Categories: C-C Bond Formation > Arenes >
Carboxylation, synthesis of benzoates and benzamides
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Phosphonium bromide ionic liquids are superior media in the carbonylation of
aryl and vinyl halides. Formation of acid bromide intermediates was detected in
control experiments providing an extended view on the overall catalytic cycle
involved. Solvent-free product isolation and recycling of the ionic liquid
containing active Pd-catalyst are also demonstrated.
J. McNulty, J. J. Nair, A. Robertson, A. Lei, Org. Lett., 2007,
9, 4575-4578.
A mild, functional group tolerant palladium-catalyzed carbonylation of aryl
chlorides using atmospheric pressure of carbon monoxide allows the preparation
of phenyl esters, alkyl esters and carboxylic acids. Phenyl esters are shown to
be useful acylating agents, delivering libraries of carbonyl derivatives,
including alkyl, allyl and thioesters, under very mild conditions.
D. A. Watson, X. Fan, S. L. Buchwald, J. Org. Chem., 2008,
73, 7096-7101.
A system derived from Pd(OAc)2 and the bulky, bidentate dcpp ligand
catalyzes the carbonylation of aryl tosylates and mesylates to form esters under
atmospheric CO pressure and temperatures of 80-110°C. A broad substrate scope
allows carbonylation of electron-rich, electron-poor, and heterocyclic tosylates
and mesylates, and the reaction shows wide functional group tolerance.
R. H. Munday, J. R. Martinelli, S. L. Buchwald, J. Am. Chem. Soc., 2008,
130, 2754-2755.
A copper(I)-catalyzed carboxylation reaction of aryl- and alkenylboronic
esters under CO2 showed wide generality with higher functional group
tolerance compared to the corresponding Rh(I)-catalyzed reaction.
J. Takaya, K. Ukai, N. Iwasawa, Org. Lett.,
2008,
10, 2697-2700.
Treatment of 2,2-dimethylpropan-1,3-diol esters of aryl- and alkenylboronic
acids with a catalytic amount of [Rh(OH)(cod)]2 in the presence
of 1,3-bis(diphenylphosphino)propane and CsF in dioxane at 60°C under carbon
dioxide atmosphere gave carboxylic acids in good yields.
K. Ukai, M. Aoki, J. Takaya, N. Iwasawa, J. Am. Chem. Soc.,
2006,
128, 8706-8707.
An operationally simple hydroxycarbonylation of aryl and vinyl triflates to
the corresponding carboxylic acids with a palladium-mediated microwave
system was carried out in water.
G. Lesma, A. Sacchetti, A. Silvani,
Synthesis, 2006, 594-596.
Sonication of a mixture of magnesium powder, 1,2-dibromoethane, aryl bromide
and diethyl dicarbonate in THF followed by treatment with BF3·OEt2
at room temperature afforded aryl ester with reasonable yield. A series of
aryl bromides were investigated and transformed to their corresponding aryl
esters.
A. S.-Y. Lee, C.-C. Wu, L.-S. Lin, H.-F. Hsu, Synthesis, 2004,
568-572.
Regioselective halogen-metal exchange reactions using isopropylmagnesium
chloride were carried out on 3-substituted 1,2-dibromo arenes.
K. Menzel, L. Dimichele, P. Mills, D. E. Frantz, T. D. Nelson, M. H. Kress, Synlett, 2006,
1948-1952.
The Pd-catalyzed coupling of ortho-substituted arylboronic esters
with carbamoyl chlorides gives tertiary benzamides in good yield.
M. Lysen, S. Kelleher, M. Betrup, J. L. Kristensen, J. Org. Chem.,
2005,
70, 5342-5343.
Nickel catalysis enables a very efficient aminocarbonylation reaction to be
performed between aryl iodides or bromides and N,N-dimethylformamide (DMF)
in the presence of sodium methoxide and a phosphite ligand, which is very stable
to air and moisture and, furthermore, inexpensive.
J. Ju, M. Jeong, J. Moon, H. M. Jung, S. Lee, Org. Lett., 2007,
9, 4615-4618.
Tertiary amides can be synthesized by a palladium-catalyzed coupling of
N,N-dimethylformamide with aryl or alkenyl halides in the presence of
phosphoryl chloride.
K. Hosoi, K. Nozaki, T. Hiyama, Org. Lett., 2002, 4,
2849-2851.
Cycloadditions of Diels-Alder dienophiles containing linked enyne sites, each
substituted with activating groups, occurred specifically at the acetylenic
center. A remote acrylyl group bound to the olefinic site totally dominated the
regiochemical course of the cycloaddition. Explanations for these findings at
the computational level are provided.
M. Dai, D. Sarlah, M. Yu, S. J. Danishefsky, G. O. Jones, K. N. Houk, J. Am. Chem. Soc., 2007,
129, 645-657.
