Ullmann condensation

The Ullmann condensation or Ullmann ether synthesis is a variation of the Ullmann reaction, in which a phenol is coupled to an aryl halide to a diaryl ether in the presence of a copper compound, named after Fritz Ullmann. [cite journal
title = Ueber die Phenylirung von Phenolen
author = Fritz Ullmann, Paul Sponagel
journal = Berichte der deutschen chemischen Gesellschaft
volume = 38
issue = 2
pages = 2211–2212
year = 1905
url =
doi = 10.1002/cber.190503802176 ] The corresponding aniline or aryl amide reaction is sometimes called Goldberg reaction, named after Irma Goldberg. [cite journal
title = Ueber Phenylirungen bei Gegenwart von Kupfer als Katalysator
author = Iram Goldberg
journal = Berichte der deutschen chemischen Gesellschaft
volume = 39
issue = 2
pages = 1691–1692
year = 1906
url =
doi = 10.1002/cber.19060390298]

An example is the synthesis of "p-nitrophenyl phenyl ether" [Ray Q. Brewster and Theodore Groening, "Ether, p-nitrophenyl phenyl", "Organic Syntheses", Coll. Vol. 2, p.445 [http://www.orgsyn.org/orgsyn/prep.asp?prep=cv2p0445 Online article] ]

An active copper powder that is required for this reaction can be prepared by the reduction of copper sulfate by zinc metal in hot water causing the precipitation of elementary copper.

Goldberg reaction

An example of a Goldberg reaction is the synthesis of "N"-phenyl-anthranilic acid, an intermediate of acridone via the Goldberg reaction [C. F. H. Allen and G. H. W. McKee, "Acridone", "Organic Syntheses", Coll. Vol. 2, p.15. ( [http://www.orgsyn.org/orgsyn/prep.asp?prep=cv2p0015 Online article] )]

An Ullmann-type aromatic amination reaction between an aryl iodide and an aryl amine as coupling partners has been published. [cite journal
title = Ligand-Accelerated Catalysis of the Ullmann Condensation: Application to Hole Conducting Triarylamines
author = H.B. Goodbrand, Nan-Xing Hu
journal = Journal of Organic Chemistry
volume = 64
issue =
pages = 670–674
year = 1999
url =
doi = 10.1021/jo981804o ] The catalyst used is formed from copper(I) iodide and phenanthroline. As this reaction proceeds well with an electron-rich aryl iodide it is a valuable alternative to the Buchwald-Hartwig amination reaction, which gives best yields with electron-poor aryl halides.

The scope is extended to amides [cite journal
title = A General and Efficient Copper Catalyst for the Amidation of Aryl Halides and the N-Arylation of Nitrogen Heterocycles
author = Klapars, A.; Antilla, J. C.; Huang, X.; Buchwald, S. L.
journal = J. Am. Chem. Soc. (Communication)
volume = 123
issue = 31
pages = 7727–7729
year = 2001
url =
doi = 10.1021/ja016226z ] [cite journal
title = A General and Efficient Copper Catalyst for the Amidation of Aryl Halides
author = Klapars, A.; Huang, X.; Buchwald, S. L.
journal = J. Am. Chem. Soc. (Article)
volume = 124
issue = 25
pages = 7421–7428
year = 2002
url =
doi = 10.1021/ja0260465 ] [cite journal
title = The Role of Chelating Diamine Ligands in the Goldberg Reaction: A Kinetic Study on the Copper-Catalyzed Amidation of Aryl Iodides
author = Strieter, E. R.; Blackmond, D. G.; Buchwald, S. L.
journal = J. Am. Chem. Soc. (Communication)
volume = 127
issue = 12
pages = 4120–4121
year = 2005
url =
doi = 10.1021/ja050120c] for example in the synthesis of this Camps cyclization precursor [cite journal
title = Sequential Cu-Catalyzed Amidation-Base-Mediated Camps Cyclization: A Two-Step Synthesis of 2-Aryl-4-quinolones from o-Halophenones
author = Jones, C. P.; Anderson, K. W.; Buchwald, S. L.
journal = J. Org. Chem.
volume = 72
issue = 21
pages = 7968–7973
year = 2007
url =
doi = 10.1021/jo701384n ] :

References