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Current Organocatalysis

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ISSN (Print): 2213-3372
ISSN (Online): 2213-3380

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Research Article

A Simple and Modified One Pot Conversion of Carboxylic Acid to Ketone

Author(s): Debasis Sahoo, Samaresh Jana* and Sharmistha Sahoo

Volume 10, Issue 1, 2023

Published on: 09 March, 2023

Page: [58 - 65] Pages: 8

DOI: 10.2174/2213337210666221223145319

Price: $65

Abstract

Background: Ketone is one of the important functional groups in synthetic chemistry. For this reason, organic chemists focused on the synthesis of ketone starting from various functionalities since nineties. One of the method deals with the conversion of carboxylic acids to ketones in a one pot manner. We have recently reported a one pot transformation of carboxylic acid to ketone using TsCl or MsCl as an activator of carboxylc acid. In our previous reports, two equivalents of organometallic reagent have been used which may not be useful in medicinal chemistry. In this report, we have developed an alternative process for the transformation where only one equivalent of organometallic reagent has been employed.

Objective: In present scenario, we are interested to develop a process for the transformation of carboxylic acid to ketone using one equivalent of an organometallic reagent.

Methods: A carboxylic acid reacted with tosyl chloride in the presence of a sodium hydride to form a mixed anhydride. Here, the acidic proton was removed from the reaction mixture as hydrogen gas. This mixed anhydride was then treated with one equivalent of an organomagnesium reagent at -30°C to obtain the desired ketone.

Results: Following the optimum conditions, a few commercially available carboxylic acids were treated with TsCl, followed by the treatment of phenyl magnesium and methyl magnesium bromide to obtain phenyl and methyl ketones, respectively, in good to excellent yields.

Conclusion: A simple and modified one pot method for the conversion of carboxylic acids to ketone has been reported. In this developed process, one equivalent of the organomagnesium reagent has been used to obtain the desired ketone under the optimized reaction conditions.

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[1]
Dieter, R.K. Reaction of acyl chlorides with organometallic reagents: A banquet table of metals for ketone synthesis. Tetrahedron, 1999, 55(14), 4177-4236.
[http://dx.doi.org/10.1016/S0040-4020(99)00184-2]
[2]
Lawrence, N.J. Aldehydes and ketones. J. Chem. Soc. Perkin Trans., 1998, 1(10), 1739-1750.
[http://dx.doi.org/10.1039/a800646f]
[3]
McDaniel, R.; Thamchaipenet, A.; Gustafsson, C.; Fu, H.; Betlach, M.; Betlach, M.; Ashley, G. Multiple genetic modifications of the erythromycin polyketide synthase to produce a library of novel “unnatural” natural products. Proc. Natl. Acad. Sci., 1999, 96(5), 1846-1851.
[http://dx.doi.org/10.1073/pnas.96.5.1846] [PMID: 10051557]
[4]
Cuquerella, M.C.; Lhiaubet-Vallet, V.; Cadet, J.; Miranda, M.A. Benzophenone photosensitized DNA damage. Acc. Chem. Res., 2012, 45(9), 1558-1570.
[http://dx.doi.org/10.1021/ar300054e] [PMID: 22698517]
[5]
Kamat, P.V. Photochemistry on nonreactive and reactive (semiconductor) surfaces. Chem. Rev., 1993, 93(1), 267-300.
[http://dx.doi.org/10.1021/cr00017a013]
[6]
Rubottom, G.M.; Kim, C. Preparation of methyl ketones by the sequential treatment of carboxylic acids with methyllithium and chlorotrimethylsilane. J. Org. Chem., 1983, 48(9), 1550-1552.
[http://dx.doi.org/10.1021/jo00157a038]
[7]
Genna, D.T.; Posner, G.H. Cyanocuprates convert carboxylic acids directly into ketones. Org. Lett., 2011, 13(19), 5358-5361.
[http://dx.doi.org/10.1021/ol202237j] [PMID: 21894954]
[8]
Alonso, F.; Lorenzo, E.; Yus, M. Direct easy synthesis of ketones from carboxylic acid and chlorinated compounds. J. Org. Chem., 1996, 61(17), 6058-6059.
[http://dx.doi.org/10.1021/jo9605962]
[9]
Lubell, W.D.; Rapoport, H. Alpha. amino acids as chiral educt for asymmetric products. Alkylation of N-phenylfluoroenyl. alpha. amino ketones. Synthesis of optically pure. alpha.-alkyl carboxylic acids. J. Am. Chem. Soc., 1988, 110(22), 7447-7455.
[http://dx.doi.org/10.1021/ja00230a027]
[10]
Wilkinson, M.C. “Greener” friedel-crafts acylations: A metal- and halogen-free methodology. Org. Lett., 2011, 13(9), 2232-2235.
[http://dx.doi.org/10.1021/ol200482s] [PMID: 21438589]
[11]
Amani, J.; Molander, G.A. Direct conversion of carboxylic acids aryl ketones. Org. Lett., 2017, 19(13), 3612-3615.
[http://dx.doi.org/10.1021/acs.orglett.7b01588] [PMID: 28604003]
[12]
Colas, K.; Santos, A.C.V.D.; Kohlhepp, S.V.; Mendoza, A. Direct addition of grignard reagents to aliphatic carboxylic acids enabled by bulky turbo organomagnesium anilides. Chemistry, 2022, 28(9)e202104053
[http://dx.doi.org/10.1002/chem.202200295] [PMID: 35084063]
[13]
Hamashima, Y.; Kanai, M.; Shibasaki, M. Catalytic enantioselective cyanosilylation of ketone. J. Am. Chem. Soc., 2000, 122(30), 7412-7413.
[http://dx.doi.org/10.1021/ja001643h]
[14]
Sibi, M.P. Org. chemistry of n-methoxy-n-methylamides. applications in synthesis. Org. Prep. Proced. Int., 1993, 25(1), 15-40.
[http://dx.doi.org/10.1080/00304949309457931]
[15]
Heller, S.T.; Sarpong, R. Chemoselective esterification and amidation of carboxylic acids with imidazole carbamates and ureas. Org. Lett., 2010, 12(20), 4572-4575.
[http://dx.doi.org/10.1021/ol1018882] [PMID: 20857922]
[16]
Park, A.; Park, K.; Kim, Y.; Lee, S. Pd-catalyzed carbonylative reactions of aryl iodides and alkynyl carboxylic acids via decarboxylative couplings. Org. Lett., 2011, 13(5), 944-947.
[http://dx.doi.org/10.1021/ol102993y] [PMID: 21275411]
[17]
Gooßen, L.J.; Rodríguez, N.; Gooßen, K. Carboxylic acids as substrates in homogeneous catalysis. Angew. Chem. Int. Ed., 2008, 47(17), 3100-3120.
[http://dx.doi.org/10.1002/anie.200704782] [PMID: 18357604]
[18]
Ohki, M.; Asaoka, M. Synthesis of ketones from carboxylic acids with R(PrNH). Mg. Chem. Lett., 2009, 38(8), 856-857.
[http://dx.doi.org/10.1246/cl.2009.856]
[19]
Zhang, M.; Xie, J.; Zhu, C. A general deoxygenation approach for synthesis of ketones from aromatic carboxylic acids and alkenes. Nat. Commun., 2018, 9(1), 3517-3527.
[http://dx.doi.org/10.1038/s41467-018-06019-1] [PMID: 30158628]
[20]
Miyoshi, N.; Matsuo, T.; Asaoka, M.; Matsui, A.; Wada, M. A new synthetic method for methyl ketones from carboxylic acids using metallic strontium and methyl iodide. Chem. Lett., 2007, 36(1), 28-29.
[http://dx.doi.org/10.1246/cl.2007.28]
[21]
Zhao, C.; Jia, X.; Wang, X.; Gong, H. Ni-catalyzed reductive coupling of alkyl acids with unactivated tertiary alkyl and glycosyl halides. J. Am. Chem. Soc., 2014, 136(50), 17645-17651.
[http://dx.doi.org/10.1021/ja510653n] [PMID: 25415424]
[22]
Wang, J.; Hoerrner, M.E.; Watson, M.P.; Weix, D.J. Nickel catalyzed synthesis of dialkyl ketones from the coupling of N-alkyl pyridinium salts with activated carboxylic acids. Angew. Chem. Int. Ed., 2020, 59(32), 13484-13489.
[http://dx.doi.org/10.1002/anie.202002271] [PMID: 32374951]
[23]
Ruzi, R.; Liu, K.; Zhu, C.; Xie, J. Upgrading ketone synthesis direct from carboxylic acids and organohalides. Nat. Commun., 2020, 11(1), 3312-3321.
[http://dx.doi.org/10.1038/s41467-020-17224-2] [PMID: 32620758]
[24]
Zhang, M.; Yuan, X.A.; Zhu, C.; Xie, J. Deoxygenative deuteration of carboxylic acids with D2O. Angew. Chem. Int. Ed., 2019, 58(1), 312-316.
[http://dx.doi.org/10.1002/anie.201811522] [PMID: 30352142]
[25]
Gais, H.J. Synthesis of Thiol and Selenol Esters from Carboxylic Acids and Thiols or Selenols, Respectively. Angew. Chem. Int. Ed., 1977, 16(4), 244-246.
[http://dx.doi.org/10.1002/anie.197702441]
[26]
Si, S.; Wang, C.; Zhang, N.; Zou, G. Palladium catalyzed room temperature acylative suzuki coupling of high order aryl boron with carboxylic acid. J. Org. Chem., 2016, 81(10), 4364-4370.
[http://dx.doi.org/10.1021/acs.joc.6b00421] [PMID: 27100118]
[27]
Gooßen, L.J.; Ghosh, K. Palladium catalyzed synthesis of aryl ketones from boronic acids and carboxylic acids or anhydrides. Angew. Chem. Int. Ed., 2001, 40(18), 3458-3460.
[http://dx.doi.org/10.1002/1521-3773(20010917)40:18<3458:AID-ANIE3458>3.0.CO;2-0] [PMID: 11592170]
[28]
De Luca, L.; Giacomelli, G.; Porcheddu, A. A very mild and chemoselective oxidation of alcohols to carbonyl compounds. Org. Lett., 2001, 3(19), 3041-3043.
[http://dx.doi.org/10.1021/ol016501m] [PMID: 11554838]
[29]
Mekonnen, H.G.; Jana, S. Simple one pot synthesis of ketone from carboxylic acid using DCC as an activator. Tetrahedron Lett., 2019, 60(20), 1382-1384.
[http://dx.doi.org/10.1016/j.tetlet.2019.04.030]
[30]
Sahoo, D.; Sarkar, S.; Jana, S. A simple synthesis of ketone from carboxylic acid using tosyl chloride as an activator. Tetrahedron Lett., 2019, 60(39), 151084-151087.
[http://dx.doi.org/10.1016/j.tetlet.2019.151084]
[31]
Mekonnen, H.G.; Sahoo, D.; Jana, S.; Maji, S.K. Exploration of mesyl chloride in a one pot conversion of carboxylic acid to ketone. Curr. Organocatal., 2020, 7(3), 242-247.
[http://dx.doi.org/10.2174/2213337207999200611160509]
[32]
Mekonnen, H.G.; Jana, S. One pot conversion of carboxylic acid to ketone using trimethylsilyl chloride. Curr. Organocatal., 2021, 8(2), 195-199.
[http://dx.doi.org/10.2174/2213337207999200727143040]
[33]
Biju, A.T.; Glorius, F. Intermolecular N-heterocyclic carbene catalyzed hydroacylation of arynes. Angew. Chem. Int. Ed., 2010, 49(50), 9761-9764.
[http://dx.doi.org/10.1002/anie.201005490] [PMID: 21077079]
[34]
Zhang, W.; Zheng, B.; Jin, X.; Cheng, H.; Liu, J. Rapid epoxidation of α,β-unsaturated olefin in microdroplets without any catalysts. ACS Sustain. Chem. Eng., 2019, 7(17), 14389-14393.
[http://dx.doi.org/10.1021/acssuschemeng.9b04059]
[35]
Bai, C.; Li, A.; Yao, X.; Liu, H.; Li, Y. Efficient and selective aerobic oxidation of alcohols catalysed by MOF-derived Co catalysts. Green Chem., 2016, 18(4), 1061-1069.
[http://dx.doi.org/10.1039/C5GC02082D]
[36]
Lindh, J.; Sjöberg, P.J.R.; Larhed, M. Synthesis of aryl ketones by palladium(II)-catalyzed decarboxylative addition of benzoic acids to nitriles. Angew. Chem. Int. Ed., 2010, 49(42), 7733-7737.
[http://dx.doi.org/10.1002/anie.201003009] [PMID: 20839200]

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