Radical Chlorination with Hypervalent Iodine(III) Generated by Ligand Exchange: Revisiting Palladium(II)-Catalyzed Directed CH Chlorination

2015 ◽  
Vol 4 (2) ◽  
pp. 137-140 ◽  
Author(s):  
Kyungjun Kang ◽  
Suyeon Lee ◽  
Hyunwoo Kim
Keyword(s):  
Ligand Exchange ◽  
Hypervalent Iodine ◽  
Radical Chlorination

Employing exchange reactions involving hypervalent iodine compounds for the direct synthesis of azide-containing linear and branched polymers

2014 ◽  
Vol 5 (12) ◽  
pp. 4599-4609 ◽  
Author(s):  
Hongzhang Han ◽  
Nicolay V. Tsarevsky
Keyword(s):  
Ligand Exchange ◽  
Direct Synthesis ◽  
Branched Polymers ◽  
Hypervalent Iodine ◽  
Exchange Reactions ◽  
One Pot ◽  
Iodine Compounds

Azide-containing polymers were prepared by one-pot polymerizations initiated by azide radicals produced by ligand exchange reactions involving hypervalent iodine(iii) compounds.

scholarly journals [18F]fluoro-benziodoxole: a no-carrier-added electrophilic fluorinating reagent. Rapid, simple radiosynthesis, purification and application for fluorine-18 labelling

2018 ◽  
Vol 54 (34) ◽  
pp. 4286-4289 ◽  
Author(s):  
Miguel A. Cortés González ◽  
Patrik Nordeman ◽  
Antonio Bermejo Gómez ◽  
Denise N. Meyer ◽  
Gunnar Antoni ◽  
...  
Keyword(s):  
Ligand Exchange ◽  
Hypervalent Iodine ◽  
No Carrier Added

An electrophilic 18F transfer reagent was synthetized by rapid, operationally simple ligand exchange from a hypervalent iodine and [18F]TBAF.

Diaryliodonium Salts: Structures and Synthesis

2020 ◽  
Vol 24 (18) ◽  
pp. 2070-2105
Author(s):  
Yu Wang ◽  
Guoqiang An ◽  
Limin Wang ◽  
Jianwei Han
Keyword(s):  
Organic Synthesis ◽  
Ligand Exchange ◽  
Hypervalent Iodine ◽  
Ligand Exchange Reaction ◽  
Elementary Reactions ◽  
Organometallic Reagents ◽  
Diaryliodonium Salts ◽  
Synthetic Utility ◽  
Electrophilic Reagents ◽  
Target Molecules

Due to similar reactivity in comparison with aromatic organometallic reagents, diaryliodonium salts are currently in broad usage as less toxic, highly efficient, stable and mild electrophilic reagents in organic synthesis. The hypervalent iodine center of diaryliodonium salts can lead to unique reactivity, which thus is frequently presented in metal-free arylations or metal-involved elementary reactions such as oxidative addition, reduction elimination, ligand coupling and ligand exchange reaction. As such, diaryliodonium salts have experienced explosive growth by transferring aromatics to the target molecules. In contrast to the reviews on the synthetic utility or aryl transformations by using diaryliodonium salts, this review provides a summary of their structures and the synthetic strategies towards them during recent decades.

Hypervalent iodine-based dynamic and self-healing network polymers

2019 ◽  
Vol 10 (29) ◽  
pp. 3943-3950 ◽  
Author(s):  
Avichal Vaish ◽  
Nicolay V. Tsarevsky
Keyword(s):  
Ligand Exchange ◽  
Uv Light ◽  
Hypervalent Iodine ◽  
Self Healing ◽  
Linear Polymers ◽  
Exchange Reactions ◽  
Network Polymers ◽  
Radical Coupling

Linear polymers with carboxylate pendant groups participate in ligand-exchange reactions with (diacetoxyiodo)benzene to afford dynamic and self-healing networks, which become set when exposed to UV light or heat due to irreversible radical coupling.

Separation of fudosteine on an achiral C18column by HPLC with chiral ligand-exchange selectors as mobile phase additives

2008 ◽  
Vol 20 (4) ◽  
pp. 585-594 ◽  
Author(s):  
J. Ma ◽  
J. Cao ◽  
M. J. Ding ◽  
L. H. Yuan ◽  
M. J. Zhai ◽  
...  
Keyword(s):  
Ligand Exchange ◽  
Mobile Phase ◽  
Chiral Ligand ◽  
Mobile Phase Additives ◽  
Chiral Ligand Exchange

Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazole-2-ylidene Ligands

2020 ◽  
Author(s):  
Matthew Stout ◽  
Brian Skelton ◽  
Alexandre N. Sobolev ◽  
Paolo Raiteri ◽  
Massimiliano Massi ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Ligand Exchange ◽  
Ligand Substitution ◽  
Bidentate Ligand ◽  
The Other ◽  
Ligand Exchange Reaction ◽  
Multiple Products ◽  
Ligand Charge Transfer ◽  
Photochemical Properties

<p>Three Re(I) tricarbonyl complexes, with general formulation Re(N^L)(CO)<sub>3</sub>X (where N^L is a bidentate ligand containing a pyridine functionalized in the position 2 with a thione or a thiazol-2-ylidene group and X is either chloro or bromo) were synthesized and their reactivity explored in terms of solvent-dependent ligand substitution, both in the ground and excited states. When dissolved in acetonitrile, the complexes bound to the thione ligand underwent ligand exchange with the solvent resulting in the formation of Re(NCMe)<sub>2</sub>(CO)<sub>3</sub>X. The exchange was found to be reversible, and the starting complex was reformed upon removal of the solvent. On the other hand, the complexes appeared inert in dichloromethane or acetone. Conversely, the complex bound to the thiazole-2-ylidene ligand did not display any ligand exchange reaction in the dark, but underwent photoactivated ligand substitution when excited to its lowest metal-to-ligand charge transfer manifold. Photolysis of this complex in acetonitrile generated multiple products, including Re(I) tricarbonyl and dicarbonyl solvato-complexes as well as free thiazole-2-ylidene ligand.</p>

Oxidase Catalysis via an Aerobically Generated Dess-Martin Periodinane Analogue

2018 ◽  
Author(s):  
Asim Maity ◽  
Sung-Min Hyun ◽  
Alan Wortman ◽  
David Powers
Keyword(s):  
Chemical Synthesis ◽  
Aerobic Oxidation ◽  
Substrate Oxidation ◽  
Oxidation Catalysis ◽  
Hypervalent Iodine ◽  
Oxidation Reactions ◽  
Broad Array ◽  
Oxidation Chemistry ◽  
Reactive Oxidants

<p>Hypervalent iodine(V) reagents, such as Dess-Martin periodinane (DMP) and 2-iodoxybenzoic acid (IBX), are broadly useful oxidants in chemical synthesis. Development of strategies to access these reagents from O2 would immediately enable use of O2 as a terminal oxidant in a broad array of substrate oxidation reactions. Recently we disclosed the aerobic synthesis of I(III) reagents by intercepting reactive oxidants generated during aldehyde autoxidation. Here, we couple aerobic oxidation of iodobenzenes with disproportionation of the initially generated I(III) compounds to generate I(V) reagents. The aerobically generated I(V) reagents exhibit substrate oxidation chemistry analogous to that of DMP. Further, the developed aerobic generation of I(V) has enabled the first application of I(V) intermediates in aerobic oxidation catalysis.</p>

Regioselective C3-H Trifluoromethylation of 2H-Indazole Under Transition-Metal-Free Photoredox Catalysis

2019 ◽  
Author(s):  
Arumugavel Murugan ◽  
Venkata Nagarjuna Babu ◽  
Nagaraj Sabarinathan ◽  
Sharada Duddu. S
Keyword(s):  
Transition Metal ◽  
Visible Light ◽  
Practical Approach ◽  
Hypervalent Iodine ◽  
Radical Mechanism ◽  
Photoredox Catalysis ◽  
Metal Free

Here we report a visible-light-promoted metal-free regioselective C3-H trifluoromehtylation reaction that proceeds via radical mechanism and which supported by control experiments. The combination of photoredox catalysis and hypervalent iodine reagent provides a practical approach for the present trifluoromethylation reaction and synthesis of a library of trifluoromethylated indazoles.

Electrochemical Vicinal Difluorination of Alkenes: Sustainable, Scalable, and Amenable to Electron-rich Substrates

2019 ◽  
Author(s):  
Sayad Doobary ◽  
Alexi Sedikides ◽  
Henry caldora ◽  
Darren poole ◽  
Alastair Lennox
Keyword(s):  
Bioactive Compounds ◽  
Hypervalent Iodine ◽  
Electrochemical Generation ◽  
Oxidative Decomposition ◽  
Alkyl Groups ◽  
Rich Functionality

Fluorinated alkyl groups are important motifs in bioactive compounds, positively influencing pharmacokinetics, potency and F conformation. The oxidative difluorination of alkenes represents an H important strategy for their preparation, yet current methods are limited in their alkene-types and tolerance of electron-rich, readily oxidized functionalities, as well as in their scalability. Herein, we report a method for the difluorination of a number of unactivated alkene-types that is tolerant of electron-rich functionality, giving products that are otherwise unattainable. Key to success is the electrochemical generation of a hypervalent iodine mediator (in the presence of nucleophilic fluoride and HFIP) using an ‘ex-cell’ approach, which avoids the oxidative decomposition of the substrate. The more sustainable conditions give good to excellent yields of product in up to decagram scales<br>

Recent Computational Studies on Mechanisms of Hypervalent Iodine(III)-Promoted Dearomatization of Phenols

2020 ◽  
Vol 24 (18) ◽  
pp. 2106-2117
Author(s):  
Hanliang Zheng ◽  
Xiao-Song Xue
Keyword(s):  
Hypervalent Iodine ◽  
Computational Studies ◽  
Mechanistic Studies

Hypervalent iodine-promoted dearomatization of phenols has received intense attention. This mini-review summarizes recent computational mechanistic studies of phenolic dearomatizations promoted by hypervalent iodine(III) reagents or catalysts. The first part of this review describes mechanisms of racemic dearomatization of phenols, paying special attention to the associative and dissociative pathways. The second part focuses on mechanisms and selectivities of diastereo- or enantio-selective dearomatization of phenols.

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