Nashrieh Shimi va Mohandesi Shimi Iran

Nashrieh Shimi va Mohandesi Shimi Iran

Using a Deep Eutectic Solvent Mixture of N,N-Dimethylethylenediamine and Tetrabutylammonium Bromide with Triple Action in Carbon-Carbon Ullman Coupling Reaction in the Presence of Copper(I) Terpyridine Complex as Catalyst

Document Type : Research Article

Authors
Akbar Mobaraki 1
Zhila Hosseinzadeh 2
Ali Roostaie 3
1 Department of Organic and Polymer Chemistry, Faculty of Chemistry, Kharazmi University, Tehran, I.R. IRAN
2 Department of Chemistry, K.N. Toosi University of Technology, Tehran, I.R. IRAN
3 Police Equipment and Technology Research Institute, Police Science and Social Studies Research Institute, Faraja, Tehran, I.R. IRAN
Abstract
In this research, a highly effective approach is introduced for the improvement of carbon-carbon coupling through Ullmann reaction to synthesize a variety of biaryl compounds with a level of efficiency ranging from good to excellent. To achieve this objective, the compound 4′-(4-methoxyphenyl)-2,2′:6′,2″-terpyridine (Mtpy) was employed as a tridentate ligand with electron-rich properties and CuI served as the catalytically active sites. In the investigated reaction, a combination of N,N-Dimethylethylenediamine (DMED) and Tetrabutylammonium Bromide (TBAB) was utilized as a novel Deep Eutectic Solvent (DES), fulfilling triple roles: functioning as a base, facilitating the reaction process as an additive, and plays its main role as a solvent for the carbon-carbon coupling reaction. The results acquired are compared with existing literature reports, demonstrating the efficacy of the approach. Furthermore, the triple functionality of the deep eutectic solvent, coupled with its capability to be recovered three times during the reaction, highlights its robustness under reaction conditions and presents promising opportunities in the field of green chemistry.
Keywords
Deep eutectic solvent
Ullmann reaction
Catalyst
Green chemistry
Biphenyl derivatives

Subjects

[1] Perna F.M., Vitale P., Capriati V., Deep Eutectic Solvents and Their Applications as Green Solvents, Curr. Opin. Green Sustain. Chem. 21: 27–33 (2020).
[2] Hansen B.B., Spittle S., Chen B., Poe D., Zhang Y., Klein J.M., Horton A., Adhikari L., Zelovich T., Doherty B.W., Gurkan B., Maginn E.J., Ragauskas A., Dadmun M., Zawodzinski T.A., Baker G.A., Tuckerman M.E., Savinell R.F., Sangoro J.R., Deep Eutectic Solvents: A Review of Fundamentals and Applications Chem. Rev. 121: 1232–1285 (2021).
[3] Prabhune A., Dey R., Green and Sustainable Solvent of the Future: Deep Eutectic Solvents, J. Mol. Liq. 379: 121676 (2023).
[4] El-Achkar T., Gerges H.G., Fourmentin S., Basics and Properties of Deep Eutectic Solvents: a Review, Environ. Chem. Lett. 19: 3397–3408 (2021).
[5] Piryaei M., Deep Eutectic Solvents as an Efficient Solvent System Determination the Volatile Compounds with Microextraction, Iran. J. Chem. Chem. Eng. 41: 135–142 (2022).
[6] Abbasi F., Sardarian A.R., Triethanolamine-based Deep Eutectic Solvent as a Novel, Biocompatible, Reusable, and Efficient Dual Catalyst/Solvent Media for the Selective Tosylation and Mesylation of Phenols, Tetrahedron 152: 133780 (2024).
[7] Zainal-Abidin M.H., Hayyan M., Matmin J., Al-Fakih A.M., Jamaluddin N., Mahmood W.M., Abdul Wahab R., Abdullah F., Greening Industrial Applications with Magnetic-Based Deep Eutectic Solvents: A Promising Future, J. Ind. Eng. Chem. 124: 1–16 (2023).
[8] Cao T.P., Hang C.N., Quang H.V., Kabtamu D.M., Kumar S., Nguyen V.C., Cao X.T., Catalyst-Free Synthesis of Poly (Furfuryl Alcohol) Using Deep Eutectic Solvents, New J. Chem. 46: 3786–3793 (2022).
[9] Ma Y., Yang Y., Li T., Hussain Sh., Zhu M., Deep Eutectic Solvents as an Emerging Green Platform for the Synthesis of Functional Materials, Green Chem.26: 3627–3669 (2024).
[10] Yin L., Liebscher J., Carbon-Carbon Coupling Reactions Catalyzed by Heterogeneous Palladium Catalysts, Chem. Rev. 107: 133–173 (2007).
[11] خانلری ط.، تهیه پلیمر حمایت کننده پالادیوم، برپایه پلی وینیل الکل و استفاده از آن در واکنش هِک، نشریه شیمی و مهندسی شیمی ایران، (2)34: 25 تا 40 (1394).
[12] فرجادیان ف.، قاسمی، س.، خلیلی د.، زارع ف.، قلی­نژاد م.، تمامی ب.، پلی (2ـوینیل پیریدین) پیوند شده بروی سیلیکا دارای نانو ذره­های پالادیوم: سنتز، شناسایی و کاربرد کاتالسیتی در واکنش‌های جفت­شدن کربن­ـکربن، نشریه شیمی و مهندسی شیمی ایران، (3)39: 67 تا 79 (1399).
[13] قاسمی م.ه.، کوثری ا.، روشی مؤثر برای سنتز ماده اولیه دارویی آداپالن با استفاده از نانوذره­ های روی، نشریه شیمی و مهندسی شیمی ایران، (2)36: 45 تا 53 (1396).
[14] Heydari N., Bikas R., Siczek M., Lis T., Green Carbon-Carbon Homocoupling of Terminal Alkynes by a Silica Supported Cu(II)-Hydrazone Coordination Compound, Dalton Trans. 52: 421–433 (2023).
[15] El-Maghrabey M., Kishikawa N., Kuroda N., Unique Biomedical Application of Fluorescence Derivatization Based on Palladium-Catalyzed Coupling Reactions for HPLC Analysis of Pharmaceuticals and Biomolecules, Biomedical Chromatography 38: e5857 (2024).
[16] Budarin V.L., Shuttleworth P.S., Clark J.H., Luque R., Industrial Applications of C-C Coupling Reactions, Curr. Org. Synth. 7: 614–627 (2010).
[17] Torborg C., Beller M., Recent Applications of Palladium‐Catalyzed Coupling Reactions in the Pharmaceutical, Agrochemical, and Fine Chemical Industries, Adv. Synth. Catal. 351: 3027–3043 (2009).
[18] Noroozi M., Saremi Sh.Gh., Synthesis of Schiff Base-functionalized Fullerene Anchored Palladium Complex as a Recyclable Nanocatalyst in the Heck Reaction and Oxidation of Alcohols, Iran. J. Chem. Chem. Eng. 40: 1395–1405 (2021).
[19] Beletskaya I.P., Cheprakov A.V., Copper in Cross-Coupling Reactions: The Post-Ullmann Chemistry, Coord. Chem. Rev. 248: 2337–2364 (2004).
[20] Ley S.V., Thomas A.W., Modern Synthetic Methods for Copper-Mediated C(aryl)-O, C(aryl)-N, and C(aryl)-S Bond Formation, Angew. Chem. Int. Ed. 42: 5400–5449 (2003).
[21] Talukdar V., Mondal K., Halder P., Das P., Ullmann-Type N-, S-, and O-Arylation Using a Well-Defined 7-Azaindole-N-oxide (7-AINO)-Based Copper(II) Catalyst: Scope and Application to Drug Synthesis, J. Org. Chem.  89: 7455–7471 (2024).
[22] Monnier F., Taillefer M., Catalytic CC, CN, and CO Ullmann-Type Coupling Reactions: Copper Makes a Difference, Angew. Chem. Int. Ed. 47: 3096–3099 (2008).
[23] Evano G., Blanchard N., Toumi M., Copper-Mediated Coupling Reactions and Their Applications in Natural Products and Designed Biomolecules Synthesis, Chem. Rev. 108: 3054–3131 (2008).
[24] Kumar S., Singh S., Mathur N., Roy P., Joshi H., Titania Nanorod-Supported Mercaptoundecanoic Acid-Grafted Palladium Nanoparticles as a Highly Reusable Heterogeneous Catalyst for Substrate-Dependent Ullmann Coupling and Debromination of Aryl Bromides, Inorg. Chem. 62: 3993–4002 (2023).
[25] Bagheri H., Baharfar R., Magnetic MCR-Functionalized Graphene Oxide Complexed with Copper Nano-Particles: An Efficient and Recyclable Nanocatalyst for Ullmann C–N Coupling Reaction, Polycycl. Aromat. Comp. 43: 7580–7596 (2023).
[26] Wang L., Zhu X., Liang Z., Huang M., Wan Y., Design and Application of a Novel and Effective Ligand for the Cu-Catalyzed Amination of Aryl Halides in Water, Green chem. lett. rev. 16(6): 2147027–2147034 (2023).
[27] Ma D., Cai Q., Zhang H., Mild Method for Ullmann Coupling Reaction of Amines and Aryl Halides, Org. Lett. 5: 2453–2455 (2003).
[28] Vorobiev D., Heintz N., Korina E., Grafov O., Gusev S., Abramyan A., Avdin V., Bol'shakov O., Testing the Support Effect on Deposited CuO Nanoparticles in Ullmann Reaction, Inorg. Chem. Commun. 151: 110608 (2023).
[29] Zuo B., Zuo J., Chen H., Deng Q., Yamauchi Y., Kim J., Xu X., Ion-Imprinted Magnetic Adsorbents for the Selective Capture of Cu(II) and Their Cascade Application as Heterogeneous Recyclable Catalysts for Ullmann and Glaser Coupling Reactions, Chem Eng. J. 471: 143893 (2023).
[30] Mo B., Li Zh., Peng J., Chen Ch., Novel Lignin-Supported Copper Complex as a Highly Efficient and Recyclable Nanocatalyst for Ullmann Reaction, Int. J. Biol. Macromol. 239: 124263 (2023).
[31] Sambiagio C., Marsden S.P., Blackera A.J., McGowan P.C., Copper Catalysed Ullmann Type Chemistry: from Mechanistic Aspects to Modern Development, Chem. Soc. Rev. 43: 3525–3550 (2014).
[32] Lin H., Sun D., Recent Synthetic Developments and Applications of the Ullmann Reaction. A Review, Org. Prep. Proced. Int. 45: 341–394 (2013).
[33] Crabbe B.W., Kuehm O.P., Bennett J.C., Hallett-Tapley G.L., Light-Activated Ullmann Homocoupling of Aryl Halides Catalyzed Using Gold Nanoparticle-Functionalized Potassium Niobium Oxides, Catal. Sci. Technol. 8: 4907–4915 (2018).
[34] Gao A., Liu H., Hu L., Zhang H., Hou A., Xie K., Synthesis of Fe3O4@SiO2-Au/Cu Magnetic Nanoparticles and Its Efficient Catalytic Performance for the Ullmann Coupling Reaction of Bromamine Acid, Chin. Chem. Lett. 29: 1301–1304 (2018).
[35] Zhang P., Liu Y., Li X., Siri G., Wang J., Li Zh., Jian Y., Gao Z., Copper Catalyzed Three-Component Ullmann C–S Coupling in PEG for the Synthesis of 6-Aryl/alkylthio-Purines, J. Org. Chem.  89: 2212–2222 (2024).
[36] Ojha N.K., Zyryanov G.V., Majee A., Charushin V.N., Chupakhin O.N., Santra S., Copper Nanoparticles as Inexpensive and Efficient Catalyst: A Valuable Contribution in Organic Synthesis, Coord. Chem. Rev. 353: 1–57 (2017).
[37] Rahman M.L., Sarjadi M.S., Fui C.J., Guerin S., Pillai S.C., Sarkar S.M., Natural Cellulose-Based Cu(II) Complex: An Eco-Friendly Nanocatalyst for Ullmann Condensations at Room Temperature, J. Clean. Prod. 390: 136015 (2023).
[38] Corma A., Garcia H., Crossing the Borders Between Homogeneous and Heterogeneous Catalysis: Developing Recoverable and Reusable Catalytic Systems, Top. Catal. 48: 8–31 (2008).
[39] Mastalir A., Molná A., A Novel Insight into the Ullmann Homocoupling Reactions Performed in Heterogeneous Catalytic Systems, Molecules 28: 1769–1791 (2023).
[40] Patil S.P., Rajmane A.S., Jadhav S.N., Rajmane V.S., Rode Ch.V., Kumbhar A.S., ZrO2 Supported Cu Nanoparticles for Sonogashira and Ullmann Coupling Reactions Under Palladium-Free Conditions, Catal. Letters 154: 3078–3090 (2024).
[41] Pourshahi M., Mansoori Y., Ghahramani F., Bezaatpour A., Esquivel D., Navarro M.A., John M., Copper(II)-Polymer Chelate Grafted from Magnetic Mesoporous Silica for the O-arylation of Phenols via the Ullmann Reaction, J. Organomet. Chem. 1014: 123191 (2024).
[42] Sonawane H.R., Deore J.V., Chavan P.N., Reusable Nano Catalysed Synthesis of Heterocycles: An Overview, ChemistrySelect 7: e202103900 (2022).
[43] Tang Ch., Yang W., Zou Zh., Liao F., Zeng Ch., Song K., Facile Synthesis Hyper-Crosslinked PdFe Bimetallic Polymer as Highly Active Catalyst for Ullmann Coupling Reaction of Chlorobenzene, Polymers  15: 2748–2758 (2023).
[44] Wu Q.; Wang L., Immobilization of Copper(II) in Organic-Inorganic Hybrid Materials: A Highly Efficient and Reusable Catalyst for the Classic Ullmann Reaction Silica Gel Immobilized Coper(I) Catalyst for the Classic Ullmann Reaction, Synthesis 13: 2007–2012 (2008).
[45] Puthiaraj P., Suresha P., Pitchumani K., Aerobic Homocoupling of Arylboronic Acids Catalysed by Copper Terephthalate Metal Organic Frameworks, Green Chem. 16: 2865–2875 (2014).
[46] Cahiez G., Chaboche Ch., Mahuteau-Betzer F., Ahr M., Iron-Catalyzed Homo-Coupling of Simple and Functionalized Arylmagnesium Reagents, Org. Lett. 7: 1943–1946 (2005).
[47] Aghajani M., Dabiri M., Ultrasound-Assisted Cu(II) Strecker-Functionalized Organocatalyst for Green Azide-Alkyne Cycloaddition and Ullmann Reactions, Sci. Rep. 14: 12141–12158 (2024).
[48] Dabiri M., Banifatemi Kashi S.R., Farajinia Lehi N., Bashiribod S., Synthesis of Gold Nanoparticles Decorated on Sulfonated Three‐Dimensional Graphene Nanocomposite and Application as a Highly Efficient and Recyclable Heterogeneous Catalyst for Ullmann Homocoupling of Aryl Iodides and Reduction of p‐Nitrophenol, Appl. Organomet. Chem. 32: e4189 (2018).
[49] Dubey A.V., Kumar A.V., A Bio-Inspired Magnetically Recoverable Palladium Nanocatalyst for the Ullmann Coupling Reaction of Aryl Halides and Arylboronic Acids in Aqueous Media, Appl. Organomet. Chem. 34: e5570 (2020).
[50] Chen L., Gao Zh., Li Y., Immobilization of Pd(II) on MOFs as a Highly Active Heterogeneous Catalyst for Suzuki–Miyaura and Ullmann-Type Coupling Reactions, Catal. Today 245: 122–128 (2015).
[51] Liu Q., Xu M., Wang Y., Feng R., Yang Zh., Zuo Sh., Qi Ch., Zeng M., Co-Immobilization of Pd and Zn Nanoparticles in Chitosan/Silica Membranes for Efficient, Recyclable Catalysts Used in Ullmann Reaction, Int. J. Biol. Macromol. 105: 575–583 (2017).
[52] Beletskaya I.P., Cheprakov A.V., Copper in Cross-Coupling Reactions, The Post-Ullmann Chemistry, Coord. Chem. Rev. 248: 2337–2364 (2004).
[53] Sambiagio C., Marsden S.P., Blacker A.J., McGowan P.C., Copper Catalysed Ullmann Type Chemistry: from Mechanistic Aspects to Modern Development, Chem. Soc. Rev. 43: 3525-3550 (2014).
[54] Mobaraki A., Sakhaee N., Takallou A., Habibi A., Triple Action of an Attractive Deep Eutectic Solvent in the Synthesis of Aryl Nitriles and Substituted Triazoles Using a Magnetically Reusable Fe3O4@SiO2@PrNCu Catalyst, ChemistrySelect 8: e202204932 (2023).
[55] Wang J., Hanan G.S., A Facile Route to Sterically Hindered and Non-Hindered 4′-Aryl-2,2′:6′,2′′-Terpyridines, Synlett 8: 1251–1254 (2005).