一类有机可溶聚合物固载手性环己二胺负载钌催化剂的合成、表征及在不对称催化中的应用
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摘要
本文以廉价的1R,2R-环己二胺为原料,通过一系列(磺酰胺化、烯烃聚合)化学反应,合成不同聚合度含有机膦酸官能团的聚合物载体。通过氮原子的配位络合作用将[RuCl2(p-cymene)]负载于该有机聚合物载体上,制备了在酸性介质中能溶于四氢呋喃、乙腈、氯仿和N,N-二甲基甲酰胺等有机溶剂的有机聚合物负载钌催化剂。在催化反应结束后,加入乙酸乙酯等有机溶剂,该负载钌催化剂可从均相反应体系中析出,通过过滤可回收(87-93%)。
用IR, TEM, XRD和N2等温吸附曲线对有机聚合物载体和负载手性催化剂的结构和表面形貌进行了分析,并确定了其组成。实验表明：与其他有机高分子载体不同,含有机膦酸官能团的聚合物载体具有微孔结构(1-20 A)、线形(宽20-50 nm)的网状结构。负载过渡金属钉后,载体的线状形貌结构被打断,形成了团簇状结构。
将该负载钌手性催化剂应用于苯乙酮及其衍生物的不对称转移氢化,探索了不同钌负载量、溶剂、温度和反应时间等条件对催化性能的影响,筛选了最佳的催化反应条件。在最佳的催化反应条件下(10 wt%钌负载量、m苯乙酮/mRu=100：1、V甲酸/V三乙胺=1：3,底物浓度为1.72 mol/mL,甲醇溶剂、50℃、反应6 h),反应产物的转化率和对映选择性分别为41.3-99%和80.1-97.3%ee,没有其它副产物产生。
In this article, the organosoluble polystyrene polymer containing phosphonate group had been synthesized by using 1R,2R-Diaminocyclohexane as raw material through several steps (p-toluenesulfonyl and radical polymerization reaction). Upon the immobilization of [RuCl2(p-cymene)]2 on the synthesized polystyrene polymer by the complexation reaction of amino group with metal ruthenium, catalysts 4a-c organosoluble in THF, DMF, DMSO, CH2Cl2, CHCl3, CH3CN, CH3OH and so on in acidic medium were prepared. After the catalytic reaction was completed, ethyl acetate was added, and then supported ruthenium catalyst 4c precipitated out and recycled in 87-93% yield.
The structure and surface morphology had been characteried by IR, TG, XPRD, SEM, TEM, and N2 adsorption-desorption isotherm. It was shown that 3c is a novel type of catalyst support possessed the filiform and microporous structure with 20-50 nm width and 1-20A micropores.
In the asymmetric transfer hydrogenation of acetophenone and it derivatives, the optinum catalytic conditions such as the supported amount of transitional metal ruthenium, solvent, temperature and reaction time were screened in details. The products of acetophenone and it derivatives in 41.3-99% conversion and 80.1-97.3% ee without side-products (100% chemical selectivity) were obtained at 50℃for 6 h in methanol containing 1.72 mol/mL substrates by using 10 wt% Ru catalyst (S/C=100).
用IR, TEM, XRD和N2等温吸附曲线对有机聚合物载体和负载手性催化剂的结构和表面形貌进行了分析,并确定了其组成。实验表明：与其他有机高分子载体不同,含有机膦酸官能团的聚合物载体具有微孔结构(1-20 A)、线形(宽20-50 nm)的网状结构。负载过渡金属钉后,载体的线状形貌结构被打断,形成了团簇状结构。
将该负载钌手性催化剂应用于苯乙酮及其衍生物的不对称转移氢化,探索了不同钌负载量、溶剂、温度和反应时间等条件对催化性能的影响,筛选了最佳的催化反应条件。在最佳的催化反应条件下(10 wt%钌负载量、m苯乙酮/mRu=100：1、V甲酸/V三乙胺=1：3,底物浓度为1.72 mol/mL,甲醇溶剂、50℃、反应6 h),反应产物的转化率和对映选择性分别为41.3-99%和80.1-97.3%ee,没有其它副产物产生。
In this article, the organosoluble polystyrene polymer containing phosphonate group had been synthesized by using 1R,2R-Diaminocyclohexane as raw material through several steps (p-toluenesulfonyl and radical polymerization reaction). Upon the immobilization of [RuCl2(p-cymene)]2 on the synthesized polystyrene polymer by the complexation reaction of amino group with metal ruthenium, catalysts 4a-c organosoluble in THF, DMF, DMSO, CH2Cl2, CHCl3, CH3CN, CH3OH and so on in acidic medium were prepared. After the catalytic reaction was completed, ethyl acetate was added, and then supported ruthenium catalyst 4c precipitated out and recycled in 87-93% yield.
The structure and surface morphology had been characteried by IR, TG, XPRD, SEM, TEM, and N2 adsorption-desorption isotherm. It was shown that 3c is a novel type of catalyst support possessed the filiform and microporous structure with 20-50 nm width and 1-20A micropores.
In the asymmetric transfer hydrogenation of acetophenone and it derivatives, the optinum catalytic conditions such as the supported amount of transitional metal ruthenium, solvent, temperature and reaction time were screened in details. The products of acetophenone and it derivatives in 41.3-99% conversion and 80.1-97.3% ee without side-products (100% chemical selectivity) were obtained at 50℃for 6 h in methanol containing 1.72 mol/mL substrates by using 10 wt% Ru catalyst (S/C=100).
引文
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[20]Mikhailine, Alexandre A.; Morris, Robert H. Effect of the Structure of the Diamine Backbone of P-N-N-P ligands in Iron(II) Complexes on Catalytic Activity in the Transfer Hydrogenation of Acetophenone. Inorg. Chem.2010,49,11039-11044.
[21]Chen, Gui; Xing, Yan; Zhang, Hui; Gao, Jing-Xing. Synthesis of novel chiral macrocyclic ONNO-type ligands and use in asymmetric transfer hydrogenation. J. Mol. Catal. A:Chem. 2007,273,284-288.
[22]Zhao, Baoguo; Wang, Zheng; Ding, Kuiling. Practical by ligand design:a new class of monodentate phosphoramidite ligands for rhodium-catalyzed enantioselective hydrogenation. Adv. Syn & Cat.2006,348,1049-1057.
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[24]Canivet, Jerome; Labat, Gael; Stoeckli-Evans, Helen; Suss-Fink, Georg. Water-soluble arene ruthenium complexes containing a trans-1,2-diaminocyclohexane ligand as enantioselective transfer hydrogenation catalysts in aqueous solution. Eur. J. Inorg. Chem.2005,22, 4493-4500.
[25]Xu, Yingjian; Docherty, Gordon F.; Woodward, Gary; Wills, Martin. Ru (II) complexes of cyclohexanediamine and monodentate phosphorus ligands for asymmetric ketone hydrogenation. Tetrahedron:Asymmetry.2006,17,2925-2929.
[26]Cortez, Norma A.; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy. Ruthenium (Ⅱ) and rhodium (Ⅲ) catalyzed asymmetric transfer hydrogenation (ATH) of acetophenone in isopropanol and in aqueous sodium formate using new chiral substituted aromatic monosulfonamide ligands derived from (1R,2R)-diaminocyclohexane. Tetrahedron:Asymmetry. 2008,19,1304-1309.
[27]Yang, Qihua; Liu, Jian; Yang, Jie; Zhang, Lei; Feng, Zhaochi; Zhang, Jing; Li, Can. Acid catalyzed synthesis of ordered bifunctionalized mesoporous organosilicas with large pore. Microporous Mesoporous Mater.2005,77,257-264.
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[29]Tian, Hua; Li. Jinjun; Zou, Linda; Mu, Zhen; Hao, Zhengping. Removal of DDT from aqueous solutions using mesoporous silica materials. J. Chem. Technol. Biotechnol.2009,84,490-496.
[30]Hao, Na; Wang, Huanting; Webley, Paul A.; Zhao, Dongyuan. Synthesis of uniform periodic mesoporous organosilica hollow spheres with large-pore size and efficient encapsulation capacity for toluene and the large biomolecule bovine serum albumin. Microporous Mesoporous Mater.2010,132,543-551.
[31]Yang, Hengquan; Han, Xiaojing; Li, Guang; Ma, Zhancheng; Hao, Yajuan. Mesoporous ethane-silicas functionalized with a bulky N-heterocyclic carbene for Suzuki-Miyaura coupling of aryl chlorides and benzyl chlorides. J. Phys. Chem.2010,24,53-56
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[2]Arai, Noriyoshi; Azuma, Keita; Nii, Noriyuki; Ohkuma, Takeshi. Highly enantioselective hydrogenation of aryl vinyl ketones to allylic alcohols catalyzed by the tol-binap/dmapen ruthenium(Ⅱ) complex. Angew. Chem, Int. Ed.2008,47,7457-7460.
[3]Wu, Xiaofeng; Li, Xiaoguang; King, Frank; Xiao, Jianliang. Insight into and practical application of pH-controlled asymmetric transfer hydrogenation of aromatic ketones in water. Angew. Chem, Int. Ed.2005,44,3407-3411.
[4]Liu, Pei Nian; Gu, Pei Ming; Deng, Jin Gen; Tu*; Yong Qiang; Ma, Ya Ping. Efficient heterogeneous asymmetric transfer hydrogenation catalyzed by recyclable silica-supported Ru-TsDPEN complexes. Eur. J. Org. Chem.2005,3221-3227.
[5]Zhou, Haifeng; Li, Zhiwei; Wang, Zhijian; Wang, Tianli; Xu, Lijin; He, Yanmei; Fan, QingHua; Pan, Jie; Gu, Lianquan; Chan, Albert S. C. Hydrogenation of quinolines using a recyclable phosphine-free chiral cationic ruthenium catalyst:enhancement of catalyst stability and selectivity in an ionic liquid. Angew. Chem.,2008,47,8464-8467.
[6]Zhu, GongJian; Da, Chao-Shan; Jia, Ya-Ning; Ma, Xiao; Yi, Lei. Direct asymmetric aldol reaction catalyzed by C2-symmetrical chiral primary amine catalysts. Lett. Org. Chem.2010, 7,15-20.
[7]Hu, Shenshen; Li, Jiuyuan; Xiang, Junfeng; Pan, Jie; Luo, Sanzhong; Cheng, Jin-Pei. Asymmetric Supramolecular Primary Amine Catalysis in Aqueous Buffer:Connections of Selective Recognition and Asymmetric Catalysis. J. Am. Chem. Soc.,2010,132,7216-7228.
[8]Huang, Huicai; Yu, Feng; Jin, Zhichao; Li, Wenjun; Wu, Wenbin; Liang, Xinmiao; Ye, Jinxing. Asymetiic vinylogous Michael reaction of unsaturated ketones with butenolide under multifunctional catalysis. Chem Commun.2010,46,5957-5959.
[9]Tomotaka, Okino, Satoru Nakamura, Tomihiro Furukawa, and Yoshiji Takemoto. Enantioselective aza-Henry reaction catalyzed by a bifunctional organocatalyst Org. Lett,2004, 6,625-627
[10]Yujiro Hayashi,* Hiroaki Gotoh, Tomohiro Tamura, Hirofumi Yamaguchi, Ryouhei Masui, and Mitsuru Shoji. Cysteine-Derived Organocatalyst in a Highly Enantioselective Intramolecular Michael Reaction.J Am. Chem. Soc.2005,127,16028-16029
[11]Wang, Xiao; Chen, YongFei; Niu, LiangFeng; Xu, PengFei. Diastereo-and Enantioselective Aza-MBH-Type Reaction of Nitroalkenes to N-Tosylimines Catalyzed by Bifunctional Organocatalysts. Org. Lett.2009,11,3310-3313.
[12]Baratta, Walter; Barbato, Cinzia; Magnolia, Santo; Siega, Katia; Rigo, Pierluigi. Chiral and Nonchiral[OsX2(diphosphane)(diamine)](X:Cl, OCH2CF3) Complexes for Fast Hydrogenation of Carbonyl Compounds. Chem. Eur. J.2010,16,3201-3206.
[13]Carril, Monica; SanMartin, Raul; Dominguez, Esther; Tellitu, Imanol. Simple and efficient recyclable catalytic system for performing copper-catalyzed S-arylation reactions in the presence of water. Chem. Eur. J.2007,13,5100-5105.
[14]Zhang, Guoqi; Yashima, Eiji; Woggon, Wolf-D. Versatile supramolecular copper (II) complexes for Henry and Aza-Henry reactions. Adv. Syn & Cat.2009,351,1255-1262.
[15]Nguyen, Quang Trung; Jeong, Jong Hwa. Syntheses and X-ray structures of Cu (Ⅱ) and Zn (Ⅱ) complexes of N, N'-dibenzyl-(R, R)-1,2-diaminocyclohexane and application to nitroaldol reaction. Polyhedron.2008,27,3227-3230.
[16]Alakonda, Laxhmaiah; Periasamy, Mariappan. Copper(Ⅰ) catalysis:Synthesis of N,N'-diarylated and N-aryl,N'-formylated chiral C2-symmetric diamines.J. Organomet. Chem. 2009,694,3859-3863.
[17]Wang, NaiXing; Zhao, Jia. A Novel NADH Model:Design, Synthesis, and its Chiral Reduction and Fluorescent Emission. Adv. Syn & Cat.2009,351,3045-3050.
[18]Kull, Thomas; Peters, Rene. Contact ion pair directed Lewis acid catalysis:asymmetric synthesis of trans-configured lactones. Angew. Chem. Int. Edition.2008,47,5461-5464.
[19]Egami, Hiromichi; Katsuki, Tsutomu. Fe (salan)-Catalyzed Asymmetric Oxidation of Sulfides with Hydrogen Peroxide in Water. J. Am. Chem. Soc.2007,129,8940-8941.
[20]Mikhailine, Alexandre A.; Morris, Robert H. Effect of the Structure of the Diamine Backbone of P-N-N-P ligands in Iron(II) Complexes on Catalytic Activity in the Transfer Hydrogenation of Acetophenone. Inorg. Chem.2010,49,11039-11044.
[21]Chen, Gui; Xing, Yan; Zhang, Hui; Gao, Jing-Xing. Synthesis of novel chiral macrocyclic ONNO-type ligands and use in asymmetric transfer hydrogenation. J. Mol. Catal. A:Chem. 2007,273,284-288.
[22]Zhao, Baoguo; Wang, Zheng; Ding, Kuiling. Practical by ligand design:a new class of monodentate phosphoramidite ligands for rhodium-catalyzed enantioselective hydrogenation. Adv. Syn & Cat.2006,348,1049-1057.
[23]Hodgson, Richard; Douthwaite, Richard E. Synthesis and asymmetric catalytic application of chiral imidazolium-phosphines derived from (1R,2R)-trans-diaminocyclohexane. J. Organomet. Chem.2005,690,5822-5831.
[24]Canivet, Jerome; Labat, Gael; Stoeckli-Evans, Helen; Suss-Fink, Georg. Water-soluble arene ruthenium complexes containing a trans-1,2-diaminocyclohexane ligand as enantioselective transfer hydrogenation catalysts in aqueous solution. Eur. J. Inorg. Chem.2005,22, 4493-4500.
[25]Xu, Yingjian; Docherty, Gordon F.; Woodward, Gary; Wills, Martin. Ru (II) complexes of cyclohexanediamine and monodentate phosphorus ligands for asymmetric ketone hydrogenation. Tetrahedron:Asymmetry.2006,17,2925-2929.
[26]Cortez, Norma A.; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy. Ruthenium (Ⅱ) and rhodium (Ⅲ) catalyzed asymmetric transfer hydrogenation (ATH) of acetophenone in isopropanol and in aqueous sodium formate using new chiral substituted aromatic monosulfonamide ligands derived from (1R,2R)-diaminocyclohexane. Tetrahedron:Asymmetry. 2008,19,1304-1309.
[27]Yang, Qihua; Liu, Jian; Yang, Jie; Zhang, Lei; Feng, Zhaochi; Zhang, Jing; Li, Can. Acid catalyzed synthesis of ordered bifunctionalized mesoporous organosilicas with large pore. Microporous Mesoporous Mater.2005,77,257-264.
[28]Zapilko, Clemens; Liang, Yucang; Nerdal, Willy; Anwander, Reiner. A general strategy for the rational design of size-selective mesoporous catalysts. Chem. Eur. J.2007,13,3169-3176.
[29]Tian, Hua; Li. Jinjun; Zou, Linda; Mu, Zhen; Hao, Zhengping. Removal of DDT from aqueous solutions using mesoporous silica materials. J. Chem. Technol. Biotechnol.2009,84,490-496.
[30]Hao, Na; Wang, Huanting; Webley, Paul A.; Zhao, Dongyuan. Synthesis of uniform periodic mesoporous organosilica hollow spheres with large-pore size and efficient encapsulation capacity for toluene and the large biomolecule bovine serum albumin. Microporous Mesoporous Mater.2010,132,543-551.
[31]Yang, Hengquan; Han, Xiaojing; Li, Guang; Ma, Zhancheng; Hao, Yajuan. Mesoporous ethane-silicas functionalized with a bulky N-heterocyclic carbene for Suzuki-Miyaura coupling of aryl chlorides and benzyl chlorides. J. Phys. Chem.2010,24,53-56
[32]Jiang, Dongmei; Yang, Qihua; Wang, Hong; Zhu, Guiru; Yang, Jie; Li, Can. Periodic mesoporous organosilicas with trans-(1R,2R)-diaminocyclohexane in the framework:A potential catalytic material for asymmetric reactions. J. Catal.2006,239,65-73.
[33]Mihalcik, David J.; Lin, Wenbin. Mesoporous silica nanosphere supported ruthenium catalysts for asymmetric hydrogenation. Angew. Chem. Int. Ed.2008,47,6229-6232.
[34]Hopkins, J. Matthew; Dalrymple, Sean A.; Parvez, Masood; Keay, Brian A.3,3'-Disubstituted BINAP Ligands:Synthesis, Resolution, and Applications in Asymmetric Hydrogenation. Org. Lett.2005,7,3765-3768.
[35]Gao, JingXing; Yi, Xiao Dong; Tang, ChunLiang; Xu, PianPian; Wan, HuiLin. Preparation and use of polymer-supported chiral ruthenium complex catalyst. Poly. Adv.Tech.2001,12, 716-719.
[36]Bandini, Marco; Pietrangelo, Agostino; Sinisi, Riccardo; Umani-Ronchi, Achille; Wolf, Michael O. New Electrochemically Generated Polymeric Pd Complexes as Heterogeneous Catalysts for Suzuki Cross-Coupling Reactions. Eur. J. Org. Chem.2009,21,3554-3561,
[37]Michalek, F.; Madge, D.; Ruhe, J.; Bannwarth, W. Ring-Closure Metathesis in Supercritical Carbon Dioxide as Sole Solvent with Use of Covalently Immobilized Ruthenium Catalysts. Eur. J. Org. Chem.2006,577.
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