The aryl iodine-catalyzed organic transformation via hypervalent iodine species generated in situ

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Xuemin Li ◽  
Guangchen Li ◽  
Yifu Cheng ◽  
Yunfei Du
Keyword(s):  
Organic Synthesis ◽  
Oxidative Coupling ◽  
Hypervalent Iodine ◽  
Organic Transformations ◽  
Aryl Iodide ◽  
Oxidative Reaction ◽  
Iodine Species ◽  
Iodine Chemistry

Abstract The application of hypervalent iodine species generated in situ in organic transformations has emerged as a useful and powerful tool in organic synthesis, allowing for the construction of a series of bond formats via oxidative coupling. Among these transformations, the catalytic aryl iodide can be oxidized to hypervalent iodine species, which then undergoes oxidative reaction with the substrates and the aryl iodine regenerated again once the first cyclic cycle of the reaction is completed. This review aims to systematically summarize and discuss the main progress in the application of in situ-generated hypervalent iodine species, providing references and highlights for synthetic chemists who might be interested in this field of hypervalent iodine chemistry.

A Concise Review of Hypervalent Iodine with Special Reference to Dess- Martin Periodinane

2020 ◽  
Vol 17 (8) ◽  
pp. 946-957
Author(s):  
Ravindra V. Kupwade
Keyword(s):  
Organic Synthesis ◽  
Oxidative Coupling ◽  
Carbonyl Compounds ◽  
Hypervalent Iodine ◽  
Organic Transformations ◽  
Oxidative Functionalization ◽  
The Past ◽  
Concise Review ◽  
Iodine Compounds ◽  
Related Compounds

The chemistry of hypervalent iodine compounds has been experiencing considerable attention of organic chemists during the past few years. Hypervalent iodine reagents have found ubiquitous applications in organic synthesis because of their mild and highly chemoselective oxidizing properties, easy commercial availability, and environmental benign character. Along with oxidation of alcohol, they have also shown to be useful in number of organic transformations which include oxidative functionalization of carbonyl compounds, catalytic imidations, cyclization, oxidative coupling of phenols, amines and related compounds. Among various hypervalent iodine reagents, iodine-V compounds (λ5-iodanes) have attracted much attention in recent years. This review narrates the particular advances in iodine (V) reagents with special emphasis on the use of DMP in organic transformations.

Synthesis of Oxazoline and Oxazole Derivatives by Hypervalent-Iodine-Mediated Oxidative Cycloaddition Reactions

Synthesis ◽  
2020 ◽  
Vol 52 (16) ◽  
pp. 2299-2310 ◽  
Author(s):  
Akira Yoshimura ◽  
Akio Saito ◽  
Viktor V. Zhdankin ◽  
Mekhman S. Yusubov
Keyword(s):  
Heterocyclic Compounds ◽  
Short Review ◽  
Active Species ◽  
Hypervalent Iodine ◽  
Cycloaddition Reactions ◽  
Iodine Species ◽  
Oxazole Derivatives

Organohypervalent iodine reagents are widely used for the preparation of various oxazolines, oxazoles, isoxazolines, and isoxazoles. In the formation of these heterocyclic compounds, hypervalent iodine species can serve as the activating reagents for various substrates, as well as the heteroatom donor reagents. In recent research, both chemical and electrochemical approaches toward generation of hypervalent iodine species have been utilized. The in situ generated active species can react with appropriate substrates to give the corresponding heterocyclic products. In this short review, we summarize the hypervalent-iodine­-mediated preparation of oxazolines, oxazoles, isoxazolines, and isoxazoles starting from various substrates.1 Introduction2 Synthesis of Oxazolines3 Synthesis of Oxazoles4 Synthesis of Isoxazolines5 Synthesis of Isoxazoles6 Conclusion

scholarly journals Selective benzylic C–H monooxygenation mediated by iodine oxides

2019 ◽  
Vol 15 ◽  
pp. 602-609
Author(s):  
Kelsey B LaMartina ◽  
Haley K Kuck ◽  
Linda S Oglesbee ◽  
Asma Al-Odaini ◽  
Nicholas C Boaz
Keyword(s):  
Selective Oxidation ◽  
High Yield ◽  
Hypervalent Iodine ◽  
Iodine Species ◽  
Mechanistic Analysis ◽  
Substrate Tolerance ◽  
Iodine Oxides ◽  
Moderate Yield

A method for the selective monooxdiation of secondary benzylic C–H bonds is described using an N-oxyl catalyst and a hypervalent iodine species as a terminal oxidant. Combinations of ammonium iodate and catalytic N-hydroxyphthalimide (NHPI) were shown to be effective in the selective oxidation of n-butylbenzene directly to 1-phenylbutyl acetate in high yield (86%). This method shows moderate substrate tolerance in the oxygenation of substrates containing secondary benzylic C–H bonds, yielding the corresponding benzylic acetates in good to moderate yield. Tertiary benzylic C–H bonds were shown to be unreactive under similar conditions, despite the weaker C–H bond. A preliminary mechanistic analysis suggests that this NHPI-iodate system is functioning by a radical-based mechanism where iodine generated in situ captures formed benzylic radicals. The benzylic iodide intermediate then solvolyzes to yield the product ester.

Hofmann Rearrangement of Carboxamides Mediated by Hypervalent Iodine Species Generated in Situ from Iodobenzene and Oxone: Reaction Scope and Limitations

2010 ◽  
Vol 12 (20) ◽  
pp. 4644-4647 ◽  
Author(s):  
Aleksandra A. Zagulyaeva ◽  
Christopher T. Banek ◽  
Mekhman S. Yusubov ◽  
Viktor V. Zhdankin
Keyword(s):  
Hypervalent Iodine ◽  
Hofmann Rearrangement ◽  
Iodine Species

New synthesis of spirocycles by utilizing in situ forming hypervalent iodine species

2011 ◽  
Vol 9 (20) ◽  
pp. 6899 ◽  
Author(s):  
Toshifumi Dohi ◽  
Tomofumi Nakae ◽  
Yohei Ishikado ◽  
Daishi Kato ◽  
Yasuyuki Kita
Keyword(s):  
Hypervalent Iodine ◽  
Iodine Species ◽  
In Situ Forming ◽  
New Synthesis

A Triazole-Substituted Aryl Iodide with Omnipotent Reactivity in Enantioselective Oxidative Couplings

2019 ◽  
Author(s):  
Ayham Abazid ◽  
Boris Nachtsheim
Keyword(s):  
Dft Calculations ◽  
Oxidative Coupling ◽  
Coupling Reactions ◽  
Efficient Catalyst ◽  
Aryl Iodide ◽  
Oxidative Coupling Reactions

A triazole-substituted chiral aryl iodide is described as an efficient catalyst for a variety of diverse oxidative coupling reactions such as the Kita-spirocyclization, phenol-dearomatizations, alpha-oxygenations and oxidative rearrangements. Structures of the in situ oxidized hydroxy(tosyloxy)iodoarenes are discussed based on DFT-calculations.<br>

ChemInform Abstract: New Synthesis of Spirocycles by Utilizing in situ Forming Hypervalent Iodine Species.

ChemInform ◽  
2012 ◽  
Vol 43 (12) ◽  
pp. no-no
Author(s):  
Toshifumi Dohi ◽  
Tomofumi Nakae ◽  
Yohei Ishikado ◽  
Daishi Kato ◽  
Yasuyuki Kita
Keyword(s):  
Hypervalent Iodine ◽  
Iodine Species ◽  
In Situ Forming ◽  
New Synthesis

An I(I)/I(III) Catalysis Route to the Heptafluoroisopropyl Group: A Privileged Module in Contemporary Agrochemistry

Synthesis ◽  
2021 ◽  
Author(s):  
Victor Martín-Heras ◽  
Constantin G. Daniliuc ◽  
Ryan Gilmour
Keyword(s):  
Functional Groups ◽  
Hypervalent Iodine ◽  
Aryl Ring ◽  
Iodine Species ◽  
Single Operation ◽  
Group A ◽  
Molecule Design ◽  
In Situ Generation

The heptafluoroisopropyl group is emerging as a privileged chemotype in contemporary agrochemistry and features prominently in the current portfolio of leading insecticides. To reconcile the expansive potential of this module with the synthetic challenges associated with preparing crowded, fluorinated motifs, I(I)/I(III) catalysis has been leveraged. Predicated on in situ generation of p-TolIF2, this route enables the direct difluorination of α-trifluoromethyl-β-difluoro-styrenes in a single operation. This formal addition of fluorine across the alkene π-bond is efficient (up to 91%) and is compatible with a broad range of functional groups. The ArCF(CF3)2 moiety is conformationally pre-organized, with the C(sp3)-F bond co-planar to the framework of the aryl ring, thereby minimizing 1,3-allylic strain. Moreover, orthogonal multipolar C-F•••C=O interactions have been identified in a phathalimide derivative. It is envisaged that this programmed vicinal difluorination enabled by a hypervalent iodine species will find application in functional molecule design in a broader sense.

scholarly journals Reactions Promoted by Hypervalent Iodine Reagents and Boron Lewis Acids

2021 ◽  
Author(s):  
Ayan Dasgupta ◽  
Christian Thiehoff ◽  
Paul David Newman ◽  
Thomas Wirth ◽  
Rebecca Melen
Keyword(s):  
Organic Synthesis ◽  
Lewis Acids ◽  
Hypervalent Iodine ◽  
Iodine Chemistry

Understanding the role of boranes in hypervalent iodine chemistry will open up new reactivities which can be utilised in organic synthesis. Due to similar reactivities, λ3-iodanes have presented themselves as...

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