasawa S;Yamazaki M;Shibuya M Park J Iwabuchi Y .[J].ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2014,53:3236. |
| [19] | Semmelhack M F;Schmid C R;Cortes D A;Chou C S .[J].Journal of the American Chemical Society,1984,106:3374. |
| [20] | Mark?I E;Giles P R;Tsukazaki M;Chellé-Regnaut I Gautier A Brown S M Urch C J .[J].Journal of Organic Chemistry,1999,64:2433. |
| [21] | Hoover, J.M.;Stahl, S.S. .Highly practical copper(I)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols[J].Journal of the American Chemical Society,2011(42):16901-16910. |
| [22] | Greene J F;Hoover J M;Mannel D S;Root T W Stahl S S .[J].Org Pro-cess Res Dev,2013,17:1247. |
| [23] | Steves, J.E.;Stahl, S.S. .Copper(I)/ABNO-catalyzed aerobic alcohol oxidation: Alleviating steric and electronic constraints of Cu/TEMPO catalyst systems[J].Journal of the American Chemical Society,2013(42):15742-15745. |
| [24] | Hoover J M;Ryland B L;Stahl S S .[J].ACS Catal,2013,3:2599. |
| [25] | Hoover, J.M.;Ryland, B.L.;Stahl, S.S. .Mechanism of copper(I)/TEMPO-catalyzed aerobic alcohol oxidation[J].Journal of the American Chemical Society,2013(6):2357-2367. |
| [26] | Mannam S;Alamsetti S K;Sekar G .[J].Advanced Synthesis and Catalysis,2007,349:2253. |
| [27] | Jiang N;Ragauskas A J .[J].ChemSusChem,2008,1:823. |
| [28] | Lu ZL;Costa JS;Roubeau O;Mutikainen I;Turpeinen U;Teat SJ;Gamez P;Reedijk J .A copper complex bearing a TEMPO moiety as catalyst for the aerobic oxidation of primary alcohols[J].Dalton transactions: An international journal of inorganic chemistry,2008(27):3567-3573. |
| [29] | Velusamy S;Punniyamurthy T.[J].Eur J Org Chem,2003:3913. |
| [30] | Contel M;Izuel C;Laguna M;Villuendas P R Alonso P J Fish R H .[J].Chemistry-A European Journal,2003,9:4168. |
| [31] | Miao C X;Wang J Q;Yu B;Cheng W G Sun J Chanfreau S He L N Zhang S J .[J].Chemistry Communications,2011,47:2697. |
| [32] | Miao C X;He L N;Wang J L;Wu F .[J].Journal of Organic Chemistry,2010,75:257. |
| [33] | Miao, CX;He, LN;Wang, JQ;Gao, J .Biomimetic Oxidation of Alcohols Catalyzed by TEMPO-Functionalized Polyethylene Glycol and Copper(I) Chloride in Compressed Carbon Dioxide[J].Synlett,2009(20):3291-3294. |
| [34] | Miao C X;He L N;Wang J Q;Wang J L .[J].Advanced Synthesis and Catalysis,2009,351:2209. |
| [35] | Karmakar T K;Aromi G;Ghosh B K;Usman A Fun H K Mallah T Behrens U Solans X Chandra S K .[J].Journal of Materials Chemistry,2006,16:278. |
| [36] | Yu S J;Miao C X;Wang D Q;Wang S F Xia C G Sun W .[J].Journal of Molecular Catalysis A:Chemical,2012,353-354:185. |
| [37] | Semmelhack M F;Chou C S;Cortés D A .[J].Journal of the American Chemical Society,1983,105:4492. |
| [38] | Wang XL;Liu RH;Jin Y;Liang XM .TEMPO/HCl/NaNO2 catalyst: A transition-metal-free approach to efficient aerobic oxidation of alcohols to aldehydes and ketones under mild conditions[J].Chemistry: A European journal,2008(9):2679-2685. |
| [39] | Liu R H;Liang X M;Dong C Y;Hu X Q .[J].Journal of the American Chemical Society,2004,126:4112. |
| [40] | Cole R B.Electrospray Ionization Mass Spectrometry:Fundamen-tals,Instrumentation,and Applications[M].New York:Wiley,1997 |
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