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Synthesis of Anilines

Anilines (2007)

  1. John F. Hartwig*,
  2. Shashank Shekhar,
  3. Qilong Shen,
  4. Fabiola Barrios-Landeros

Published Online: 15 DEC 2009

DOI: 10.1002/9780470682531.pat0391

Patai's Chemistry of Functional Groups

Patai's Chemistry of Functional Groups

How to Cite

Hartwig, J. F., Shekhar, S., Shen, Q. and Barrios-Landeros, F. 2009. Synthesis of Anilines. Patai's Chemistry of Functional Groups. .

Author Information

  1. Yale University, Department of Chemistry, New Haven, Connecticut, USA

  1. *

    Current Address: A410 CLSL, Box 58-6, MC-712, Department of Chemistry, University of Illinois, 600 South Mathews Av., Urbana, Illinois 61801, USA. Fax: 217-244-8024; e-mail: jhartwig@uiuc.edu

Publication History

  1. Published Online: 15 DEC 2009
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Figure 1. Proposed structure of a Ni–benzyne complex

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Figure 2. Two ligands used for the aqueous reduction of nitrobenzene

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Figure 3. Ligands used for the reaction of acyclic secondary amines with aryl halides

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Figure 4. Ligands created for the reaction of acyclic secondary amines with aryl halides following the success of Kumada's ligand in catalyzing that reaction, as shown in equation 5

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Figure 5. Sterically bulky, electronically rich, monodentate alkylphosphines and a carbene for a general reaction of acyclic secondary amines with aryl halides

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Figure 6. Ligands synthesized for amination of unactivated aryl chlorides besides the ligands in Figure 5

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Figure 7. Carbenes and complexes with carbene as ancillary ligands synthesized for amination of aryl chlorides

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Figure 8. X-phos, a derivative of ligand 11 in Figure 5, synthesized for amination of unactivated aryl tosylates

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Figure 9. Josiphos ligand that generates highly active catalysts for the coupling of primary alkylamines with aryl chlorides

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Figure 10. Phanephos, similar to BINAP, synthesized for amination by primary alkylamines

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Figure 11. Ligands used for arylation of anilines

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Figure 12. Structures of palladacycles developed at Solvias

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Figure 13. Structures of phosphine ligands developed at Pfizer

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Figure 14. [Pd(P(Bu-t)2(1-adamantyl))(Ph)Br] (53), [PdP(Bu-t)3(m-xylyl)I] (54). Reprinted with permission from (185). Copyright 2002 American Chemical Society

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Figure 15. DPPF amido complexes with aryl groups of different electronic properties

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Figure 16. [PdP(Bu-t)3(4-OMeC6H4)N(3,5-(CF3)2C6H3)2]

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Figure 17. Ligands used by Bayer for monoarylation of aniline with activated aryl chlorides

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Figure 18. Novel resin-bound triarylbismuth diacetate as N-arylation reagent

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Figure 19. Monoarylation products of amines with triphenylbismuthane

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Figure 20. Novel resin-bound bismuthanes as N-arylation reagents

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Figure 21. N-Arylation using aryl iodonium salts

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Figure 22. Ligands screened by Buchwald and coworkers for improvements of the Goldberg reaction

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Figure 23. Amidation using amino acids as ligands

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Scheme 1. Synthesis of the anionic and neutral palladium pyrrolyl complexes and their reactivities.

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Scheme 2. Mechanism for the activation of the palladacyclic catalyst precursor 38 to produce [Pd{P(tol− o)3}2].

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Scheme 3. Tautomeric phosphine oxides and phosphinous acids used as ligands.

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Scheme 4. General mechanism for palladium-catalyzed amination of aryl halides.

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Scheme 5. Distinct mechanisms for the oxidative addition of ArX (X = I, Br, Cl) to Pd(Q-phos-tol)2.

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Scheme 6. Concurrent mechanisms for reductive elimination of amines.

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Scheme 7. N-Arylation of α-amino acids with aryl halides.

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Scheme 8. Early progress toward reactions of aryl halides with aliphatic amines.

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Scheme 9. Anionic O-donors screened for N-arylation of primary alkyl amines.

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Scheme 10. General mechanism of copper-catalyzed amination reactions with hypervalent organometallic reagents.

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Scheme 11. Potential mechanism for the formation of arenes and polymeric species during copper-catalyzed N-arylation of anilines.

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Scheme 12. Potential mechanisms for copper-catalyzed amination reactions with low-valent organometallic reagents.

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Scheme 13. Mechanism of coupling of imidazole with arylboronic acids.

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Scheme 14. Mechanism of copper-catalyzed amination of aryl halides.