|
钯基催化制备具有活性基团取代的苯基硼酸
|
Abstract:
活性基团取代的苯基硼酸是新型电子材料、医药和农药的重要中间体,其制备研究既具备重要的科学意义,又具备实际的工业生产价值。本文基于Suzuki-Miyaura交叉偶联反应,以活性取代苯为原料,实现了在CH3COOK为碱,[(C6H5)3P]2PdCl2为催化剂的条件下与联硼酸频那醇酯在适宜溶剂协同作用下,获得高收率活性基团取代的苯硼酸频那醇酯,并进一步水解获得对应硼酸化合物,该催化反应特别是对硝基、羰基、酯基的催化效果极好,产品收率可达90%以上。该催化反应是一类优异的准备芳基硼酸衍生物的方法。
Phenylboric acid substituted by active groups is an important intermediate of new electronic materials, medicine and pesticides. Its preparation has important scientific significance and practical industrial production value. In this paper, based on the Suzuka-Miyaura cross-coupling reaction, with active substituted benzene as raw material, under the condition of CH3COOK as base, [(C6H5)3P]2PdCl2 as catalyst and biboratefenalyl ester under the synergic action of suitable solvent, the high yield of active group substituted fenalyl phenyl ester was obtained. The boric acid was further hydrolyzed to obtain the corresponding boric acid compound. The catalytic reaction, especially for nitro group, carbonyl group and ester group, was very good, and the yield of the product could reach more than 90%. This catalytic reaction is an excellent method for preparing arylboric acid derivatives.
[1] | Khurana, L., Fu, B.Q., Duddupudi, A.L., et al. (2017) Pyrimidinyl Biphenylureas: Identification of New Lead Compounds as Allosteric Modulators of the Cannabinoid Receptor CB1. Journal of Medicinal Chemistry, 60, 1089-1104.
https://doi.org/10.1021/acs.jmedchem.6b01448 |
[2] | 徐剑霄. 一种2-硝基苯硼酸频那醇酯的合成方法[P]. 中国, 110964046. 2020-04-07. |
[3] | Oikawa, A., Kindaichi, G., Shimotori, Y. and Hoshi, M. (2016) First Synthesis of both 1-aryl-4-[(E)-alk-1-enyl]-1H-1, 2,3-Triazoles and 1-aryl-4-[(Z)-1-(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles: Assembly of π-Extended 1,2,3-Triazoles Using a Cross-Coupling/Click Reaction Sequence. Tetrahedron, 72, 4205-4213.
https://doi.org/10.1016/j.tet.2016.05.055 |
[4] | Fang, H., Kaur, G., Yan, J. and Wang, B. (2005) An Efficient Synthesis of Sterically Hindered Arylboronic Acids. Tetrahedron Letters, 46, 1671-1674. https://doi.org/10.1016/j.tetlet.2005.01.064 |
[5] | Stones, D., Manku, S., Lu, X.S. and Hall, D.G. (2004) Modular Solid-Phase Synthetic Approach to Optimize Structural and Electronic Properties of Oligo-Boronic Acid Receptors and Sensors for the Aqueous Recognition of Oligosaccha-Rides. Chemistry—A European Journal, 10, 92-100. https://doi.org/10.1002/chem.200305400 |
[6] | 张永强, 贺全国, 蒋欢妹, 邓燕, 等. 2,6-二甲基苯硼酸制备方法的改进[J]. 应用化学, 2007, 24(10): 1216-1218. |
[7] | Ando, S., Matsunaga, H. and Ishizuka, T. (2015) A Bicyclic N-Heterocyclic Carbene as a Bulky but Accessible Ligand: Application to the Copper-Catalyzed Borylations of Aryl Halides. Journal of Organic Chemistry, 80, 9671-9681.
https://doi.org/10.1021/acs.joc.5b01721 |
[8] | Leermann, T., Leroux, F.R. and Colobert, F. (2011) Highly Efficient One-Pot Access to Functionalized Arylboronic Acids via Noncryogenic Bromine Magnesium Exchanges. Organic Letters, 13, 4479-4481.
https://doi.org/10.1021/ol2016252 |
[9] | Appukkuttan, P., Dehaen, W. and Van, D.E. (2007) Microwave-Assisted Transition-Metal-Catalyzed Synthesis of N-Shifted and Ring-Expanded Buflavine Analogues. Chemistry—A European Journal, 13, 6452-6460.
https://doi.org/10.1002/chem.200700177 |
[10] | Collibee, S.E. (2005) A Facile and Convenient Synthesis of Func-tionalized Ortho-Nitrophenylboronic Acids. Tetrahedron Letters, 46, 4453-4455. https://doi.org/10.1016/j.tetlet.2005.04.129 |
[11] | Lu, J., Guan, Z. and Gao, J. (2011) An Improved Procedure for the Synthesis of Arylboronates by Palladium-Catalyzed Coupling Reaction of Aryl Halides and Bis(pinacolato)diboron in Polyethylene Glycol. Applied Organometallic Chemistry, 25, 537-541. https://doi.org/10.1002/aoc.1799 |
[12] | Martin, R. and Jones, J.B. (1995) Rational Design and Synthesis of a Highly Effective Transition State Analog Inhibitor of the RTEM-1 β-Lactamase. Tetrahedron Letters, 36, 8399-8402. https://doi.org/10.1016/0040-4039(95)01799-N |
[13] | Norsikian, S., Soule, J.F., Cannillo, A., Guillot, R., Dau, M.E.T.H. and Beau, J.M. (2012) Remarkable Stereoselectivity in Intramolecular Borono-Mannich Reactions: Synthesis of Conduramines. Organic Letters, 14, 544-547.
https://doi.org/10.1021/ol203162s |
[14] | Snow, R.J., Bachovchin, W.W., Barton, R.W., et al. (1994) Studies on Proline Boronic Acid Dipeptide Inhibitors of Dipeptidyl Peptidase IV: Identification of a Cyclic Species Containing a B-N Bond. Journal of the American Chemical Society, 116, 10860-10869. https://doi.org/10.1021/ja00103a002 |
[15] | Sun, J., Perfetti, M.T. and Santos, W.L. (2011) A Method for the Deprotection of Alkylpinacolyl Boronate Esters. Journal of Organic Chemistry, 76, 3571-3575. https://doi.org/10.1021/jo200250y |