HClO_4和HClO_4-SiO_2催化的β-二羰基化合物与醇、烯烃化合物的加成反应及TfOH-SiO_2催化的磺酰胺类化合物与烯烃的加成反应
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摘要
本论文以1mol%用量的HClO4为催化剂,实现了β-二羰基化合物与仲醇或烯烃的直接加成反应。该反应可以很方便的在空气中和未经处理的溶剂中进行,对绝大部分底物都得到了85%以上的产率。另外,本论文将HClO4吸附在硅胶上,制备了硅胶负载的HClO4(HClO4-SiO2),与液体HClO4催化的β-二羰基化合物与仲醇或烯烃的加成反应相比,HClO4-SiO2催化的非均相加成反应对一些底物获得了更好的产率。HClO4-SiO2可以通过过滤的方法,方便的回收,并且在催化反应中可以循环利用四次。本论文还通过动力学实验,证明了HClO4催化的β-二羰基化合物与仲醇或烯烃的加成反应是SN1的反应机理。
本论文第一次利用易得、廉价的硅胶负载的三氟甲磺酸(TfOH-SiO2)为催化剂,催化了磺酰胺类化合物对不饱和烯烃的加成反应。在5mol%的催化剂用量下,该反应可以很方便的在空气中和未经处理的溶剂中进行,催化剂可以循环使用6次,而催化剂的反应活性和产物的收率都不会降低,每次循环反应的收率都在95%以上。多种磺酰胺类化合物与烯烃的加成反应,在该非均相催化体系中都获得了80%以上的产率。
In this thesis, the direct additions ofβ-diketones to secondary alcohols or alkenes have been achieved using perchloric acid (HClO4) as the catalyst in low catalytic loading (lmol%). The HClO4-catalyzed reactions could be conveniently conducted in air with undried solvents and majority of the substrate gave more than 85%yields. Moreover, when HClO4 was absorbed onto silica gel, the silica gel-supported HClO4-catalyzed heterogeneous additions also proceeded smoothly to give similar or even better results in comparison with the homogenous ones. The supported catalyst could be readily recovered by filtering method and reused for 4 runs. Furthermore, the mechanism for the HClO4 catalyzed-addition of theβ-diketone to alcohol was investigated thoroughly through experiments and the SN1 mechanism was established ambiguously.
Highly efficient hydroamination reactions of sulfonamides, benzamide with inactivate olefins catalyzed by readily available and inexpensive silia gel-supported TfOH was achieved for the first time. The silica gel-supported TfOH catalyzed addition reactions could be conveniently conducted in air with unpredried solvent in catalytic loading (5mol%). The supproted catalyst could be readily recovered and reused for 6 runs with maitained reactivity and yields, and each yield of the reaction in run is more than 95%. These processes gave more than 80%yields for the addition reaction of various sulfonamides with alkenes.
本论文第一次利用易得、廉价的硅胶负载的三氟甲磺酸(TfOH-SiO2)为催化剂,催化了磺酰胺类化合物对不饱和烯烃的加成反应。在5mol%的催化剂用量下,该反应可以很方便的在空气中和未经处理的溶剂中进行,催化剂可以循环使用6次,而催化剂的反应活性和产物的收率都不会降低,每次循环反应的收率都在95%以上。多种磺酰胺类化合物与烯烃的加成反应,在该非均相催化体系中都获得了80%以上的产率。
In this thesis, the direct additions ofβ-diketones to secondary alcohols or alkenes have been achieved using perchloric acid (HClO4) as the catalyst in low catalytic loading (lmol%). The HClO4-catalyzed reactions could be conveniently conducted in air with undried solvents and majority of the substrate gave more than 85%yields. Moreover, when HClO4 was absorbed onto silica gel, the silica gel-supported HClO4-catalyzed heterogeneous additions also proceeded smoothly to give similar or even better results in comparison with the homogenous ones. The supported catalyst could be readily recovered by filtering method and reused for 4 runs. Furthermore, the mechanism for the HClO4 catalyzed-addition of theβ-diketone to alcohol was investigated thoroughly through experiments and the SN1 mechanism was established ambiguously.
Highly efficient hydroamination reactions of sulfonamides, benzamide with inactivate olefins catalyzed by readily available and inexpensive silia gel-supported TfOH was achieved for the first time. The silica gel-supported TfOH catalyzed addition reactions could be conveniently conducted in air with unpredried solvent in catalytic loading (5mol%). The supproted catalyst could be readily recovered and reused for 6 runs with maitained reactivity and yields, and each yield of the reaction in run is more than 95%. These processes gave more than 80%yields for the addition reaction of various sulfonamides with alkenes.
引文
[1]G Guillena, D. J. Ramon, M. Yus; C-C-Kupplungen mit Alkoholen as Elektrophilen: der Wasserstoff-Autotransfer. Angew. Chem.2007,119,2410-2416;
[2]B. M. Trost, On Inventing Reactions for Atom Economy. Acc. Chem. Res.2002,35, 695-705.
[3]F. Bisaro, G Prestat, M. Vitale, G Poli, Alkylation of Active Methylenes via Benzhydryl Cations. Synlett.2002,1823-1826.
[4]R.V. Nguyen, D. S. Bohle. Gold and Silver Catalyzed Highly Regioselective Addition of Active Methylenes to Dienes, Triene, and Cyclic Enol Ethers. Org.Lett.2005,7,673-675.
[5]S. Roberto, M. Delia Brensted Acid Catalyzed Propargylation of 1,3-Dicarbonyl Derivatives. Synthesis of Tetrasubstituted Furans. Org. lettl.2007,9,727-730.
[6]K. Ebitani, K. Kaneda, Angew. Brvonsted Acid Mediated Heterogeneous Addition Reaction of 1,3-Dicarbonyl Compounds to Alkenes and Alcohols Chem.Int. Ed.2006,45, 2605-2609.
[7]李述文,范如霖.编译.实用有机化学手册[M].上海：上海科技出版社,1981：319
[8]刘守信,张红利,李振朝.路易斯酸催化缩酮的合成[J].精细化工,1996,13(1)：42-44
[9]刘彩华,梁学正等Al-MSU-S-Y介孔分子筛的合成及其催化合成缩醛(酮)的研究.[J]分子催化,2007,21(5)：391-395
[10]罗锡平,葛忠华.蒙脱土负载试剂固体酸催化剂的研究[J].浙江工业大学硕士学位论文.2001：8-10
[11]肖晓明,蔡先平,陈其良；固体超强碱催化剂及其在有机合成中的应用.石油化工1994,23,342-346
[12]M. Yasuda, T. Somyo, A. Baba, Direct Carbon-Carbon Bond Formation from Alcohols and Active Methylenes, Alkoxyketones, or Indoles Catalyzed by Indium Trichloride Angew. Chem. Int. Ed.2006,45,793-796.
[13]U. Jana, S. Biswas, S. Maiti, A simple and efficient FeCl3-catalyzed direct alkylation of active methylene compounds with benzylic and allylic alcohols under mild conditions Tetrahedron Lett.2007,48,4065-4069.
[14]M. Rueping, B. J. Nachtsheim, A. Kuenkel; Efficient Metal-Catalyzed DirectBenzylation and Allylic Alkylation of 2,4-Pentanediones. Org. Lett.2007,9,825-828.
[15](a) M. Noji, Y. Konno, K. Ishii, Metal Triflate-Catalyzed Cationic Benzylation and Allylation of1,3-Dicarbonyl Compounds. J. Org. Chem.2007,72,5161-5167; (b) W. Huang, J. Wang, Q. Shen, X. Zhou, An efficient Yb(OTf)3 catalyzed alkylation of
1,3-dicarbonyl compounds using alcohols as substrates. Tetrahedron Lett.2007,48, 3969-3973.
[16]W. Rao, A. H. L. Tay, P. J. Goh, J. M. L. Choy, J. K. Ke, P. W. H. Chan, Iodine-catalyzed allylation of 1,3-dicarbonyl compounds with allylic alcohols at room temperature Tetrahedron Lett.2008,49,122-126.
[17](a) K. Motokura, N. Fujita, K. Mori, T. Mizugaki, K. Ebitani, K. Kaneda; Bronsted Acid Mediated Heterogeneous Addition Reaction of 1,3-Dicarbonyl Compounds to Alkenes and Alcohols. Angew. Chem. Int. Ed.2006,45,2605-2609; (b) K. Motokura, N. Nakagiri, T. Mizugaki, K. Ebitani, K. Kaneda; Nucleophilic Substitution Reactions of Alcohols with Use of Montmorillonite Catalysts as Solid Br(?)nsted Acids. J. Org. Chem. 2007,72,6006-6015.
[18]R. Sanz, D. Miguel, A. Martinez, J. M. Alvarez-Gutierrez, F. Rodriguez; Bransted Acid Catalyzed Propargylation of 1,3-Dicarbonyl Derivatives. Synthesis of Tetrasubstituted Furans. Org. Lett.2007,9,727-730.
[19]G. W. Wang, Y. B. Shen, X. L. Wu; Phosphotungstic Acid Catalyzed DirectBenzylation of β-Dicarbonyl Compounds. Eur. J. Org. Chem.2008,29,4999-5004.
[20]S. Shirakawa, S. Kobayashi; Surfactant-Type Bronsted Acid Catalyzed Dehydrative Nucleophilic Substitutions of Alcohols in Water. Org. Lett.2007,9,311-314.
[21]N. R. Christopher. J.Chem Soc Faraday Trans,1992,88 (15):2269-2274
[22]N. R. Christopher. J Chem Soc Faraday Trans,1993,89(9):1387-1391
[23]M. Misono. Heterogeneous catalysis by heteropoly compounds of molybdenum and tungsten. Catal. Rev Sci. Eng,1987,29:269-321.
[24]P. Laszlo, Catalysis of Organic Reactions by Inorganic Solids. Acc. Chem. Res.1986,19, 121-127.
[25]V. Ramamurthy, P. Lakshminarasimhan, C. P. Grey, L. J. Johnston; Energy transfer, proton transfer and electron transfer reactions within zeolites. Chem. Commun.1998, 2411-2424;
[26]K. Ebitani, T. Kawabata, K. Nagashima, T. Mizugaki, K. Kaneda; Simple and clean synthesis of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene from the aromatic alkylation of phenoxyethanol with fluoren-9-one catalysed by titanium cation-exchanged montmorillonite. Green Chem.2000,2,157-160;
[27]陈奠宇,吴正兴.固载型杂多酸催化剂研究新进展.应用化工.2006,35：802-806.
[28]张富民,袁超树,王军.硅胶负载磷钨酸(盐)催化剂上乙酰乙酸乙酯与乙二醇缩合反应中的催化性能.石油化工,2005,34(12)1172—1176.
[29]J. P. Richard, W. P. Jencks, A Simple Relationship between Carbocation Lifetime and Reactivity-Selectivity Relationships for the Solvolysis of Ring-Substituted 1-Phenylethyl Derivatives. J. Am. Chem. Soc.1982,104,4689-4691; 1396-1401;
[30]Yu. Zhi-Xiang, Li. Xin, Ye. Siyu, He. Chuan; Mechanisms of Brensted Acid Catalyzed Additions of Phenols and Protected Amines to Olefins:A DFT Study. Eur. J. Org. Chem. 2008,25,4296-4303
[31]R. Kumar, D. Kumar, A. K. Chakraborti, Perchloric Acid Adsorbed on Silica Gel (HClO_4-SiO_2) as an Inexpensive, Extremely Efficient, and Reusable Dual Catalyst System for Acetal/Ketal Formation and Their Deprotection to Aldehydes/Ketones. Synthesis,2007,299-303;
[32]J. S. Ryu, G.Y. Li; T.J. Marks; Organolathanide-Catalyzed Regioselective Intermolecular Hydroamination of Alkenes, Alkynes,Vinylarenes, Di-and Trivinylarenes, and Methylenecyclopropanes. Scope and Mechanistic Comparison to Intramolecular Cyclohydroaminations. J. Am. Chem. Soc.2003,725,12584-12605.
[33]I. Bytschkov, S. Doye; Group-IV Metal Complexes as Hydroamination Catalysts. Eur. J. Org. Chem.2003,6,935-946.
[34]X. Y. Liu, C. Li, C. M. Che; Phosphine Gold(I)-Catalyzed Hydroamination of Alkenes underThermal and Microwave-Assisted Conditions. Org. Lett.2006,8,2707-2710.
[35]C. Brouwer, Efficient Gold-Catalyzed Hydroamination of 1,3-Dienes. Angew. Chem. int.Ed.2006,45,1744-1747.
[36]D. R. Coulson, Catalytic addition of secondary amines to ethylene. Tetrahedron Lett. 1971,429-430.
[37]A. L. Casalnuovo; J. C. Calabrese; D. Milstein, Rational Design in Homogeneous Catalysis. Ir(I)-Catalyzed Addition of Aniline to Norbornylene via N-H Activation. J. Am. Chem. Soc.1988,110,6738-6744.
[38](a) H.Qian; R. A.Widenhoefer; Platinum-Catalyzed Intermolecular Hydroamination of Vinyl Arenes with Carboxamides. Org. Lett.2005,7,2635-2638. (b) D. Karshtedt; A. T, Bell; T. D. Tilley, Platinum-Based Catalysts for the Hydroamination of Olefins with Sulfonamides and Weakly Basic Anilines. J. Am. Chem. Soc.2005,127,12640-12646.
[39]J. L. Zhang, C. G. Yang; Gold(I)-Catalyzed Intra-and Intermolecular Hydroamination of Unactivated Olefins. J. Am. Chem. Soc.2006,128,1798-1799.
[40]J. G. Taylor, N.Whittall, K. K. Hii; Copper-Catalyzed Intermolecular Hydroamination of Alkenes. Org. Lett.2006,8,3561-3564.
[41]H. Qin, N.Yamagiwa, S. Matsunaga; Bismuth-Catalyzed Intermolecular Hydroamination of 1,3-Dienes with Carbamates, Sulfonamides, and Carboxamide. J. Am. Chem. Soc. 2006,128,16111614.
[42]S. K. Talluri, A. Sudalai; NBS-Catalyzed Hydroamination and Hydroalkoxylation of Activated Styrenes. Org. Lett.2005,7,855-857.
[43]Y. Lei, X. L.Wen; Zirconium-Catalyzed Intermolecular Hydroamination of Unactivated Olefins. Synlett.2009,7.1167-1171
[44]M. Julien, T.Vincent. M. Sylvain; Intermolecular FeCl3-Catalyzed Hydroamination of Styrenes. Eur. J. Org. Chem.2007,2601-2603
[2]B. M. Trost, On Inventing Reactions for Atom Economy. Acc. Chem. Res.2002,35, 695-705.
[3]F. Bisaro, G Prestat, M. Vitale, G Poli, Alkylation of Active Methylenes via Benzhydryl Cations. Synlett.2002,1823-1826.
[4]R.V. Nguyen, D. S. Bohle. Gold and Silver Catalyzed Highly Regioselective Addition of Active Methylenes to Dienes, Triene, and Cyclic Enol Ethers. Org.Lett.2005,7,673-675.
[5]S. Roberto, M. Delia Brensted Acid Catalyzed Propargylation of 1,3-Dicarbonyl Derivatives. Synthesis of Tetrasubstituted Furans. Org. lettl.2007,9,727-730.
[6]K. Ebitani, K. Kaneda, Angew. Brvonsted Acid Mediated Heterogeneous Addition Reaction of 1,3-Dicarbonyl Compounds to Alkenes and Alcohols Chem.Int. Ed.2006,45, 2605-2609.
[7]李述文,范如霖.编译.实用有机化学手册[M].上海：上海科技出版社,1981：319
[8]刘守信,张红利,李振朝.路易斯酸催化缩酮的合成[J].精细化工,1996,13(1)：42-44
[9]刘彩华,梁学正等Al-MSU-S-Y介孔分子筛的合成及其催化合成缩醛(酮)的研究.[J]分子催化,2007,21(5)：391-395
[10]罗锡平,葛忠华.蒙脱土负载试剂固体酸催化剂的研究[J].浙江工业大学硕士学位论文.2001：8-10
[11]肖晓明,蔡先平,陈其良；固体超强碱催化剂及其在有机合成中的应用.石油化工1994,23,342-346
[12]M. Yasuda, T. Somyo, A. Baba, Direct Carbon-Carbon Bond Formation from Alcohols and Active Methylenes, Alkoxyketones, or Indoles Catalyzed by Indium Trichloride Angew. Chem. Int. Ed.2006,45,793-796.
[13]U. Jana, S. Biswas, S. Maiti, A simple and efficient FeCl3-catalyzed direct alkylation of active methylene compounds with benzylic and allylic alcohols under mild conditions Tetrahedron Lett.2007,48,4065-4069.
[14]M. Rueping, B. J. Nachtsheim, A. Kuenkel; Efficient Metal-Catalyzed DirectBenzylation and Allylic Alkylation of 2,4-Pentanediones. Org. Lett.2007,9,825-828.
[15](a) M. Noji, Y. Konno, K. Ishii, Metal Triflate-Catalyzed Cationic Benzylation and Allylation of1,3-Dicarbonyl Compounds. J. Org. Chem.2007,72,5161-5167; (b) W. Huang, J. Wang, Q. Shen, X. Zhou, An efficient Yb(OTf)3 catalyzed alkylation of
1,3-dicarbonyl compounds using alcohols as substrates. Tetrahedron Lett.2007,48, 3969-3973.
[16]W. Rao, A. H. L. Tay, P. J. Goh, J. M. L. Choy, J. K. Ke, P. W. H. Chan, Iodine-catalyzed allylation of 1,3-dicarbonyl compounds with allylic alcohols at room temperature Tetrahedron Lett.2008,49,122-126.
[17](a) K. Motokura, N. Fujita, K. Mori, T. Mizugaki, K. Ebitani, K. Kaneda; Bronsted Acid Mediated Heterogeneous Addition Reaction of 1,3-Dicarbonyl Compounds to Alkenes and Alcohols. Angew. Chem. Int. Ed.2006,45,2605-2609; (b) K. Motokura, N. Nakagiri, T. Mizugaki, K. Ebitani, K. Kaneda; Nucleophilic Substitution Reactions of Alcohols with Use of Montmorillonite Catalysts as Solid Br(?)nsted Acids. J. Org. Chem. 2007,72,6006-6015.
[18]R. Sanz, D. Miguel, A. Martinez, J. M. Alvarez-Gutierrez, F. Rodriguez; Bransted Acid Catalyzed Propargylation of 1,3-Dicarbonyl Derivatives. Synthesis of Tetrasubstituted Furans. Org. Lett.2007,9,727-730.
[19]G. W. Wang, Y. B. Shen, X. L. Wu; Phosphotungstic Acid Catalyzed DirectBenzylation of β-Dicarbonyl Compounds. Eur. J. Org. Chem.2008,29,4999-5004.
[20]S. Shirakawa, S. Kobayashi; Surfactant-Type Bronsted Acid Catalyzed Dehydrative Nucleophilic Substitutions of Alcohols in Water. Org. Lett.2007,9,311-314.
[21]N. R. Christopher. J.Chem Soc Faraday Trans,1992,88 (15):2269-2274
[22]N. R. Christopher. J Chem Soc Faraday Trans,1993,89(9):1387-1391
[23]M. Misono. Heterogeneous catalysis by heteropoly compounds of molybdenum and tungsten. Catal. Rev Sci. Eng,1987,29:269-321.
[24]P. Laszlo, Catalysis of Organic Reactions by Inorganic Solids. Acc. Chem. Res.1986,19, 121-127.
[25]V. Ramamurthy, P. Lakshminarasimhan, C. P. Grey, L. J. Johnston; Energy transfer, proton transfer and electron transfer reactions within zeolites. Chem. Commun.1998, 2411-2424;
[26]K. Ebitani, T. Kawabata, K. Nagashima, T. Mizugaki, K. Kaneda; Simple and clean synthesis of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene from the aromatic alkylation of phenoxyethanol with fluoren-9-one catalysed by titanium cation-exchanged montmorillonite. Green Chem.2000,2,157-160;
[27]陈奠宇,吴正兴.固载型杂多酸催化剂研究新进展.应用化工.2006,35：802-806.
[28]张富民,袁超树,王军.硅胶负载磷钨酸(盐)催化剂上乙酰乙酸乙酯与乙二醇缩合反应中的催化性能.石油化工,2005,34(12)1172—1176.
[29]J. P. Richard, W. P. Jencks, A Simple Relationship between Carbocation Lifetime and Reactivity-Selectivity Relationships for the Solvolysis of Ring-Substituted 1-Phenylethyl Derivatives. J. Am. Chem. Soc.1982,104,4689-4691; 1396-1401;
[30]Yu. Zhi-Xiang, Li. Xin, Ye. Siyu, He. Chuan; Mechanisms of Brensted Acid Catalyzed Additions of Phenols and Protected Amines to Olefins:A DFT Study. Eur. J. Org. Chem. 2008,25,4296-4303
[31]R. Kumar, D. Kumar, A. K. Chakraborti, Perchloric Acid Adsorbed on Silica Gel (HClO_4-SiO_2) as an Inexpensive, Extremely Efficient, and Reusable Dual Catalyst System for Acetal/Ketal Formation and Their Deprotection to Aldehydes/Ketones. Synthesis,2007,299-303;
[32]J. S. Ryu, G.Y. Li; T.J. Marks; Organolathanide-Catalyzed Regioselective Intermolecular Hydroamination of Alkenes, Alkynes,Vinylarenes, Di-and Trivinylarenes, and Methylenecyclopropanes. Scope and Mechanistic Comparison to Intramolecular Cyclohydroaminations. J. Am. Chem. Soc.2003,725,12584-12605.
[33]I. Bytschkov, S. Doye; Group-IV Metal Complexes as Hydroamination Catalysts. Eur. J. Org. Chem.2003,6,935-946.
[34]X. Y. Liu, C. Li, C. M. Che; Phosphine Gold(I)-Catalyzed Hydroamination of Alkenes underThermal and Microwave-Assisted Conditions. Org. Lett.2006,8,2707-2710.
[35]C. Brouwer, Efficient Gold-Catalyzed Hydroamination of 1,3-Dienes. Angew. Chem. int.Ed.2006,45,1744-1747.
[36]D. R. Coulson, Catalytic addition of secondary amines to ethylene. Tetrahedron Lett. 1971,429-430.
[37]A. L. Casalnuovo; J. C. Calabrese; D. Milstein, Rational Design in Homogeneous Catalysis. Ir(I)-Catalyzed Addition of Aniline to Norbornylene via N-H Activation. J. Am. Chem. Soc.1988,110,6738-6744.
[38](a) H.Qian; R. A.Widenhoefer; Platinum-Catalyzed Intermolecular Hydroamination of Vinyl Arenes with Carboxamides. Org. Lett.2005,7,2635-2638. (b) D. Karshtedt; A. T, Bell; T. D. Tilley, Platinum-Based Catalysts for the Hydroamination of Olefins with Sulfonamides and Weakly Basic Anilines. J. Am. Chem. Soc.2005,127,12640-12646.
[39]J. L. Zhang, C. G. Yang; Gold(I)-Catalyzed Intra-and Intermolecular Hydroamination of Unactivated Olefins. J. Am. Chem. Soc.2006,128,1798-1799.
[40]J. G. Taylor, N.Whittall, K. K. Hii; Copper-Catalyzed Intermolecular Hydroamination of Alkenes. Org. Lett.2006,8,3561-3564.
[41]H. Qin, N.Yamagiwa, S. Matsunaga; Bismuth-Catalyzed Intermolecular Hydroamination of 1,3-Dienes with Carbamates, Sulfonamides, and Carboxamide. J. Am. Chem. Soc. 2006,128,16111614.
[42]S. K. Talluri, A. Sudalai; NBS-Catalyzed Hydroamination and Hydroalkoxylation of Activated Styrenes. Org. Lett.2005,7,855-857.
[43]Y. Lei, X. L.Wen; Zirconium-Catalyzed Intermolecular Hydroamination of Unactivated Olefins. Synlett.2009,7.1167-1171
[44]M. Julien, T.Vincent. M. Sylvain; Intermolecular FeCl3-Catalyzed Hydroamination of Styrenes. Eur. J. Org. Chem.2007,2601-2603