The I2/DMSO pair has emerged as a versatile, efficient, practical, and eco-friendly catalyst system, playing a significant role as a mild oxidative system, and thus employed as a good alternative to metal catalysts in synthetic chemistry. Presently, I2/DMSO is a thriving catalytic system that is used in preparing C-C and C-X (X = O/S/N/Se/Cl/Br) bonds, resulting in the formation of various bioactive molecules. Many processes utilize this system, including in situ glyoxal synthesis by diverse sp, sp2, and sp3 functionalities via iodination and subsequent Kornblum oxidation. Focusing on oxidation processes, this study examines the synergistic effect of dimethyl sulfoxide (DMSO) and molecular iodine in improving synthetic techniques. We provide a comprehensive overview of the research progress on the I2/DMSO catalytic system for the formation of C-C and C-heteroatom bonds from 2018 to the present. Additionally, the future prospects of this research field are discussed.
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