Table of contents

1. A Review of General Chemistry5h 5m
2. Molecular Representations1h 14m
3. Acids and Bases2h 46m
4. Alkanes and Cycloalkanes4h 17m
5. Chirality3h 39m
6. Thermodynamics and Kinetics1h 22m
7. Substitution Reactions1h 48m
8. Elimination Reactions2h 30m
9. Alkenes and Alkynes2h 9m
10. Addition Reactions3h 19m
11. Radical Reactions1h 58m
12. Alcohols, Ethers, Epoxides and Thiols2h 42m
13. Alcohols and Carbonyl Compounds2h 17m
14. Synthetic Techniques1h 26m
15. Analytical Techniques:IR, NMR, Mass Spect7h 3m
16. Conjugated Systems6h 13m
17. Ultraviolet Spectroscopy51m
18. Aromaticity2h 34m
19. Reactions of Aromatics: EAS and Beyond5h 1m
20. Phenols55m
21. Aldehydes and Ketones: Nucleophilic Addition4h 56m
22. Carboxylic Acid Derivatives: NAS2h 51m
23. The Chemistry of Thioesters, Phophate Ester and Phosphate Anhydrides1h 10m
24. Enolate Chemistry: Reactions at the Alpha-Carbon1h 53m
25. Condensation Chemistry2h 9m
26. Amines1h 43m
27. Heterocycles2h 0m
28. Carbohydrates5h 53m
29. Amino Acids4h 20m
30. Peptides and Proteins2h 42m
31. Catalysis in Organic Reactions1h 30m
32. Lipids 2h 50m
33. The Organic Chemistry of Metabolic Pathways2h 52m
34. Nucleic Acids1h 32m
35. Transition Metals6h 14m
36. Synthetic Polymers1h 49m

35. Transition Metals

Buchwald-Hartwig Amination Reaction

Organic Chemistry

35. Transition Metals

Buchwald-Hartwig Amination Reaction

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3:32 minutes

Problem 55j

Textbook Question

Predict the product(s) of the reactions shown.
(j)

Verified step by step guidance

Identify the type of reaction: The presence of Pd(PPh3)4 and NaOt-Bu suggests a Buchwald-Hartwig amination reaction, which is used to form C-N bonds by coupling aryl halides with amines.

Examine the reactants: The aryl halide is a bromobenzene derivative with methoxy (OMe) and trifluoromethyl (CF3) substituents. The amine is a cyclic secondary amine, pyrrolidine.

Consider the mechanism: The palladium catalyst facilitates the oxidative addition of the aryl bromide, forming a palladium-aryl complex. The amine then coordinates to the palladium, followed by reductive elimination to form the C-N bond.

Predict the product: The reaction will replace the bromine atom on the benzene ring with the pyrrolidine group, resulting in the formation of an aryl amine.

Evaluate the regioselectivity: The methoxy and trifluoromethyl groups are ortho and para directing, but since the bromine is already positioned, the reaction will proceed at the bromine site without affecting the substituents.

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Buchwald-Hartwig Amination

The Buchwald-Hartwig amination is a palladium-catalyzed coupling reaction that forms carbon-nitrogen bonds between aryl halides and amines. In this reaction, the palladium catalyst facilitates the replacement of the halide (Br) on the aromatic ring with an amine group, resulting in the formation of an aryl amine. This reaction is widely used in the synthesis of pharmaceuticals and organic materials.

Role of Palladium Catalyst

Palladium catalysts, such as Pd(PPh3)4, are crucial in facilitating cross-coupling reactions like the Buchwald-Hartwig amination. The palladium catalyst undergoes oxidative addition with the aryl halide, forming a palladium complex that can then react with the amine. This process allows for the formation of a new C-N bond, and the catalyst is regenerated at the end of the reaction cycle.

Base in Cross-Coupling Reactions

In cross-coupling reactions, a base like NaOt-Bu is often used to deprotonate the amine, increasing its nucleophilicity and facilitating its reaction with the palladium complex. The base also helps in the regeneration of the active palladium catalyst by removing the halide ion. This step is essential for the completion of the catalytic cycle and the successful formation of the desired product.

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