Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Сен. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Язык: Английский

---

Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Green Chemistry, Год журнала: 2024, Номер 26(4), С. 1846 - 1875

Опубликована: Янв. 1, 2024

Organocatalytic enantioselective cross-dehydrogenative coupling reaction provides a great opportunity for the synthesis of highly enantioenriched molecules. In this review, recent progress in field is summarized.

Язык: Английский

---

Iodoarene Activation: Take a Leap Forward toward Green and Sustainable Transformations

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

Constructing chemical bonds under green sustainable conditions has drawn attention from environmental and economic perspectives. The dissociation of (hetero)aryl-halide is a crucial step most arylations affording (hetero)arene derivatives. Herein, we summarize the (hetero)aryl halides activation enabling direct (hetero)arylation trapping reagents construction highly functionalized (hetero)arenes benign conditions. strategies for aryl iodides are classified into (a) hypervalent iodoarene followed by functionalization thermal/photochemical conditions, (b) aryl-I bond in presence bases with/without organic catalysts promoters, (c) photoinduced presence/absence organophotocatalysts, (d) electrochemical direct/indirect electrolysis mediated organocatalysts mediators acting as electron shuttles, (e) electrophotochemical redox-active organocatalysts. These modes result exhibiting diverse reactivity formal cations/radicals/anions aryne precursors. coupling these reactive intermediates with leads to facile selective formation C-C C-heteroatom bonds. ecofriendly, inexpensive, functional group-tolerant offer alternatives transition metal-based catalysis.

Язык: Английский

---

Advances in Catalytic Enantioselective Transformations Using Diaryliodonium Reagents

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3096 - 3115

Опубликована: Фев. 5, 2025

Язык: Английский

---

Halogen Bonds Formed by Halogen’s p/π-Hole in Molecules Help Shape Crystalline Materials

Crystal Growth & Design, Год журнала: 2025, Номер unknown

Опубликована: Апрель 24, 2025

Язык: Английский

---

Iodine(V)-Based Oxidants in Oxidation Reactions

Molecules, Год журнала: 2023, Номер 28(13), С. 5250 - 5250

Опубликована: Июль 6, 2023

The chemistry of hypervalent iodine reagents has now become quite valuable due to the reactivity these compounds under mild reaction conditions and their resemblance in chemical properties transition metals. environmentally friendly nature makes them suitable for Green Chemistry. Reagents with a dual nature, such as iodine(III) reagents, are capable electrophiles, while iodine(V) known strong oxidant behavior. Various including IBX DMP have been used oxidants organic synthesis either stoichiometric or catalytic amounts. In this review article, we describe various oxidation reactions induced by reported past decade.

Язык: Английский

---

Copper-Catalyzed/Hypervalent Iodine-Mediated Functionalization of Unactivated Compounds

Catalysts, Год журнала: 2023, Номер 13(9), С. 1243 - 1243

Опубликована: Авг. 26, 2023

The functionalization of unactivated substrates through the combination copper catalysts and hypervalent iodine reagents represents a versatile tool in organic synthesis to access various classes compounds. derivatives can be used simply as oxidizing agents regenerate catalytic species or they associate starting material. In this review, special attention will paid methodologies which provide introduction nucleophiles into reagent by use suitable benziodoxol(on)es iodonium salts. Many reactions concern C- N-arylations, but may also involve formation different carbon–carbon carbon–nitrogen bonds, carbon–oxygen well carbon–halogen carbon–phosphorus bonds.

Язык: Английский

---

Hypervalent Iodine Compounds in Carbohydrate Chemistry: Glycosylation, Functionalization and Oxidation

Chemistry - A European Journal, Год журнала: 2024, Номер 30(25)

Опубликована: Фев. 13, 2024

Abstract This mini review article provides an overview on the use of hypervalent iodine compounds (HICs) in carbohydrate synthesis, focusing their chemistry and recent applications. HICs are similar to transition metals reactivity but have added benefit being environmentally benign, therefore commonly used as selective oxidants eco‐friendly reagents organic synthesis. Herein, we summarize various synthetic uses reactions such glycosylation, oxidations, functionalization, C−C bond‐forming reactions. The goal this is illustrate advantages versatility using sustainable alternative heavy chemistry.

Язык: Английский

---

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

Beilstein Journal of Organic Chemistry, Год журнала: 2024, Номер 20, С. 2891 - 2920

Опубликована: Ноя. 13, 2024

Diaryliodonium salts have become widely recognized as arylating agents in the last two decades. Both, symmetrical and unsymmetrical forms of these serve effective electrophilic reagents various organic syntheses. The use diaryliodoniums C–C carbon–heteroatom bond formations, particularly under metal-free conditions, has further enhanced popularity reagents. In this review, we concentrate on arylation reactions involving carbon other heteroatoms, encompassing rearrangement absence any metal catalyst, summarize advancements made five years.

Язык: Английский

---

Unraveling Alcohol Additive Effects on Hypervalent Iodine(III)-Catalyzed Asymmetric Phenolic Dearomatization: Ligand Substitution and Low-Barrier Hydrogen Bonds

ACS Catalysis, Год журнала: 2024, Номер 15(1), С. 370 - 380

Опубликована: Дек. 18, 2024

Despite the widespread use of hexafluoropropanol (HFIP) as a "magic" solvent or additive in organic synthesis, its fundamental mechanisms lag far behind. This study presents mechanistic insights into puzzling alcohol effects observed Ishihara's conformationally flexible C2-symmetric iodoarene-catalyzed asymmetric phenolic dearomatization through density functional theory calculations. The results reveal that due to "booster effect" fluorinated alcohols, HFIP assembles trimeric hydrogen bond cluster displaces ligand from active iodine(III) catalyst and forms low-barrier with substrate, which significantly enhances oxidizing power center, thus facilitating electron-deficient phenols. Conversely, methanol is found promote electron-rich phenols via formally similar yet distinct mechanism, highlighting unique role an additive. gained this investigation advance our molecular-level understanding synergistic interactions between catalysts additives, potentially guiding design catalytic systems exploit these for broader applications.

Язык: Английский

---