Hypervalent iodine-mediated synthesis and late-stage functionalization of heterocycles

Abstract

Hypervalent iodine chemistry has witnessed exponential growth in organic synthesis in recent times. Because of the electrophilic and good-leaving nature of hypervalent iodine reagents, they react with different nucleophiles in various synthetic transformations such as rearrangements, α-functionalization of carbonyl compounds, alkene difunctionalization and oxidation reactions. Importantly, the application of hypervalent iodine reagents in the construction of heterocycles is of great interest and has been well studied over the years. This review article highlights the recent developments accomplished by hypervalent iodine reagents in the synthesis and functionalization of heterocyclic compounds.

Palladium-Catalyzed Organic Reactions Involving Hypervalent Iodine Reagents

“…Various scientific papers, book chapters, and review articles have been published on the chemistry of hypervalent iodine. [10][11][12][13][14][15][16][17][18]. The functionalization of carbonyl compounds [19,20], cyclization [21][22][23][24], oxidative rearrangements [25][26][27], alkene difunctionalizations [28][29][30][31], and atom-transfer reactions [32], in the presence of hypervalent iodine compounds as reagents or catalysts, is now well established.…”

Aqueous Mediated Reactions Involving Hypervalent Iodine Reagents

“…However, in contrast to precious metals, iodine is relatively low‐cost element with annual production of about 30,000 tons mainly in Chile and Japan with an estimated world's total reserves of 15 million metric tons [40] . Hypervalent iodine reagents are widely employed in numerous organic transformations because of their commercial availability, lenient and chemoselective oxidising nature, easy handling and experimental procedure, ecologically benign and non‐hazardous nature [41–43] . Hypervalent iodine bond has lower dissociation energy due to which corresponding free radicals are readily generated by these reagents through homolytic fission [44] .…”

Introduction to hypervalent iodine chemistry. Part 3

“…Specific topics of these papers include the following: theoretical and computational studies of HI compounds, [2][3][4] structural studies, 5 development of new synthetic approaches to HI reagents, [6][7][8][9] photochemical reactions involving HI chemistry, 10,11 industrial applications of hypervalent polyiodides, 12 and numerous synthetic applications of HI reagents. [13][14][15][16][17][18][19][20] Part 3 of the HI series will be published in 2022 covering all topics of iodine chemistry involving hypervalent species and halogen bonding.…”

“…1 Since then, just in two years, between winter 2020 and spring 2022, about 60 major reviews dedicated to different aspects of HI chemistry have been published. [10][11][12]15,18,19, Very recently, in spring 2022, an excellent, comprehensive book "Iodine Catalysis in Organic Synthesis" edited by Ishihara and Muñiz and covering the dynamic area of hypervalent iodine catalysis was published. 62 The development of highly efficient, enantioselective molecular catalysts based on the unique redox and photoredox chemistry of iodine has been one of the most impressive recent achievements in the field of HI chemistry.…”

“…47,57 Applications of iodine(III) reagents in the synthesis of heterocycles was summarized in numerous reviews. 15,44,45,49,51,53,56 The HI based methodologies have found wide application in the synthesis of natural products. 25,41,44,48 Several recent reviews have been dedicated to synthetic applications of specific classes of hypervalent iodine compounds.…”