室温下无配体体系钯催化苯乙烯氧化反应研究
PDF下载 (22336)赵延超,梁洪泽,骆钧飞*.室温下无配体体系钯催化苯乙烯氧化反应研究[J].宁波大学学报(理工版),2018,31(3):50-54.DOI:
ZHAO Yan-chao,LIANG Hong-ze,LUO Jun-fei*.Ligand-free Pd-catalyzed oxidation of styrenes at room temperature[J].Journal of Ningbo University(Natural Science & Engineering Edition),2018,31(3):50-54.DOI:
| Title: | Ligand-free Pd-catalyzed oxidation of styrenes at room temperature |
| 作者: | 赵延超, 梁洪泽, 骆钧飞* |
| Author(s): | ZHAO Yan-chao, LIANG Hong-ze, LUO Jun-fei* |
| 关键词: | 钯催化; 无配体; Wacker氧化; 苯乙烯; 酮 |
| Keywords: | Pd-catalyzed; ligand-free; Wacker oxidation; styrene; ketone |
| 分类号: | O625.41 |
| 文献标识码: | A |
| 摘要: | 报道了一种操作简单且有效的钯金属催化苯乙烯及其衍生物转化为苯乙酮类化合物的方法. 研究表明, 该反应在温室下, 使用商业化的三氟乙酸钯催化剂以及廉价的过氧叔丁醇水溶液即可实现Wacker氧化, 且无需额外配体稳定或活化催化剂. 该方法具有高官能团兼容性, 且末端脂肪烯烃、双取代末端烯烃以及中间体均可在该条件下转化为相应的酮. |
| Abstract: | A convenient protocol for the oxidation of a styrene to the corresponding methyl ketone was developed. Without the requirement of an extra additive or ligand, this method allows Wacker-type oxidation to proceed efficiently at room temperature in the presence of a commercially available palladium trifluoroacetate catalyst and inexpensive aqueous tert-butyl peroxide. This transformation is highly functional group tolerant. Furthermore, aliphatic alkenes, di-substituted alkenes and internal alkenes could also be converted into the corresponding ketones. |
| 参考文献 /References: | [1] Gaunt M J, Yu J Q, Spencer J B. Evidence that the availability of an allylic hydrogen governs the regioselectivity of the Wacker oxidation[J]. Chemical Communications, 2001, 33(2):1844-1845. [2] Keith J A, Henry P M. The mechanism of the Wacker reaction: A tale of two hydroxypalladations[J]. Angewandte Chemie International Edition, 2010, 41(7): 9038-9049. [3] Mann S E, Benhamou L, Sheppard T D. Palladium(II)- catalysed oxidation of alkenes[J]. Synthesis, 2015, 47(20): 3079-3117. [4] Smidt J, Hafner W, Jira R, el at. The oxidation of olefins with palladium chloride catalysts[J]. Angewandte Chemie International Edition, 1962, 1(2):80-88. [5] Clement W H, Selwitz, C M. Improved procedures for converting higher α-olefins to methyl ketones with palladium chloride[J]. The Journal of Organic Chemistry, 1964, 29(1):241-243. [6] Tang H G, Sherrington, D C. Polymer-supported Pd(II) Wacker-type catalysts. Part III. Isomerisation of alkene double bond[J]. Journal of Molecular Catalysis, 1994, 94(1):7-17. [7] Smith A B, Cho Y S, Friestad G K. Convenient Wacker oxidations with substoichiometric cupric acetate[J]. Tetrahedron Letters, 1998, 39(48):8765-8768. [8] Cornell C N, Sigman M S. Recent progress in Wacker oxidations: Moving toward molecular oxygen as the sole oxidant[J]. Inganic Chemistry, 2007, 46(6):1903-1909. [9] Mistsudome T, Umetani T, Nosaka N. Convenient and efficient Pd-catalyzed regioselective oxyfunctionaliza- tion of terminal olefins by using molecular oxygen as sole reoxidant[J]. Angewandte Chemie International Edition, 2006, 45(3):481-485. [10] Winston M S, Oblad P F, Labinger J A, et al. Activator-free olefin oligomerization and isomerization reactions catalyzed by an air- and water-tolerant Wacker oxidation intermediate[J]. Angewandte Chemie Interna- tional Edition, 2012, 124(39):9960-9962. [11] Baiju T V, Grave E, Doris E, et al. Recent developments in Tsuji-Wacker oxidation[J]. Tetrahedron Letters, 2016, 57(36):3993-4000. [12] Zhang G, Xie X, Wang Y, el at. Highly selective Wacker reaction of styrene derivatives: A green and efficient aerobic oxidative process promoted by benzoquinone/ NaNO2/HClO4 under mild conditions[J]. Organic & Biomolecular Chemistry, 2013, 11(18):2947-2950. [13] Piera J, Bckvall J E. Catalytic oxidation of organic substrates by molecular oxygen and hydrogen peroxide by multistep electron transfer: A biomimetic approach[J]. Angewandte Chemie International Edition, 2008, 47(19): 3506-3523. [14] Kulkaeni M G, Shaikh Y B, Borhade, A S, et al. Greening the Wacker process[J]. Tetrahedron Letters, 2013, 54(19): 2293-2295. [15] Fernandes R A, Bethi, V. Synthesis of methyl ketones from terminal olefins using PdCl2/CrO3 system mimicking the Wacker process[J]. Tetrahedron, 2014, 70 (32):4760-4767. [16] Morandi B, Wickens Z K, Grubbs R H. Regioselective Wacker oxidation of internal alkenes: Rapid access to functionalized ketones facilitated by cross-metathesis[J]. Angewandte Chemie International Edition, 2013, 52(37): 9751-9756. [17] Fernandes R A, Chaudhari D A. Iron(III) sulfate as terminal oxidant in the synthesis of methyl ketones via Wacker oxidation[J]. The Journal of Organic Chemistry, 2014, 79(12):5787-5793. [18] Chaudhari D A, Fernandes, R A. Hypervalent iodine as a terminal oxidant in Wacker-type oxidation of terminal olefins to methyl ketones[J]. The Journal of Organic Chemistry, 2016, 81(5):2113-2121. [19] Brink G J T, Arends I W C E, Papadogianakis G, et al. Catalytic conversions in water. Part 10. Aerobic oxidation of terminal olefins to methyl ketones catalysed by water soluble palladium complexes[J]. Cheminform, 1999, 30 (8):2359-2360. [20] Mitsudome T, Mizumoto K, Mizugakii T. Wacker-type oxidation of internal olefins using a PdCl2/N, N-dimethylacetamide catalyst system under copper-free reaction conditions[J]. Angewandte Chemie International Edition, 2010, 49(7):1238-1240. [21] Mitsudome T, Yoshida S, Mizugak T, el at. Highly atom-efficient oxidation of electron-deficient internal olefins to ketones using a palladium catalyst[J]. Angewandte Chemie International Edition, 2013, 125(23): 5961-5964. [22] Roussel M, Mimoun H. Palladium-catalyzed oxidation of terminal olefins to methyl ketones by hydrogen peroxide[J]. The Journal of Organic Chemistry, 1980, 45 (26):5387-5390. [23] Noyorii R, Aoki M, Sato K. Green oxidation with aqueous hydrogen peroxide[J]. Chemical Communications, 2003, 34(16)1977-1986. [24] Caron S, Duger R W, Ruggeri S G, et al. Large-scale oxidations in the pharmaceutical industry[J]. Chemical Reviews, 2006, 106(7):2943-2989. [25] Chiapple C, Sanzone A, Dyson P J. Styrene oxidation by hydrogen peroxide in ionic liquids: The role of the solvent on the competition between two Pd-catalyzed processes, oxidation and dimerization[J]. Green Chemistry, 2011, 13(6):1437-1441. [26] Barak G, Sasson Y. Dual-function phase-transfer catalysis in the metal-assisted oxidation by hydrogen peroxide of styrene to benzaldehyde or acetophenone[J]. Journal of the Chemical Society, Chemical Communications, 1987, 16(16):1266-1267. [27] Cao Q, Bailie D S, Fu R, et al. Cationic palladium(II) complexes as catalysts for the oxidation of terminal olefins to methyl ketones using hydrogen peroxide[J]. Green Chemistry, 2015, 46(38):2750-2757. [28] Cornell C N, Sigman M S. Discovery of and mechanistic insight into a ligand-modulated palladium-catalyzed Wacker oxidation of styrenes using TBHP[J]. Journal of the American Chemical Society, 2005, 127(9):2796-2797. [29] Michel B W, Mcombs J R, Winkle A, et al. Catalyst-controlled Wacker-type oxidation of protected allylic amines[J]. Angewandte Chemie International Edition, 2010, 49(40):7312-7315. [30] Sommovigo M, Alper H. Aerobic oxidation of ethers and alkenes catalyzed by a novel palladium complex[J]. Journal of Molecular Catalysis 1994, 88(2):151-158. [31] Xia X, Gao X, Xu J, et al. Selective oxidation of styrene derivatives to ketones over palladium(0)/carbon with hydrogen peroxide as the sole oxidant[J]. Synlett, 2017, 28(5):607-610. [32] Wang Y F, Gao Y R, Mao S, et al. Wacker-type oxidation and dehydrogenation of terminal olefins using molecular oxygen as the sole oxidant without adding ligand[J]. Organic Letters, 2014, 16(6):1610-1613. [33] Fraile J, Garcia N, Mayoral J A, el at. Multifunctional catalysis promoted by solvent effects: Ti-MCM41 for a one-pot, four-step, epoxidation-rearrangement-oxidation- decarboxylation reaction sequence on stilbenes and styrenes[J]. ACS Catalysis, 2015, 5(6):3552-3561. |
| 备注/Memo: | 收稿日期: 2017?10?08. 宁波大学学报(理工版)网址: http://journallg.nbu.edu.cn/ 基金项目: 宁波大学人才引进项目(ZX2016000748); 宁波大学王宽诚幸福基金. 第一作者: 赵延超(1992-), 男, 山东济宁人, 在读硕士研究生, 主要研究方向: 合成化学. E-mail: 1976319312@qq.com *通信作者: 骆钧飞(1987-), 男, 浙江杭州人, 副教授, 主要研究方向: C-H活化. E-mail: luojunfei@nbu.edu.cn 宁波大学学报(理工版)网址:http://journallg.nbu.edu.cn/ |