Convenient Syntheses of Fluorous Aryl Iodides and Hypervalent Iodine Compounds: ArI(L)n Reagents That Are Recoverable by Simple Liquid/Liquid Biphase Workups, and Applications in Oxidations of Hydroquinones

Rocaboy, Christian; Gladysz, J. A.

doi:10.1002/chem.200390034

Cited by 50 publications

(49 citation statements)

References 73 publications

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“…[11] IBA (1) and its derivatives are seldom used in synthesis owing to the decreased reactivity of these reagents as oxidants, especially as hypernucleofuges. [12] Inspired by the increased solubility and reactivity of [bis(trifluoroacetoxy)iodo]pentafluorobenzene [13] and other hypervalent iodine reagents with fluorous side chains, [14] we proposed that fluorination of the arene in the parent 2-iodobenzoic acid should solve many of the problems associated with cyclic iodanes. In this communication, we report what we believe to be the first hypervalent derivatives of 2,3,4,5-tetrafluoro-6-iodobenzoic acid (5) and discuss their structures and reactivities.…”

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confidence: 99%

Tetrafluoro‐IBA and‐IBX: Hypervalent Iodine Reagents

et al. 2007

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Fluorine makes the difference: FIBX (see structure), the tetrafluoro derivative of the hypervalent iodine reagent, is more soluble and has higher reactivity than its nonfluorinated counterpart. An efficient synthesis of FIBX and initial reactions are presented. Some of these reactions can be conducted in standard organic solvents. Owing to the increased reactivity, new transformations and catalytic reactions may be possible.

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confidence: 99%

Tetrafluoro‐IBA and‐IBX: Hypervalent Iodine Reagents

et al. 2007

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“…Results obtained in the present work are also intended to provide further guidelines for the rational design of fluorous-tagged stable nitroxyl radicals and for the development of all-fluorous catalytic systems. In this context, the combination of fluoroustagged TEMPO derivatives with a recyclable fluorous version of BAIB [48] and the use of molecular oxygen as the primary oxidant are worth investigating.…”

Section: Resultsmentioning

confidence: 99%

Selective Oxidation of Alcohols to Carbonyl Compounds Mediated by Fluorous-Tagged TEMPO Radicals

Holczknecht

Cavazzini

Quici

et al. 2005

Advanced Synthesis & Catalysis

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Oxidation of primary, benzylic and secondary alcohols into their corresponding aldehydes and ketones with safe, inexpensive oxidants was achieved in good yields under mild conditions in the presence of catalytic amounts of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radicals bearing perfluoroalkyl substituents. These "fluorous-tagged" TEMPOs were readily isolated from the reaction products by liquid-liquid or solid-phase extraction, considerably simplifying the purification step. Their recyclability was strongly influenced by the nature of the oxidizing system. The best results were obtained using either [bis(acetoxy)iodo]benzene (BAIB) or aqueous NaOCl as the primary oxidants. Fluorous TEMPO 10 could be reused up to six times in the BAIB oxidation of 1-octanol with only minor loss of catalytic activity.

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“…[41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59] Therefore, various types of recyclable hypervalent iodine reagents have been reported. First, the polymer-supported hypervalent iodine reagents, such as poly(diacetoxyiodo) styrene (PDAIS) and poly[bis(trifluoroacetoxyiodo)] styrene (PBTIS), incorporating phenyliodine(III) diacetate (PIDA) and phenyliodine(III) bis(trifluoroacetate) (PIFA) in their polymer backbones were developed.…”

Section: Resultsmentioning

confidence: 99%

“…First, the polymer-supported hypervalent iodine reagents, such as poly(diacetoxyiodo) styrene (PDAIS) and poly[bis(trifluoroacetoxyiodo)] styrene (PBTIS), incorporating phenyliodine(III) diacetate (PIDA) and phenyliodine(III) bis(trifluoroacetate) (PIFA) in their polymer backbones were developed. [41][42][43][44][45][46][47][48] Inspired by this study, other chemists have also reported new recyclable hypervalent iodine compounds having fluorous tags [49][50][51][52] and ionic supports. [53][54][55] We have previously developed a structurally new recyclable hypervalent iodine reagent 1a, namely, 1,3,5,7-tetrakis[4-(diacetoxyiodo) phenyl] adamantane ( Fig.…”

Section: Resultsmentioning

confidence: 99%

Clean Synthesis of N-Pyrrolyl Azoles by Metal-Free Oxidative Cross-Coupling Using Recyclable Hypervalent Iodine Reagent

Ogawa

Koseki

Takahashi

et al. 2015

CHEMICAL & PHARMACEUTICAL BULLETIN

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The facile and clean oxidative coupling reaction of pyrroles with azoles has been achieved using the recyclable hypervalent iodine(III) reagents having adamantane structures. These iodine(III) reagents could be recovered from the reaction mixtures by a simple solid-liquid separation, i.e., filtration, for reuse.Key words oxidative coupling; hypervalent iodine reagent; recycle; pyrrole; azole; C-N bond formationThe N-pyrrolyl azoles are important fragments in the molecules of biological systems or in many pharmaceuticals, insecticides, and functional materials, especially, fluorescent dyes. [1][2][3][4] In spite of this interest, the preparations of N-aryl azoles are severely restricted because the nitrogen heteroaromatics are sometimes not a good substrate to use in the traditional arylation methods such as the Ullmann coupling, [5][6][7][8][9][10][11] since the pyrrole-based metal and halide compounds are sometimes unstable. Katritzky et al. reported the synthesis of pyrrolyl-benzotriazoles by the Mannich condensation of o-phthalaldehyde and 2,5-dimethoxy-2,5-dihydrofuran with primary amines, 12) but this method was not effective for pyrroles, and the desired products were produced only in less than 10% yields. As a new approach, the oxidative C-H bond functionalization strategies of pyrroles [13][14][15][16][17][18][19][20][21][22] might be expected to be an attractive methodology for enabling rapid access to these molecules. Recently, we have developed a new hypervalent iodine-induced oxidative coupling of pyrroles at the N 1 -positions of the azoles. 23) In 2014, Chen and colleagues reported the oxidative coupling method of 1,2,3-triazoles with pyrroles using N-iodosuccinimide (NIS) as an oxidant, in which the reactions preferentially occurred at the N 2 -position of the 1,2,3-triazoles.24) However, these methods produced stoichiometric quantities of iodoarene or succinimide as a waste product after the reaction (Chart 1).Hypervalent iodine reagents have received much attention due to their mild oxidation abilities and low toxicity, easy handling, as alternatives to toxic heavy metal reagents. [25][26][27][28][29][30][31][32] For developing a new coupling for heteroaromatic compounds, we have been engaged in the study of the oxidative C-H bond arylations using hypervalent iodine reagents that utilize the new reactivities of the heteroaromatic iodonium intermediates. [33][34][35][36][37] As mentioned, we developed a hypervalent iodineinduced oxidative coupling of pyrroles at the N 1 -positions of the azoles.23) This new method is versatile in allowing the reactions under metal-free and mild conditions, and tolerates a diverse series of functionalities of the pyrroles and azole coupling partners. We envisioned that a recycling version of this oxidative coupling should become feasible and provide an eco-friendly synthetic method (Chart 2) because a number of recent studies have demonstrated the utility of the recyclable hypervalent iodine reagents. 38-40) Results and DiscussionThe use of recyclable hypervalent ...

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Convenient Syntheses of Fluorous Aryl Iodides and Hypervalent Iodine Compounds: ArI(L)_n Reagents That Are Recoverable by Simple Liquid/Liquid Biphase Workups, and Applications in Oxidations of Hydroquinones

Cited by 50 publications

References 73 publications

Tetrafluoro‐IBA and‐IBX: Hypervalent Iodine Reagents

Tetrafluoro‐IBA and‐IBX: Hypervalent Iodine Reagents

Selective Oxidation of Alcohols to Carbonyl Compounds Mediated by Fluorous-Tagged TEMPO Radicals

Clean Synthesis of <i>N</i>-Pyrrolyl Azoles by Metal-Free Oxidative Cross-Coupling Using Recyclable Hypervalent Iodine Reagent

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