ACS Catalysis
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Picolinamide Directing Group Org. Biomol. Chem. 2014, 12, 1405-
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(7) The reaction with 1.2 equiv amount of 4a gave the product in 88% yield.
However some aryl bromides gave the corresponding ketones in mod-
erate yields. We decided to investigate the scope of aldehydes and aryl
bromides using 3 equiv amount of aryl bromides.
(8) Crawford, J. J.; Henderson, K.W.; Kerr, W. J. Direct and Efficient One-
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Sawada, N.; Sawai, Y.; Zhu, L. A Nitrogen-Assisted One-Pot Het-
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Cross-Couling: Direct Transformation of Aldehydes into Esters and
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Rana, S.; Phukan, A. K.; Maiti, D. Palladium-Catalyzed Deformylation
Reactions with Detailed Experimental and in Silico Mechanistic Studies
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(11) Almost all Pd(II)-catalyzed C-H activation reactions using a bidentate
directing group proceeded via the formation of Pd(IV) intermediate: (a)
Tremont, S. J.; Rahman, H. U. Ortho-alkylation of acetanilides using
alkyl halides and palladium acetate J. Am. Chem. Soc. 1984, 106, 5759-
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tion catalysis Chem. Sci. 2015, 6, 70-76. See also, ref. 3.
(12) For the results of DFT calculations, see the Supporting information.
(13) (a) Gou, Q.; Deng, Bin.; Qin J. Palladium-Catalyzed Arylation of
(Di)azinyl Aldoxime Ethers by Aryl Iodides: Stereoselective Synthesis
of Unsymmetrical (E)-(Di)azinylaryl Ketoxime Ethers Chem. Eur. J.
2015, 21, 12586-12591. (b) Yu, Y.; Lu, Q.; Chen. G.; Li, C.; Huang, X.
Palladium-Catalyzed Intermolecular Acylation of Aryl Diazoesters with
ortho-Bromobenzaldehydes Angew. Chem. Int. Ed. 2018, 57, 319-323.
(14) Tatamidani, H.; Kakiuchi, F.; Chatani, N. A New Ketone Synthesis by
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boron Compounds Org. Lett. 2004, 6, 3597-3599.
(4) For copper-catalyzed formation of aryl ethers using picolinamide lig-
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J.; McGowan, P. C. Picolinamides as Effective Ligands for Copper-
Catalysed Aryl Ether Formation: Structure–Activity Relationships,
Substrate Scope and Mechanistic Investigations Chem. Eur. J. 2014, 20,
17606-17615.
(5) (a) Dieter, R. K. Reaction of Acyl Chlorides with Organometallic Rea-
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(6) For several examples of the synthesis of ketones from aldehydes, see:
(a) Ishiyama, T.; Hartwig, J. A Heck-Type Reaction Involving Car-
bon−Heteroatom Double Bonds. Rhodium(I)-Catalyzed Coupling of
Aryl Halides with N-Pyrazyl Aldimines J. Am. Chem. Soc. 2000, 122,
12043. (a) Huang, Y.-C.; Majumdar, K. K.; Cheng, C.-H. Nickel-Cata-
lyzed Coupling of Aryl Iodides with Aromatic Aldehydes:ꢀ Chemose-
lective Synthesis of Ketones J. Org. Chem. 2002, 67, 1682-1684. (b)
Pucheault, M.; Darses, S.; Genet, J.-P. Direct Access to Ketones from
Aldehydes via Rhodium-Catalyzed Cross-Coupling Reaction with Po-
tassium Trifluoro(organo)borates J. Am. Chem. Soc. 2004, 126, 15356-
15357. (c) Ruan, J.; Saidi, O.; Iggo, J. A.; Xiao, J. Direct Acylation of
Aryl Bromides with Aldehydes by Palladium Catalysis J. Am. Chem.
Soc. 2008, 130, 10510-10511. (f) Tang, B.-X.; Song, R.-J.; Wu, C.-Y.;
Liu, Y.; Zhou, M.-B.; Wei, W.-T.; Deng, G.-B.; Yin, D.-L.; Li, J.-H.
Copper-Catalyzed Intramolecular C−H Oxidation/Acylation of Formyl-
N-arylformamides Leading to Indoline-2,3-diones J. Am. Chem. Soc.
2010, 132, 8900. (g) Tripathi, S.; Singh, S. N.; Yadav, L. D. S. Metal-
Free Efficient Cross Coupling of Aromatic Aldehydes with Aryldiazo-
nium tetrafluoroborates using DTBP as a Radical Initiator Tetrahedron
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Catalyzed Environmentally Benign Acylation J. Org. Chem. 2016, 81,
6409-6423. (e) Zahng, X.; MacMillan, D. W. C. Direct Aldehyde C–H
Arylation and Alkylation via the Combination of Nickel, Hydrogen
Atom Transfer, and Photoredox Catalysis J. Am. Chem. Soc. 2017, 139,
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