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Synthesis of Imidazo[4,5-b]pyridines and Imidazo[4,5-b]pyrazines by Palladium Catalyzed Amidation of 2-Chloro-3-amino-heterocycles

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Department of Chemistry, 1-014 Center for Science and Technology, Syracuse University, Syracuse, New York 13244, United States
Cite this: Org. Lett. 2012, 14, 7, 1764–1767
Publication Date (Web):March 13, 2012
Copyright © 2012 American Chemical Society

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    A facile synthesis of imidazo[4,5-b]pyridines and -pyrazines is described using a Pd-catalyzed amide coupling reaction. This reaction provides quick access to products with substitution at N1 and C2. A model system relevant to the natural product pentosidine has been demonstrated, as well as the total synthesis of the mutagen 1-Me-5-PhIP.

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    2. Christopher A. Wilhelmsen, Alexandre D.C. Dixon, John D. Chisholm, and Daniel A. Clark . Synthesis of N-Substituted 3-Amino-4-halopyridines: A Sequential Boc-Removal/Reductive Amination Mediated by Brønsted and Lewis Acids. The Journal of Organic Chemistry 2018, 83 (3) , 1634-1642.
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    5. Robert J. Wilson, Adam J. Rosenberg, Lauren Kaminsky, and Daniel A. Clark . Copper- and Palladium-Catalyzed Amidation Reactions for the Synthesis of Substituted Imidazo[4,5-c]pyridines. The Journal of Organic Chemistry 2014, 79 (5) , 2203-2212.
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    17. Gagandeep Kour Reen, Ashok Kumar, Pratibha Sharma. Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage. Beilstein Journal of Organic Chemistry 2019, 15 , 1612-1704.
    18. Yuriy A. Kvashnin, Gennady L. Rusinov, Valery N. Charushin. Metal-free protocol for the synthesis of novel 6-(het)aryl-5-aryl-5H-imidazo[4,5-b][1,2,5]oxadiazolo[3,4-e]pyrazines. Mendeleev Communications 2018, 28 (5) , 461-463.
    19. Shikha Singh, Parul Chauhan, Makthala Ravi, Prem P. Yadav. Eosin Y–Yb(OTf) 3 catalyzed visible light mediated electrocyclization/indole ring opening towards the synthesis of heterobiaryl-pyrazolo[3,4- b ]pyridines. New Journal of Chemistry 2018, 42 (9) , 6617-6620.
    20. Nisha, Gaurav Bhargava, Yogesh Kumar. Copper(I)‐Catalyzed Regioselective C‐H Amination of N ‐Pyridyl Imines Using Azidotrimethylsilane and TBHP: A One‐Pot, Domino Approach to Substituted Imidazo[4, 5‐b]pyridines. ChemistrySelect 2017, 2 (26) , 7827-7830.
    21. Malwina Krause, Henryk Foks, Katarzyna Gobis. Pharmacological Potential and Synthetic Approaches of Imidazo[4,5-b]pyridine and Imidazo[4,5-c]pyridine Derivatives. Molecules 2017, 22 (3) , 399.
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    23. Basudeb Basu, Bablee Mandal. Sustainable Synthesis of Benzimidazoles, Quinoxalines, and Congeners. 2015, 209-256.
    24. Adam J. Rosenberg, Ijaz Ahmed, Robert J. Wilson, Theresa M. Williams, Lauren Kaminsky, Daniel A. Clark. An Improved Synthesis of Imidazo[4,5- b ]pyridines and Imidazo[4,5- b ]pyrazines by Palladium Catalyzed Amidation using Xantphos in a 1,4-Dioxane: tert -Amyl Alcohol Solvent System. Advanced Synthesis & Catalysis 2014, 356 (16) , 3465-3470.
    25. R. B. Nasir Baig, Mallikarjuna N. Nadagouda, Rajender S. Varma. Carbon-coated magnetic palladium: applications in partial oxidation of alcohols and coupling reactions. Green Chemistry 2014, 16 (9) , 4333.
    26. R. B. Nasir Baig, Rajender S. Varma. Magnetic silica supported copper: a modular approach to aqueous Ullmann-type amination of aryl halides. RSC Advances 2014, 4 (13) , 6568.
    27. Li-Hsun Chen, Tz-Yi Wu, Vijaykumar Paike, Chung-Ming Sun. Palladium-catalyzed regioselective synthesis of 2(2 $$^{\prime }$$ ′ -biphenyl)benzimidazoles through C–H activation. Molecular Diversity 2013, 17 (4) , 641-649.
    28. Dhanusu Suresh, Amarajothi Dhakshinamoorthy, Kuppusamy Kanagaraj, Kasi Pitchumani. Synthesis of 2-substituted 3-ethyl-3H-imidazo[4,5-b]pyridines catalyzed by Al3+-exchanged K10 clay as solid acids. Tetrahedron Letters 2013, 54 (48) , 6479-6484.
    29. Nathan T. Jui, Stephen L. Buchwald. Cascade Palladium Catalysis: A Predictable and Selectable Regiocontrolled Synthesis of N -Arylbenzimidazoles. Angewandte Chemie 2013, 125 (44) , 11838-11841.
    30. Nathan T. Jui, Stephen L. Buchwald. Cascade Palladium Catalysis: A Predictable and Selectable Regiocontrolled Synthesis of N -Arylbenzimidazoles. Angewandte Chemie International Edition 2013, 52 (44) , 11624-11627.
    31. Jitender Bariwal, Erik Van der Eycken. C–N bond forming cross-coupling reactions: an overview. Chemical Society Reviews 2013, 42 (24) , 9283.
    32. Jonathan Macdonald, Victoria Oldfield, Vassilios Bavetsias, Julian Blagg. Regioselective C2-arylation of imidazo[4,5-b]pyridines. Organic & Biomolecular Chemistry 2013, 11 (14) , 2335.
    33. Adam J. Rosenberg, Theresa M. Williams, Abraham J. Jordan, Daniel A. Clark. Synthesis of 2-amino-imidazo[4,5-b]pyridines. Organic & Biomolecular Chemistry 2013, 11 (18) , 3064.
    34. Yuan-Yuan Xing, Chuanxiang Liu, Fanhong Wu. Efficient synthesis of substituted imidazo[4,5-b]pyridines. Heterocyclic Communications 2013, 19 (5)
    35. Adam J. Rosenberg, Jinbo Zhao, Daniel A. Clark. ChemInform Abstract: Synthesis of Imidazo[4,5-b]pyridines and Imidazo[4,5-b]pyrazines by Palladium- Catalyzed Amidation of 2-Chloro-3-aminoheterocycles.. ChemInform 2012, 43 (31) , no-no.

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