Metal-free one-pot oxidative conversion: Molecular Iodine Mediated Oxidation Organic Reactions

Keywords: Aldehyde, alkyne oxidation, halogen, molecular iodine catalysis, ketone ester and carboxylic acid, pyridine-N-oxide

Abstract

Various oxidative compounds such as aldehyde, ketone ester, and acids can be produced in large yields by an effective iodine-mediated oxidative reaction of organic molecules. Molecular iodine is a generally available and commercially extremely inexpensive substance that induces oxidative esterification. With the comparison with different Brønsted acid catalysis, molecular iodine or iodophilic activations proceed  the reaction onto a deoxygenation pathway. With only a few mol% of I2, the oxidation occurs very quickly at room temperature. This approach could also be used to transport different benzil derivatives from nonactivated alkynes, such as diaryl acetylenes. Molecular iodine with several mild reagents such as aq. NH3, ∼30% aq. H2O2 and DMSO might be used to convert various one degree alcohols, particularly benzylic alcohols, into the corresponding aromatic amides in suffiently high yields in a one-pot method. Similarly, by treating different benzylic chloride, bromide and iodide with a molecular iodine oxidation medium, the corresponding aromatic amides may be prepared in a one-pot method. The reactions in this section include transformation of several compounds into their respective oxidative products with the metal-free one-pot oxidative.

References

Iida, S., & Togo, H. (2007). Direct Oxidative Conversion of Alcohols and Amines to Nitriles with Molecular Iodine and DIH in aq. NH3. Tetrahedron. 63: 8274–8281.

Jiang, D., Jia, X., Zhang, S., Zhang, Z., Li, L., & Qiao, Y. (2021). Iodine-Catalyzed Tandem Oxidative Aromatization for the Synthesis of meta-Substituted Alkoxybenzenes. Tetrahedron. 91: 132219.

Kavale, A. C., Kalbandhe, A. H., Opai, I. A., Jichkar, A. A., & Karade, N. N. (2021). Oxidative ring expansion of 3-hydroxy-3-phenacyloxindoles using phenyliodine diacetate and molecular iodine: Synthesis of 2-hydroxy-2-aryl/alkyl-2,3-dihydroquinolin-4(1H)-ones. Tet. Lett. 62: 152631.

Kidwai, M., Bansal,V., & Mothsra, P. (2007). Molecular iodine: A highly efficient catalyst for the synthesis of 7-arylbenzopyrano[1,3]diazepines in non-protic solvents. Journal of Molecular Catalysis A: Chemical. 266: 43–46.

Kim, S.W., Um,T.W., & Shin, S. (2018). Metal-Free Iodine-Catalyzed Oxidation of Ynamides and Diaryl Acetylenes into 1,2-Diketo Compounds. J. Org. Chem. 83(8): 4703–4711.

Luo, W. K., Shi, X., Zhou, W., & Yang L. (2016). Iodine-Catalyzed Oxidative Functionalization of Azaarenes with Benzylic C(sp3)–H Bonds via N-Alkylation/Amidation Cascade: Two-Step Synthesis of Isoindolo[2,1-b]isoquinolin-7(5H)-one. Org. Lett. 18: 2036–2039.

Margarita, S. C., Igor, V. B., Zoya, A. S., Alexander, Y. T., & Tatiana, S. K. (2013). Spectroscopic and structural study of novel interaction product of pyrrolidine-2-thione with molecular iodine. Presumable mechanisms of oxidation. J. Mol. Struc. 1047: 204–208.

Rok, P.L., & Stojan, S. (2014). Aerobic oxidative a-iodination of carbonyl compounds using molecular iodine activated by a nitrate-based catalytic system. Tet. Lett. 55: 5643–5647.

Ryosuke, O., Misato, T., & Hideo, T. (2010). Metal-free one-pot oxidative conversion of benzylic alcohols and benzylic halides into aromatic amides with molecular iodine in aq ammonia, and hydrogen peroxide. Tet. Lett. 51: 4378–4381.

Shantharjun, B., Rajeswari, R., Vani, D., Unnava, R., Sridhar, B., & Reddy, K. R. (2019), Metal-Free, One-Pot Oxidative Triple Functionalization of Azaarenes with Methyl Arenes Mediated by Molecular Iodine/TBHP: Synthesis of N-Benzylated Iodo(iso)quinolinones. Asian J. Org. Chem. 8: 1–11.

Sharma, K. K., Patel, D. I., & Jain, R. (2015), Metal-free synthesis of N-fused heterocyclic iodides via C–H functionalization mediated by tert-butylhydroperoxide. Chem. Commun. 51: 15129–15132.

Sun, K., Lv, Y., Wang, J., Sun, L., Liu, M., Jia, X., Liu, Z., & Li, X.; (2015). Wang, Regioselective, Molecular Iodine-Mediated C3 Iodination of Quinolines. Org. Lett. 17: 4408–4411.

Tang, S. Kun, L., Yue, L., Xinlong, G., Meng, G., & Aiwen, L.; (2015). Iodine-Catalyzed Radical Oxidative Annulation for the Construction of Dihydrofurans and Indolizines. Org. Lett. 17(10): 2404-2407.

Vivek, T. H., & Pradeep, D. L. (2014). A metal-free protocol for direct oxidative de-alkoxycarbonylation of alkyl phenyl acetate by molecular iodine. Tet. Lett. 55: 2337–2339.

Xia, W., Xiao, G., Peng, Z., Yan-dong, W., & An-xin, W. (2017). Iodine-Catalyzed Oxidative Coupling To Construct C−O Bonds for the Synthesis of 2,3-Dihydrooxepines. Org. Lett. 19(17): 4584-4587.

Xianglin, L., Runfa, H., Qiang, L., Yanping, G., Jingqing, L., Xiuwen, C., Zhongzhi, Z., Yubing, H., & Yibiao, L. (2020). Metal-Free Oxidative Esterification of Ketones and Potassium Xanthates: Selective Synthesis of α-Ketoesters and Esters. J. Org. Chem. 85: 5220−5230.

Xu, H., Weng, Y., M., Chen, H., & Zhang, Z. (2020) Unexpected Iodine-Promoted Aerobic Oxidation of α-Cyano-δ-keto Esters: A Facile Synthesis of α,δ-Dicarbonyl Esters. Synthesis. 52: 1841-1846.

Xue, W. J., Gao, Q. H., & Wu, A. X. (2015). Molecular iodine mediated oxidative cross-coupling of sp3 C-H with sp2 C-H: direct synthesis of substituted indolo[2,3-b]carbazoles via formal [2+2+1+1] cyclization. Tet. Lett. 56(51): 7115-7119.

Yadav, V. K., Vishnu, P., Srivastava, L. D., & Yadav, S. (2016). Molecular iodine mediated oxidative coupling of enol acetates with sodium sulfinates leading to β-keto sulfones. Tet. Lett. 57(21): 2236-2238.

Zheng, J. Q., Ying, L., Zhong, J. W., Zhang, Z., Yu, X. D., & Xi, C. W. (2013). Molecular iodine-mediated S–N and C–N cross-coupling and oxidative aromatization of 3,4-dihydropyrimidin-2(1H)-thiones with secondary amines. Tet. Lett. 54: 1884–1887.

Published
2022-04-30
How to Cite
Biswas, S., & Biswas, T. (2022). Metal-free one-pot oxidative conversion: Molecular Iodine Mediated Oxidation Organic Reactions. International Journal of Experimental Research and Review, 27, 45-52. https://doi.org/10.52756/ijerr.2022.v27.005
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Articles