Categories: C-C Bond Formation > Oxygen-containing molecules > Carboxyl derivatives > Carboxylation

Hydrocarboxylations and similar reactions

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Recent Literature

The use of formic acid or TFBen as CO surrogates enables selective and effective syntheses of 4-arylbutanoic acids, 2-arylbutanoic acids, and 4-arylbutanals from allylbenzenes under carbon monoxide gas-free conditions.
F.-P. Wu, D. Li, J.-B. Peng, X.-F. Wu, Org. Lett., 2019, 21, 5699-5703.

A photochemical activation of formate salts using a thiyl radical initiator without an exogenous chromophore enables a hydrocarboxylation of unactivated alkenes. This redox-neutral method is technically simple to execute and effective across a broad range of alkene substrates.
S. N. Alektiar, H. Han, Y. Dang, C. Z. Rubel, Z. W. Wickens, J. Am. Chem. Soc., 2023, 145, 10991-10997.

A photochemical process for the preparation of carboxylic acids from formate salts and alkenes proceeds in high yields across diverse functionalized alkene substrates with excellent regioselectivity. This operationally simple and redox-neutral hydrocarboxylation can be readily scaled in batch at low photocatalyst loading (0.01% photocatalyst).
S. N. Alektiar, Z. K. Wickens, J. Am. Chem. Soc., 2021, 143, 13022-13028.

An electrosynthetic approach enables a selective hydrocarboxylation of alkenes that overcomes the limitations of current transition metal and photochemical approaches. The reported method especially allows a highly regioselective direct access to carboxylic acids derived from β,β-trisubstituted alkenes.
A. Alkayal, V. Tabas, S. Montanaro, I. A. Wrigt, A. V. Malkov, B. R. Buckley, J. Am. Chem. Soc., 2020, 142, 1780-1785.

An efficient Pd-catalyzed hydrocarboxylation of alkenes with HCOOH provides a broad range of linear carboxylic acids bearing various functional groups with excellent chemo- and regioselectivities under mild reaction conditions. The reaction process is operationally simple and requires no handling of toxic CO.
W. Ren, J. Chu, F. Sun, Y. Shi, Org. Lett., 2019, 21, 5967-5970.

In a NI-catalyzed protocol that reliably predicts and controls the site-selective incorporation of CO₂ to a wide range of unsaturated hydrocarbons, water serves as formal hydride source.
M. Gaydou, T. Moragas, F. Juliá-Hernández, R. Martin, J. Am. Chem. Soc., 2017, 139, 12161-12164.

Regioselective Pd-catalyzed hydrocarboxylations of vinyl arenes with oxalic acid provide either linear or branched carboxylic acids with high regioselectivities under mild reaction conditions. The reactions are operationally simple and requires no handling of toxic CO. Besides the ligand, the counteranion of the Pd catalyst system plays an important role for the regioselectivity.
W. Ren, X. Sheng, C. Fan, Y. Shi, Org. Lett., 2023, 25, 7786-7790.

An effective Pd-catalyzed hydrocarboxylation of aryl olefins with formic acid and Ac₂O provides 2- and 3-arylpropanoic acids regioselectively, depending on the judicious choice of ligand, without the use of toxic CO gas.
W. Liu, W. Ren, J. Li, Y. Shi, W. Chang, Y. Shi, Org. Lett., 2017, 19, 1748-1751.

Cp₂TiCl₂-catalyzed exchange of alkenes with Grignard reagents and subsequent reaction with CO₂ provides carboxylic acids in high yields. The reaction proceeds with a wide range of alkenes under mild conditions. Styrenes can be transformed to α-aryl carboxylic acids, and aliphatic alkenes give linear alkanoic acids.
P. Shao, S. Wang, C. Chen, C. Xi, Org. Lett., 2016, 18, 2050-2053.

An effective Pd-catalyzed regio- and enantioselective hydroesterification of aryl olefins with phenyl formate provides phenyl 2-arylpropanoates in good yields with high b/l ratios and ee's without using toxic CO gas.
J. Li, W. Chang, W. Ren, J. Dai, Y. Shi, Org. Lett., 2016, 18, 5456-5459.

An effective Pd-catalyzed regiodivergent hydroesterification of aryl olefins with phenyl formate gives either linear or branched phenyl arylpropanoates in good yields with high regioselectivities depending on the ligand without the use of toxic CO gas.
W. Ren, W. Chang, Y. Wang, J. Li, Y. Shi, Org. Lett., 2015, 17, 3544-3547.

Using an effective Pd-catalyzed hydrocarboxylation of olefins with phenyl formate and formic acid, various carboxylic acids are obtained in good yields with high regioselectivities under operationally simple conditions in the absence of toxic CO gas.
Y. Wang, W. Ren, J. Li, H. Wang, Y. Shi, Org. Lett., 2014, 16, 5960-5963.

A nickel-catalyzed reductive carboxylation of styrenes using CO₂ proceeds under mild conditions using diethylzinc as the reductant. The catalyst system is very robust and will fixate CO₂ in good yield even if exposed to only an equimolar amount introduced into the headspace above the reaction.
C. M. Williams, J. B. Johnson, T. Rovis, J. Am. Chem. Soc., 2008, 130, 14936-14937.

Hydrocarboxylation of aryl alkenes in the presence of FeCl₂ as precatalyst, bis(imino)pyridine as ligand, an atmospheric pressure of CO₂, and EtMgBr as a hydride source gives α-aryl carboxylic acids in excellent yields and with near-perfect regioselectivity. Various, electronically differentiated aryl alkenes were transformed to the corresponding α-aryl carboxylic acids in very good isolated yield.
M. D. Greenhalgh, S. P. Thomas, J. Am. Chem. Soc., 2012, 134, 11900-11903.

Alkylboranes, generated by hydroboration of terminal olefins with 9-BBN-H, underwent smooth coupling with carbamoyl chlorides in the presence of palladium catalyst and Cs₂CO₃ to give C1-elongated amides.
Y. Yasui, S. Tsuchida, H. Miyabe, Y. Takemoto, J. Org. Chem., 2007, 72, 5898-5900.

The combination of a decatungstate and a disulfide catalyzes hydrocarbamoylation, -acylation, -alkylation, and -silylation of styrenes under visible light irradiation. In this photoredox methodology, the use of a disulfide as a cocatalyst is crucial for the reaction efficiency. This photoredox system provides a broad range of useful building blocks and high-value molecules.
A. Prieto, M. Taillefer, Org. Lett., 2021, 23, 1484-1488.

The presence of catalytic amounts of halide salts enhanced dramatically the reaction efficiency in the Ru-catalyzed hydroesterification of alkenes and alkynes using a chelating 2-pyridylmethyl formate.
E. J. Park, J. M. Lee, H. Han, S. Chang, Org. Lett., 2006, 8, 4355-4358.

An enantioselective CuH-catalyzed hydrocarboxylation of allenes with a commercially available fluoroformate provides enantioenriched α-quaternary and tertiary carboxylic acid derivatives in good yields with exclusive branched regioselectivity. A broad range of heterocycles and functional groups on the allenes were tolerated.
S. Feng, S. L. Buchwald, J. Am. Chem. Soc., 2021, 143, 4935-4941.

PSiP-pincer type palladium-catalyzed hydrocarboxylation enables an efficient one-to-one coupling reaction of atmospheric pressure carbon dioxide with 1,3-dienes. The reaction represents a highly useful method for the synthesis of β,γ-unsaturated carboxylic acid derivatives from CO₂ and various 1,3-dienes including easily available chemical feedstock such as 1,3-butadiene and isoprene.
J. Takaya, K. Sasano, N. Iwasawa, Org. Lett., 2011, 13, 1698-1701.

A tridentate PSiP pincer-type palladium complex-catalyzed hydrocarboxylation of allenes under carbon dioxide gives synthetically useful β,γ-unsaturated carboxylic acids. This novel CO₂-fixation proceeds via hydropalladation of allenes, followed by regioselective nucleophilic addition to CO₂ in the presence of an appropriate reducing agent. Esters, carbamates, ketones, and alkenes are tolerated.
J. Takaya, N. Iwasawa, J. Am. Chem. Soc., 2008, 130, 15254-15255.

Formate salts can serve as hydride as well as a CO₂ source in a mild PGeP-palladium complex-catalyzed hydrocarboxylation of allenes through a highly efficient decarboxylation-carboxylation process.
C. Zhu, J. Takaya, N. Iwasawa, Org. Lett., 2015, 17, 1814-1817.

Related

A visible-light-driven reductive carboarylation of styrenes with CO₂ and a broad range of aryl iodides and bromides has been achieved in a regioselective manner.
H. Wang, Y. Gao, C. Zhou, G. Li, J. Am. Chem. Soc., 2020, 142, 8122-8129.

Thiourea-based ligands were evaluated for the palladium-catalyzed bis(methoxycarbonylation) of terminal olefins. The usefulness of these ligands for this reaction is demonstrated by their stability to oxidizing agents, and their superiority in preventing palladium precipitation and double-bond isomerization.
M. Dai, C. Wang, G. Dong, J. Xiang, T. Luo, B. Liang, J. Chen, Z. Yang, Eur. J. Org. Chem., 2003, 4346-4348.

Visible-light photoredox-catalyzed fragmentation of methyl N-phthalimidoyl oxalate allows direct construction of a 1,4-dicarbonyl structural motif by a regioselective conjugate addition of the methoxycarbonyl radical to reactive Michael acceptors.
Y. Slutskyy, L. E. Overman, Org. Lett., 2016, 18, 2564-2567.

In a palladium-catalyzed intermolecular aminocarbonylation of alkenes, the use of hypervalent iodine reagent can accelerate the reaction. The current transformation presents a convenient method to generate β-amino acid derivatives from simple alkenes.
J. Cheng, X. Qi, M. Li, P. Chen, G. Liu, J. Am. Chem. Soc., 2015, 137, 2480-2483.

Regioselective copper-catalyzed boracarboxylation of vinyl arenes with bis(pinacolato)diboron and carbon dioxide provides boron-functionalized α-aryl carboxylic acids in good yields. The synthetic utility of the transformation was shown through subsequent derivatization of the carbon-boron bond yielding formal hydroxy- and fluorocarboxylation products as well as anionic difluoroboralactones.
T. W. Butcher, E. J. McClain, T. G. Hamilton, T. M. Perrone, K. M. Kroner, G. C. Donohoe, N. G Akhmedov, J. L. Petersen, B. V. Popp, Org. Lett., 2016, 18, 6428-6431.