Reactant cum solvent water: generation of transient λ<sup>3</sup>-hypervalent iodine, its reactivity, mechanism and broad application

Khamarui, Saikat; Maiti, Rituparna; Mondal, Ramij R.; Maiti, Dilip K.

doi:10.1039/c5ra21932a

Cited by 8 publications

(6 citation statements)

References 87 publications

(10 reference statements)

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“…ATR‐MIR spectroscopy disclosed the formation of unknown intermediates in the reaction. NMR and labelling ( 2 H and 18 O) experiments supported the DFT‐IR predicted reaction pathway such as cleavage of triple bond, amination and amidation to afford desired amide [75] …”

Section: Coupling Reactionsmentioning

confidence: 77%

“…NMR and labelling ( 2 H and 18 O) experiments supported the DFT-IR predicted reaction pathway such as cleavage of triple bond, amination and amidation to afford desired amide. [75] In 2017, Mehra et al reported an efficient methodology for regioselective synthesis of N-arylquinolones by using easily available DAIS and quinolones in aqueous medium under metal and ligand-free conditions. Electron donating group (EDG) as well as electron withdrawing group (EWG) substituted DAIS resulted in the formation of the desired products in good to excellent yields (42-91%).…”

Section: Cà N Couplingmentioning

confidence: 99%

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Aqueous Mediated Reactions Involving Hypervalent Iodine Reagents

et al. 2022

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Several reactions mended by hypervalent iodine reagents have been developed in aqueous media recently. The evolution of reactions using hypervalent iodine reagents in aqueous medium is one of the most vital fields in organic synthesis to achieve one of the requirements of green chemistry. Hypervalent iodine reagents have the potential to replace toxic metals in numerous chemical reactions viz. oxidation reactions, coupling reactions, α-functionaliztion reactions, cyclization reactions and halogenations reactions etc. due to their stability, high selectivity, easy and simple experimentation, less toxic nature. In a chemical reaction solvents are required for several functions viz. in extractions, reactants solubility, washing and separation of final products. Water as a medium represents a safe, non-toxic, inexpensive and environmentally friendly alternative to toxic organic solvents for various organic reactions. The evolution of hypervalent iodine reagents with modified reactivities in aqueous phase now enable such chemical reactions which were thought to be illogical only a century ago. Therefore, in the present review, we summarize the various aqueous mediated reactions involving hypervalent iodine reagents.

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Section: Coupling Reactionsmentioning

confidence: 77%

Section: Cà N Couplingmentioning

confidence: 99%

Aqueous Mediated Reactions Involving Hypervalent Iodine Reagents

et al. 2022

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“…The reaction between 2‐(phenylethynyl)benzoic acid and benzyl amine using Bu 4 N+ OAc‐ as a catalytic system in an aqueous medium, under microwave irradiation gave regioselectivelly 3‐hydroxyisoindolinones 164 (Table 6, entry 6) [237] . Benzylisoindoline‐1,3‐diones 165 can be prepared in good yields by the reaction of ortho ‐alkynylbenzaldehydes with primary amines in the presence of hypervalent iodine and sodium bicarbonate (Table 6, entry 7) [238] . When the terminal position of alkyne moiety of the ortho ‐alkynylbenzaldehydes are functionalized with ketones, isoindolinones 166 were obtained in yields ranging from 43 to 95% (Table 6, entry 8) [239] .…”

Section: Synthesis Of Isoindolinesmentioning

confidence: 99%

“…[237] Benzylisoindoline-1,3-diones 165 can be prepared in good yields by the reaction of ortho-alkynylbenzaldehydes with primary amines in the presence of hypervalent iodine and sodium bicarbonate (Table 6, entry 7). [238] When the terminal position of alkyne moiety of the ortho-alkynylbenzaldehydes are functionalized with ketones, isoindolinones 166 were obtained in yields ranging from 43 to 95% (Table 6, entry 8). [239] Hydroxylamine in THF at room temperature was utilized to promote the cyclization of ortho-alkynylbenzaldehydes leading to the synthesis of N-hydroxy-isoindolinones 167 (Table 6, entry 9).…”

Section: Transition Metal-free Synthesis Of Isoindolinesmentioning

confidence: 99%

Recent Developments in the Cyclization of Alkynes and Nitrogen Compounds for the Synthesis of Indole Derivatives

Neto

Zeni

2021

Asian J Org Chem

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This review is intended to highlight the most useful approaches for the synthesis of indole derivatives (azaindoles, carbazoles, carbolines, indazoles, 3H-indoles, indolines, indolizines, isoindoles, and isoindolines), which were described by using transition-metal catalyzed cyclization reactions of alkynes and nitrogen compounds. The methodologies carried out under metal-free conditions will also be illustrated herein. This review will cover the data published mostly in the past decade. Synthesis of 6-AzaindolesAzaindoles, although rare in nature, have attracted a significant attention because some synthetic structures containing this nucleus exhibit biological activities. [17] The synthetic methods describing the preparation of azaindoles are limited. Usually their synthesis was achieved from the cyclization reaction of substrates containing aminopyridines. [18] Transition Metal-Free Synthesis of 6-AzaindolesWe have nominated two methodologies for the preparation of 6-azaindoles, which were developed using alkynes and nitrogen compounds in a metal-free protocol. In the first, an electrophilic cyclization condition, using iodine as an electrophilic source, was applied to 2-(azidomethyl)-3-alkynyl-pyrroles in the preparation of 4-iodo-6-azaindoles 1 (Scheme 1, eq 1). [19] The second approach described the preparation of 2,5-disubstituted 6azaindoles 2 from base-catalyzed intramolecular cyclization of 2-(azidomethyl)-3-alkynyl-pyrroles (Scheme 1, eq 2). [20] 3. Synthesis of 7-Azaindoles Transition Metal-Catalyzed Synthesis of 7-Azaindoles Silver-Catalyzed Synthesis of 7-AzaindolesSilver-catalyzed cyclization reactions of alkynes constitute powerful strategies for the construction of heterocycles. In particular, the 7-azaindoles could be obtained by these approaches. A general method for the preparation of aryl-[a] Dr. J.

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“…Synthetic organic chemists are involved in a continuous effort to reveal the excellent Lewis acidic oxidizing characteristics of these reagents from the last decade of the 20 th century to recent years. These reagents led to rapid development in the modern field of C–C/C–X (X = O, N, halogens) coupling and cyclization reactions . Some chiral hypervalent iodine reagents were also in the limelight for asymmetric synthesis .…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Iodosobenzene‐Mediated Construction of Heterocyclic Scaffolds: Transition‐Metal‐Free Approaches and Scope

et al. 2017

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Iodosobenzene (PhIO) is a well‐known hypervalent iodine reagent for its Lewis acidic oxidizing capability. In recent times it has been repeatedly proven to be a powerful tool for the development of toxic, costly transition‐metal‐free advanced and impressive methodologies to construct diverse array of different heterocycles. In this review some selected viable and innovative strategies from 2007 to 2016 have been contemplated. Sometimes mechanistic proposals were also taken as prime consideration since synthetic organic chemists are providing fresh stimuli to reinforce the theoretical predictions to grasp the unique nature of PhIO in dissimilar conditions. Convenient and environmentally friendly cyclization and cycloaddition protocols were delineated adequately to integrate the practical findings and mechanistic points of view.

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Reactant cum solvent water: generation of transient λ³-hypervalent iodine, its reactivity, mechanism and broad application

Abstract: We have demonstrated a benign strategy for amides, imides and their chiral analogues using water as a source of carbonyl oxygen and medium. DFT-MIR studies and controlled experiments established the mechanism involving PhI(OH)2-bearing intermediates.

Cited by 8 publications

References 87 publications

Aqueous Mediated Reactions Involving Hypervalent Iodine Reagents

Aqueous Mediated Reactions Involving Hypervalent Iodine Reagents

Recent Developments in the Cyclization of Alkynes and Nitrogen Compounds for the Synthesis of Indole Derivatives

Recent Advances in Iodosobenzene‐Mediated Construction of Heterocyclic Scaffolds: Transition‐Metal‐Free Approaches and Scope

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Reactant cum solvent water: generation of transient λ3-hypervalent iodine, its reactivity, mechanism and broad application

Abstract: We have demonstrated a benign strategy for amides, imides and their chiral analogues using water as a source of carbonyl oxygen and medium. DFT-MIR studies and controlled experiments established the mechanism involving PhI(OH)2-bearing intermediates.

Cited by 8 publications

References 87 publications

Aqueous Mediated Reactions Involving Hypervalent Iodine Reagents

Aqueous Mediated Reactions Involving Hypervalent Iodine Reagents

Recent Developments in the Cyclization of Alkynes and Nitrogen Compounds for the Synthesis of Indole Derivatives

Recent Advances in Iodosobenzene‐Mediated Construction of Heterocyclic Scaffolds: Transition‐Metal‐Free Approaches and Scope

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Reactant cum solvent water: generation of transient λ³-hypervalent iodine, its reactivity, mechanism and broad application