A REVIEW ON DIFLUOROMETHYLATION OF ARYL AND HETEROARYL COMPOUNDS
DOI:
https://doi.org/10.59367/jpcgn797Abstract
The difluoro methylated aryl andheteroaryl compounds are of immense importance in agrochemical and pharmaceutical industry owing to the various properties of difluoro methyl group (CF2H) like weakly acidic nature and capability of hydrogen-bonding interactions that improve the binding selectivity of biologically active compounds and it can act as a more-lipophilic isostere of carbinol, thiol, hydroxamic acid or amide groups.The transition metals in difluoro methylation reactions play various roles, including stabilizing the difluoro methyl anion (as difluoro methyl carriers), promoting the formation of difluoro methyl free radicals (such as transition-metal photo redox catalysts) and facilitating the formation of HF2C-C and HF2C-X bonds (through the reductive elimination of difluoro methyl-metal complexes).This review paper discuss about the various methods that have been reported for difluoro methylation reactions using various transition metals like, copper, palladium, palladium/silver (bimetallic catalyst system), silver, nickel, palladium with platinum, Iridium photo catalyst etc.
References
Aikawa K., Serizawa H., Ishii K., &Mikami K. (2016). Palladium-CatalyzedNegishi Cross-Coupling Reaction of Aryl Halides with (Difluoro methyl) zinc Reagent. Organic Letters, 18(15), 3690–3693.
Bacauanu V., Cardinal S., Yamauchi M., Kondo M., Fernández D. F., Remy R. & MacMillan D. W. C. (2018).MetallaphotoredoxDifluoromethylation of Aryl Bromides. AngewandteChemie - International Edition, 57(38).
Feng Z., Min Q.-Q., Fu X.-P., An L. & Zhang X. (2017). Chlorodifluoromethane-triggered formation of difluoromethylatedarenescatalysed by palladium. Nature Chemistry, 9(9), 918–923.
Feng Z., Min Q. Q. & Zhang X. (2016). Access to DifluoromethylatedArenes by Pd-Catalyzed Reaction of Arylboronic Acids with Bromodifluoroacetate. Organic Letters, 18(1).
Ferguson, D. M., Malapit, C. A., Bour, J. R., & Sanford, M. S. (2019). Palladium-CatalyzedDifluoromethylation of Aryl Chlorides and Bromides with TMSCF2H. Journal of Organic Chemistry, 84(6).
Fier P. S.,&Hartwig J. F. (2012). Copper-mediated difluoro methylation of aryl and vinyl iodides. Journal of the American Chemical Society, 134(12).
Gu Y., Leng X. &Shen Q. (2014). Cooperative dual palladium/silver catalyst for direct difluoro methylation of aryl bromides and iodides. Nature Communications, 5(1), 5405.
Jiang X.-L., Chen Z.-H., Xu X.-H. & Qing F.-L. (2014). Copper-mediated difluoro methylation of electron-poor aryl iodides at room temperature. Organic Chemistry Frontiers, 1(7), 774.
Lu C., Gu Y., Wu J., Gu Y. &Shen Q. (2017). Palladium-catalyzeddifluoromethylation of heteroaryl chlorides, bromides and iodides. Chemical Science, 8(7).
Lu C., Lu H., Wu J., Shen H. C., Hu T., Gu Y. &Shen Q. (2018). Palladium-CatalyzedDifluoromethylation of Aryl Chlorides and Triflates and Its Applications in the Preparation of Difluoromethylated Derivatives of Drug/Agrochemical Molecules. The Journal of Organic Chemistry, 83(2), 1077–1083.
Matheis C., Jouvin K. &Goossen L. J. (2014).SandmeyerDifluoromethylation of (Hetero-)Arenediazonium Salts. Organic Letters, 16(22), 5984–5987.
Mizuta S., Stenhagen I. S. R., O’Duill M., Wolstenhulme J., Kirjavainen A. K., Forsback S. J., Tredwell M., Sandford G., Moore P. R., Huiban M., Luthra S. K., Passchier J., Solin O. &Gouverneur V. (2013). Catalytic decarboxylative fluorination for the synthesis of Tri- and difluoromethylarenes. Organic Letters, 15(11).
Pan F., Boursalian G. B. & Ritter T. (2018). Palladium-CatalyzedDecarbonylativeDifluoromethylation of Acid Chlorides at Room Temperature. AngewandteChemie - International Edition, 57(51).
Rong J., Ni C. & Hu J. (2017). Metal-Catalyzed Direct Difluoro methylation Reactions. In Asian Journal of Organic Chemistry (Vol. 6, Issue 2).
Serizawa H., Ishii K., Aikawa K. &Mikami K. (2016). Copper-CatalyzedDifluoro methylation of Aryl Iodides with (Difluoro methyl) zinc Reagent. Organic Letters, 18(15).
Xu C., Guo W.-H., He X., Guo Y.-L., Zhang X.-Y. & Zhang X. (2018).Difluoromethylation of (hetero) aryl chlorides with chlorodifluoromethanecatalysed by nickel. Nature Communications, 9(1), 1170.
Xu L. &Vicic D. A. (2016). Direct Difluoromethylation of Aryl Halides via Base Metal Catalysis at Room Temperature. Journal of the American Chemical Society, 138(8), 2536–2539.
Xu P., Guo S., Wang L. & Tang P. (2014). Silver-Catalyzed Oxidative Activation of Benzylic C-H Bonds for the Synthesis of DifluoromethylatedArenes. AngewandteChemie International Edition, 53(23).
Xiao Y.-L., Guo W.-H., He G.-Z., Pan Q. & Zhang X. (2014). Nickel-Catalyzed Cross-Coupling of Functionalized Difluoromethyl Bromides and Chlorides with Aryl Boronic Acids: A General Method for DifluoroalkylatedArenes. AngewandteChemie International Edition, 53(37), 9909–9913.
Yerien D. E., Barata-Vallejo S. &Postigo A. (2017).Difluoro methylation Reactions of Organic Compounds. In Chemistry - A European Journal (Vol. 23, Issue 59).
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