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Carbamoylation of Aryl Halides by Molybdenum or Tungsten Carbonyl
Amine Complexes
Wei Ren and Motoki Yamane*
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences,
Nanyang Technological University, 21 Nanyang Link, Singapore 637371, Singapore
Received February 16, 2010
When aryl halide is treated with molybdenum carbonyl amine complex in the presence of base,
carbamoylation proceeds to give amide in good yield. The proposed mechanism involves oxidative
addition of aryl halide to molybdenum(0) complex, migratory insertion to carbon monoxide giving
acyl(amino)molybdenum(II) or aryl(carbamoyl)molybdenum(II) intermediate, and reductive elimi-
nation of the amide. This method is simple and provides an alternative method to the conventional
palladium-catalyzed amide formation using gaseous carbon monoxide.
Introduction
aryl halides and Group VI metal carbonyl amine complexes
(
5
Scheme 1, path B). Other than the mechanism involving
Amides are an important class of compounds in chemistry
and biology that have been used as synthetic intermediates of
acylpalladium(II) intermediate B, we proposed one involving
carbamoylpalladium(II) intermediate C. Although the me-
chanism was not clear, we could provide an alternative
palladium-catalyzed amide formation without using gaseous
1
many natural products and artificial functionalized materials.
Traditionally, amides have been synthesized by the reaction of
activated carboxylic acid derivatives such as acid chlorides,
6
carbon monoxide (Scheme 2).
2
anhydrides, and esters with amines. Since Heck and co-
During the study on the above palladium-catalyzed amide
synthesis by using Group VI metal carbonyl amine com-
plexes, we found that the amides were obtained even without
palladium catalyst when the reaction was performed at
workers reported the palladium-catalyzed three-component
coupling of aromatic halide, carbon monoxide, and amine,
3,4
this coupling has drawn much attention. By using this
reaction, one-carbon-elongated amides can be synthesized
from aryl halides. The reaction proceeds with the catalytic
mechanism depicted in Scheme 1. Oxidative addition of aryl
halide to palladium(0) complex takes place to generate
arylpalladium(II) intermediate A. Migratory insertion of car-
bon monoxide gives acylpalladium(II) complex B, followed by
the reaction with amine, to afford amide with regeneration of
palladium(0) catalyst. We recently proposed another possibi-
lity for palladium-catalyzed amide formation in the reaction of
(
4) (a) Cacchi, S.; Morera, E.; Ortar, G. Tetrahedron Lett. 1985, 26, 1109.
b) Cacchi, S.; Ciattini, P. G.; Morera, E.; Ortar, G. Tetrahedron Lett. 1986,
7, 3931. (c) Perry, R. J.; Wilson, B. D. J. Org. Chem. 1996, 61, 7482.
(
2
(d) Morera, E.; Ortar, G. Tetrahedron Lett. 1998, 39, 2835. (e) Schnyder, A.;
Beller, M.; Mehltretter, G.; Nsenda, T.; Studer, M.; Indolese, A. F. J. Org.
Chem. 2001, 66, 4311. (f) Schnyder, A.; Indolese, A. F. J. Org. Chem. 2002,
6
7, 594. (g) Skoda-Foldes, R.; Kollar, L. Curr. Org. Chem. 2002, 6, 1097.
(h) Li, Y.; Alper, H.; Yu, Z. K. Org. Lett. 2006, 8, 5199. (i) Martinelli, J. R.;
Clark, T. P.; Watson, D. A.; Munday, R. H.; Buchwald, S. L. Angew. Chem.,
Int. Ed. 2007, 46, 8460. (j) Takacs, A.; Jakab, B.; Petz, A.; Kollar, L.
Tetrahedron 2007, 63, 10372. (k) Barnard, C. F. J. Organometallics 2008,
27, 5402. (l) Martinelli, J. R.; Watson, D. A.; Freckmann, D. M. M.; Barder,
T. E.; Buchwald, S. L. J. Org. Chem. 2008, 73, 7102. (m) Worlikar, S. A.;
Larock, R. C. J. Org. Chem. 2008, 73, 7175. (n) Deagostino, A.; Larini, P.;
Occhiato, E. G.; Pizzuto, L.; Prandi, C.; Venturello, P. J. Org. Chem. 2008,
73, 1941. (o) Takacs, A.; Farkas, R.; Kollar, L. Tetrahedron 2008, 64, 61.
(p) Takacs, A.; Acs, P.; Farkas, R.; Kokotos, G.; Kollar, L. Tetrahedron
2008, 64, 9874. (q) Tambade, P. J.; Patil, Y. P.; Bhanushali, M. J.; Bhanage,
B. M. Synthesis 2008, 15, 2347. (r) Csajagi, C.; Borcsek, B.; Niesz, K.;
Kovacs, I.; Szekelyhidi, Z.; Bajko, Z.; Uerge, L.; Darvas, F. Org. Lett. 2008,
10, 1589. For a review, see: (s) Yasui, Y.; Takemoto, Y. Chem. Rec. 2008, 8,
386. (t) Beccalli, E. M.; Broggini, G.; Martinelli, M.; Sottocornola, S. Chem.
Rev. 2007, 107, 5318.
(
1) (a) Larock, R. C. Comprehensive Organic Transformations, 2nd ed.;
Wiley-VCH: New York, 1999. (b) Kim, J. W.; Kazuya, Y.; Mizuno, N. Angew.
Chem., Int. Ed. 2008, 47, 9249 and related reference therein.
(2) (a) Ziegler, T. Synthesis from Carboxylic Acids and Derivatives. In
Science of Synthesis; Weinreb, S. M., Ed.; Georg Thieme Verlag: Stuttgart,
New York, 2005; Vol. 21, pp 27-42. (b) Smith, M. B. Organic Synthesis, 2nd ed.;
McGraw-Hill: New York, 2002. (c) Naik, S.; Bhattacharjya, G.; Talukdar, B.;
Patel, B. K. Eur. J. Org. Chem. 2004, 1254. (d) Veitch, G. E.; Bridgwood, K. L.;
Ley, S. V. Org. Lett. 2008, 10, 3623. (e) Terada, Y.; Ieda, N.; Komura, K.; Sugi, Y.
Synthesis 2008, 2318.
(
3) (a) Schoenberg, A.; Bartoletti, I.; Heck, R. F. J. Org. Chem. 1974, 39,
318. (b) Schoenberg, A.; Heck, R. F. J. Org. Chem. 1974, 39, 3327.
c) Schoenberg, A.; Heck, R. F. J. Am. Chem. Soc. 1974, 96, 7761.
3
(
(5) Ren, W.; Yamane, M. J. Org. Chem. 2009, 74, 8332.
DOI: 10.1021/jo1002592
r 2010 American Chemical Society
Published on Web 03/29/2010
J. Org. Chem. 2010, 75, 3017–3020 3017