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Synthesis of carboxylic acids, esters and amides

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A user-friendly and operationally simple Ni-catalyzed carboxylation of unactivated primary alkyl bromides and sulfonates with CO2 at atmospheric pressure is characterized by its mild conditions and remarkably wide scope without the need for air- or moisture-sensitive reagents.
Y. Liu, J. Cornella, R. Martin, J. Am. Chem. Soc., 2014, 136, 11212-11215.


A catalytic carboxylation of unactivated primary, secondary, and tertiary alkyl chlorides with CO2 at atmospheric pressure features exquisite chemoselectivity, mild conditions and ease of execution.
M. Börjesson, T. Moragas, R. Martin, J. Am. Chem. Soc., 2016, 138, 7504-7507.


A mild Ni-catalyzed reductive coupling enables the synthesis of alkyl esters from readily available alkyl halides and chloroformates. Unactivated primary and secondary alkyl iodides as well as glycosyl, benzyl, and aminomethyl halides provide products in good yields with high functional group tolerance.
M. Zheng, W. Xue, T. Xue, H. Gong, Org. Lett., 2016, 18, 6152-6155.


A palladium-catalyzed alkoxycarbonylation of secondary alkyl bromides, that proceeds at low pressure (2 atm CO) under mild conditions, deliver esters from across a diverse range of substrates and represent the first catalytic carbonylations of alkyl bromides with carbon monoxide.
B. T. Sargent, E. J. Alexanian, J. Am. Chem. Soc., 2016, 138, 7520-7523.


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.


A variety of functionalized organozinc reagents undergo smooth addition reactions at ambient temperature to carbonyl compounds and carbon dioxide in the presence of stoichiometric amounts of MgCl2. Several reactions were performed on a large scale.
S. Bernhardt, A. Metzger, P. Knochel, Synthesis, 2010, 3802-3810.


An efficient cross-coupling reaction of chloroformates with organocopper reagents, derived from Grignard reagents, cuprous bromide and lithium bromide, provides esters in good yields.
D. Bottalico, V. Fiandanese, G. Marchese, A. Punzi, Synlett, 2007, 974-976.


A highly efficient palladium-catalyzed carbonylation of aryl, alkenyl, and allyl halides with phenyl formate affords one-carbon-elongated carboxylic acid phenyl esters in excellent yields. The reaction proceeds smoothly under mild conditions, avoids the use of carbon monoxide, and tolerates a wide range of functional groups including aldehyde, ether, ketone, ester, and cyano groups.
T. Ueda, H. Konishi, K. Manabe, Org. Lett., 2012, 14, 3100-3103.


A one-carbon homologation of an alcohol to the extended carboxylic acid, ester, or amide involves a Mitsunobu reaction with an alkoxymalononitrile, followed by unmasking in the presence of a suitable nucleophile. The homologation and unmasking can even be performed in a one-pot process in high yield.
N. Kagawa, A. E. Nibbs, V. H. Rawal, Org. Lett., 2016, 18, 2363-2366.


The reaction of Grignard reagents with alkyl imidazolecarboxylates, which were prepared from alcohols with carbonyl diimidazole, gave the corresponding esters in good to excellent yields.
T. Werner, A. G. M. Barrett, J. Org. Chem., 2006, 71, 4302-4304.


A Ni-catalyzed carboxylation of benzyl halides with CO2 proceeds under mild conditions at room temperature under atmospheric pressure. The method does not require well-defined and sensitive organometallic reagents and thus is user-friendly and operationally simple.
T. León, A. Correa, R. Martin, J. Am. Chem. Soc., 2013, 135, 1221-1224.


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.


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.


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.


Pd-catalyzed carbonylation of α-diazocarbonyl compounds or N-tosylhydrazone salts under atmospheric pressure of CO enables an efficient and mild approach toward ketene intermediates. These ketenes can react in situ with various nucleophiles to yield carboxylic acid derivates or in Staudinger cycloadditions to give β-lactam derivatives in good yields with excellent trans diastereoselectivity.
Z. Zhang, Y. Liu, L. Ling, Y. Li, Y. Dong, M. Gong, X. Zhao, Y. Zhang, J. Wang, J. Am. Chem. Soc., 2011, 133, 4330-4341.


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 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.


In the presence of a Cu(I)/NHC catalyst, highly regioselective reactions of allylboronic pinacol esters with CO2 (1 atm) give exclusively the more substituted β,γ-unsaturated carboxylic acids in most cases. Various substituted carboxylic acids can be prepared via this method, including compounds featuring all-carbon quaternary centers.
H. A. Duong, P. B. Huleatt, Q.-W. Tan, E. L. Shuying, Org. Lett., 2013, 15, 4034-4037.


A Ni-catalyzed regiodivergent reductive carboxylation of allyl esters with CO2 is mild, user-friendly, and operationally simple. The reaction is characterized by an exquisite selectivity profile that is dictated by the ligand backbone.
T. Moragas, J. Cornella, R. Martin, J. Am. Chem. Soc., 2014, 136, 17702-17705.


A Ni-catalyzed regiodivergent reductive carboxylation of allyl esters with CO2 is mild, user-friendly, and operationally simple. The reaction is characterized by an exquisite selectivity profile that is dictated by the ligand backbone.
T. Moragas, J. Cornella, R. Martin, J. Am. Chem. Soc., 2014, 136, 17702-17705.


In an enantioselective iridium-catalyzed allylic alkylation reaction of a masked acyl cyanide (MAC) reagent, the umpoled MAC synthon serves as a carbon monoxide equivalent. The reaction proceeds with good yield and excellent selectivity up to gram scale for a wide range of substituted allylic electrophiles to provide enantioenriched vinylated α-aryl carbonyl derivatives.
J. C. Hethcox, S. E. Shockley, B. M. Stoltz, Org. Lett., 2017, 19, 1527-1529.


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.


The palladium-catalyzed cross-coupling of allylic and benzylic halides with N,N-dimethylcarbamoyl(trimethyl)silane affords tertiary amides in good to excellent yields.
R. F. Cunico, R. K. Pandey, J. Org. Chem., 2005, 70, 9048-9050.


Treatment of widely available isocyanates with monohalolithium and dihalolithium carbenoids provides α-halo- and α,α-dihaloacetamide derivatives. While monohalolithium carbenoids can be prepared by a smooth lithium-halogen exchange, the preparation of the corresponding dihalo compounds proved to be highly dependent on the base used to realize the deprotonation, with lithium 2,2,6,6-tetramethylpiperidine emerging as optimal.
V. Pace, L. Castoldi, A. D. Mamuye, W. Holzer, Synthesis, 2014, 46, 2897-2909.


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.


A mild, Co2(CO)8-catalyzed carbonylative opening of terminal epoxides under 1 atm of carbon monoxide at room temperature in methanol provides β-hydroxy esters in good yields. This transformation tolerates various functional groups.
S. E. Denmark, M. Ahmad, J. Org. Chem., 2007, 72, 9630-9634.


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.


The reaction of chiral 1-aminoalkylepoxides with CO2, generated from acidic treatment of an aqueous solution of NaHCO3 at room temperature, efficiently afforded enantiopure cyclic carbonates with total selectivity. Carbonates were readily transformed into the corresponding diols by reaction with LiAlH4 or by basic hydrolysis.
J. M. Concellón, V. del Solar, S. Carcía-Granda, M. R. Díaz, J. Org. Chem., 2007, 72, 7567-7568.


α-Halonitriles react with alkyllithium, organomagnesium, and lithium dimethylcuprate reagents generating reactive, metalated nitriles. The rapid halogen-metal exchange with alkyllithium and Grignard reagents allows Barbier-type reactions with various electrophiles.
F. F. Fleming, Z. Zhang, W. Liu, P. Knochel, J. Org. Chem., 2005, 70, 2200-2005.


The Brønsted acid catalyzed formal insertion of an isocyanide into a C-O bond of various acyclic and cyclic acetals can be applied to form α-alkoxy imidates. Functional groups, such as nitro, cyano, halogen, ester, and alkoxy groups, are tolerant to the reaction conditions employed. The course of the reaction is highly dependent on the structure of the isocyanide.
M. Tobisu, A. Kitajima, S. Yoshioka, I. Hyodo, M. Oshita, N. Chatani, J. Am. Chem. Soc., 2007, 129, 11431-11437.


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.