A Facile and Clean Direct Cyanation of Heteroaromatic Compounds Using a Recyclable Hypervalent Iodine(III) Reagent

Dohi, Toshifumi; Morimoto, Koji; Takenaga, Naoko; Maruyama, Akinobu; Kita, Yasuyuki

doi:10.1248/cpb.54.1608

Cited by 23 publications

(9 citation statements)

References 18 publications

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“…In particular, the practically important reagent, DIB, can be prepared by the direct oxidation of iodobenzene using peracetic acid according to the procedure of Sharefkin and Saltzman . A common procedure for preparing various [bis(acyloxy)iodo]arenes consists of the treatment of substituted iodobenzenes with corresponding peracids; this method is also acceptable for preparing the polymer-supported analogues of DIB from poly(iodostyrene) or aminomethylated poly(iodostyrene), ,− and the ion-supported (diacetoxyiodo)arenes. , Likewise, treatment of various iodoarenes with peroxytrifluoroacetic acid affords the respective [bis(trifluoroacetoxy)iodo]arenes in high yield. − Other oxidants, such as periodates, − chromium(VI) oxide, sodium percarbonate, m -chloroperoxybenzoic acid ( m CPBA), − potassium peroxodisulfate, , H 2 O 2 –urea, Selectfluor, and sodium perborate, can oxidize iodoarenes in the presence of carboxylic acids to give the corresponding [bis(acyloxy)iodo]arenes. For example, oxidation of aryl iodides using sodium perborate (NaBO 3 ) in acetic acid at 40 °C has been used for preparing numerous (diacetoxyiodo)-substituted arenes and heteroarenes, such as N -tosyl-4-(diacetoxyiodo)pyrazole, N -trifluoromethanesulfonyl-4-(diacetoxyiodo)pyrazole, 2-(diacetoxyiodo)thiophene, and 3-(diacetoxyiodo)thiophene. − The chiral (diacetoxyiodo)arene 127 and its derivatives were efficiently prepared by the perborate oxidation of the corresponding aryl iodides (Figure ).…”

Section: Synthetic Applications Of Trivalent Iodine Compoundsmentioning

confidence: 99%

Advances in Synthetic Applications of Hypervalent Iodine Compounds

2016

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The preparation, structure, and chemistry of hypervalent iodine compounds are reviewed with emphasis on their synthetic application. Compounds of iodine possess reactivity similar to that of transition metals, but have the advantage of environmental sustainability and efficient utilization of natural resources. These compounds are widely used in organic synthesis as selective oxidants and environmentally friendly reagents. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various oxidations, rearrangements, aminations, C−C bond-forming reactions, and transition metal-catalyzed reactions are summarized and discussed. Recent discovery of hypervalent catalytic systems and recyclable reagents, and the development of new enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important achievement in the field of hypervalent iodine chemistry. One of the goals of this Review is to attract the attention of the scientific community as to the benefits of using hypervalent iodine compounds as an environmentally sustainable alternative to heavy metals.

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Section: Synthetic Applications Of Trivalent Iodine Compoundsmentioning

confidence: 99%

Advances in Synthetic Applications of Hypervalent Iodine Compounds

2016

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“…The recovered product was re-oxidized back to the respective reagent by reaction with m-chloroperbenzoic acid (m-CPBA). Certain non-polymeric HVI(III) reagents such as 86-89, biphenyl-based HVI(III) reagents 90-93, as well as terphenylbased HVI(III) reagents 94 and 95 have also been synthesized; [54][55][56][57][58][59][60][61][62][63][64][65][66][67][68] their reactivity patterns have already been discussed in previous reviews. 1b,6,7 The structures of these non-polymeric recyclable HVI(III) reagents are shown in Figure 6.…”

Section: Non-polymeric Recyclable Hypervalent Iodine(iii) Reagentsmentioning

confidence: 99%

Recyclable Hypervalent Iodine Reagents in Modern Organic Synthesis

et al. 2022

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Hypervalent iodine (HVI) reagents have gained much attention as versatile oxidants because of their low toxicity, mild reactivity, easy handling, and availability. Despite their unique reactivity and other advantageous properties, stoichiometric HVI reagents are associated with the disadvantage of generating non-recyclable iodoarenes as waste/co-products. To overcome these drawbacks, the syntheses and utilization of various recyclable hypervalent iodine reagents have been established in recent years. This review summarizes the development of various recyclable non-polymeric, polymer-supported, ionic-liquid-supported, and metal–organic framework (MOF)-hybridized HVI reagents.1 Introduction2 Polymer-Supported Hypervalent Iodine Reagents2.1 Polymer-Supported Hypervalent Iodine(III) Reagents2.2 Polymer-Supported Hypervalent Iodine(V) Reagents3 Non-Polymeric Recyclable Hypervalent Iodine Reagents3.1 Non-Polymeric Recyclable Hypervalent Iodine(III) Reagents3.2 Recyclable Non-Polymeric Hypervalent Iodine(V) Reagents3.3 Fluorous Hypervalent Iodine Reagents4 Ionic-Liquid/Ion-Supported Hypervalent Iodine Reagents5 Metal–Organic Framework (MOF)-Hybridized Hypervalent Iodine Reagents6 Conclusion

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“…In this project, we first developed the new recyclable reagents 1 that do not show any degradation of the backbones throughout their reuse and recovery processes. [11][12][13][14][15][16][17] By applying the unique regeneration method of the recyclable reagents 1, we next succeeded in the catalytic use of hypervalent iodine reagents, which led to the effective utilization of the reagents as "organocatalysts." [18][19][20][21] Furthermore, we challenged the asymmetric oxidations as being very difficult with hypervalent iodines and have achieved the highly selective catalytic oxidations of phenols for the first time by designing a new chiral reagent 2Ј.…”

Section: Introductionmentioning

confidence: 99%

Recycling and Catalytic Approaches for the Development of a Rare-Metal-Free Synthetic Method Using Hypervalent Iodine Reagent

Dohi

2010

CHEMICAL & PHARMACEUTICAL BULLETIN

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Oxidation reactions consist of a number of important transformations in organic synthesis. However, in spite of their utility in both laboratory-and industrial-scale production, oxidations are among the most problematic processes regarding the factors of safety, environmental friendliness, operational simplicity, etc. As oxidants, hypervalent iodines, such as phenyliodine(III) diacetate (PIDA) and phenyliodine(III) bis(trifluoroacetate) (PIFA), are among promising reagents for developing environmentally benign oxidation reactions due to their low toxicities, mild reactivity, ready availability, high stability, and easy handling. Our research objective is, largely in consideration of economic and environmental viewpoints, to enhance the synthetic values of these reagents as useful alternatives to highly toxic heavy-metal oxidants and even rare transition metals by pioneering their efficient utilization methods and unique reactivities. During this study, we have succeeded in the development of new recyclable reagents 1 and their catalytic utilization, and the design of a new chiral reagent 2 and its application to perform asymmetric oxidations. Accordingly, the recycling and catalytic use of a hypervalent iodine reagent became possible in many representative types of oxidative bond-forming reactions, some of which even include key transformations for natural product synthesis. A summary of these important achievements in hypervalent iodine chemistry are described in this review.

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A Facile and Clean Direct Cyanation of Heteroaromatic Compounds Using a Recyclable Hypervalent Iodine(III) Reagent

Cited by 23 publications

References 18 publications

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Recyclable Hypervalent Iodine Reagents in Modern Organic Synthesis

Recycling and Catalytic Approaches for the Development of a Rare-Metal-Free Synthetic Method Using Hypervalent Iodine Reagent

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