Categories: C-C Bond Formation > Arenes >
Carboxylation, synthesis of benzoates and benzamides
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The presence of LICl enabled an efficient process for the carboxylation of
functionalized organozinc reagents with CO2 in DMF as solvent.
K. Kobayashi, Y. Kondo, Org. Lett., 2009,
11, 2035-2037.
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.
Pd-catalyzed decarboxylative cross-coupling of aryl iodides, bromides, and
chlorides with potassium oxalate monoesters is potentially useful for
laboratory-scale synthesis of aryl and alkenyl esters. Bulky, electron-rich
bidentate phosphine ligands are preferred in the reaction, whereas Cu is not
needed for decarboxylation.
R. Shang, Y. Fu, J.-B. Li, S.-L. Zhang, Q.-X. Guo, L. Liu, J. Am. Chem. Soc., 2009,
131, 5738-5739.
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.
In a simple, Mo-mediated carbamoylation reaction of aryl halides, the
incorporation of carbon monoxide is so efficient that it requires only a slight
excess amount of carbon monoxide in the form of its molybdenum complex, Mo(CO)6.
The reaction is applicable for the synthesis of a wide variety of not only
secondary and tertiary amides but also primary amides by using aqueous ammonia.
W. Ren, M. Yamane, J. Org. Chem., 2010,
75, 8410-8415.
An efficient and practical molybdenum-mediated carbonylation of aryl and
heteroaryl halides with a variety of nucleophiles using microwave irradiation
offers a wide scope and proceeds in good to excellent yields.
B. Roberts, D. Liptrot, L. Alcaraz, T. Luker, M. J. Stocks, Org. Lett., 2010,
12, 4280-4283.
A new and efficient alladium-catalyzed C-C coupling of aryl halides with
isocyanides enables the synthesis of amides under mild conditions. This
transformation could extend its use to the synthesis of natural products and
significant pharmaceuticals.
H. Jiang, B. Liu, Y. Li. A. Wang, H. Huang, Org. Lett., 2011,
13, 1028-1031.
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.
A palladium-catalyzed cross-coupling reaction between organoboronic acids and
commercially available N-methoxy-N-methylcarbamoyl chloride allows
the synthesis of Weinreb benzamides and heteroaromatic analogues, as well as α,β-unsaturated Weinreb
amides. This simple protocol is also
applicable to the use of potassium organotrifluoroborates.
R. Krishnamoorthy, S. Q. Lam, C. M. Manley, R. J. Herr, J. Org. Chem., 2010,
75, 1251-1258.
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.
A simple and straightforward method for the direct carboxylation of aromatic
heterocylces such as oxazoles, thiazoles, and oxadiazoles using CO2
as the C1 source requires no metal catalyst and only Cs2CO3
as the base. A good functional group tolerance is achieved.
O. Vechorkin, N. Hirt, X. Hu, Org. Lett., 2010,
12, 3567-3569.
