Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Сен. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Язык: Английский

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Recent progress in alkynylation with hypervalent iodine reagents

Chemical Communications, Год журнала: 2023, Номер 59(12), С. 1589 - 1604

Опубликована: Янв. 1, 2023

Although alkynes are one of the smallest functional groups, they among most versatile building blocks for organic chemistry, with applications ranging from biochemistry to material sciences. Alkynylation reactions have traditionally relied on use acetylenes as nucleophiles. The discovery and development ethynyl hypervalent iodine reagents allowed greatly expand transfer electrophilic synthons. In this feature article progress in field since 2018 will be presented. After a short introduction alkynylation reagents, developments synthesis alkynyl discussed. Their recent base-mediated transition-metal catalyzed alkynylations described. Progress radical-based atom-economical transformations then

Язык: Английский

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Regioselective Difunctionalization and Annulation of Ynamide

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Апрель 8, 2023

Abstract The use of ynamides in organic synthesis has gained significant attention due to their ability provide access complex molecular structures through transformations such as 1,2‐difunctionalization and annulation reactions. These reactions enable the formation highly functionalized N‐bearing olefins unusual heterocycles. In this minireview, we present a systematic overview regioselective difunctionalization ynamides. We discuss multi‐component reactions, radical‐triggered functionalizations across carbon–carbon multiple bonds bifunctional reagents ynamides, highlighting potential expanding substrate scope. Furthermore, insights into mechanistic breakthroughs that have been achieved recent years development these Finally, emphasize promising future prospects versatile building blocks for architectures.

Язык: Английский

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Aryl-, Akynyl-, and Alkenylbenziodoxoles: Synthesis and Synthetic Applications

Molecules, Год журнала: 2023, Номер 28(5), С. 2136 - 2136

Опубликована: Фев. 24, 2023

Hypervalent iodine reagents are in high current demand due to their exceptional reactivity oxidative transformations, as well diverse umpolung functionalization reactions. Cyclic hypervalent compounds, known under the general name of benziodoxoles, possess improved thermal stability and synthetic versatility comparison with acyclic analogs. Aryl-, alkenyl-, alkynylbenziodoxoles have recently received wide applications efficient for direct arylation, alkenylation, alkynylation mild reaction conditions, including transition metal-free conditions photoredox metal catalysis. Using these reagents, a plethora valuable, hard-to-reach, structurally complex products can be synthesized by convenient procedures. The review covers main aspects chemistry benziodoxole-based aryl-, alkynyl-, alkenyl- transfer preparation applications.

Язык: Английский

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Organohypervalent heterocycles

Chemical Society Reviews, Год журнала: 2024, Номер 53(9), С. 4786 - 4827

Опубликована: Янв. 1, 2024

This review summarizes structural and synthetic aspects of heterocyclic molecules incorporating an atom a hypervalent main-group element. The higher thermal stability heterocycles, as compared to their acyclic analogs, adds special feature chemistry.

Язык: Английский

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Light-mediated sulfonyl-iodination of ynamides and internal alkynes

Chemical Communications, Год журнала: 2023, Номер 59(43), С. 6584 - 6587

Опубликована: Янв. 1, 2023

We synthesized tetrasubstituted olefins regioselectively and stereoselectively from ynamides internal alkynes with sulfonyl iodides under blue LEDs in few minutes. The key features are being metal-free, easy to handle, simple, broad scope, environmentally friendly. Furthermore, a gram-scale experiment was conducted, the corresponding sulfonyl-iodinated products were smoothly altered into various other products.

Язык: Английский

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Reductive Elimination Reactions in Gold(III) Complexes Leading to C(sp³)–X (X = C, N, P, O, Halogen) Bond Formation: Inner-Sphere vs S_N2 Pathways

Inorganic Chemistry, Год журнала: 2023, Номер 62(4), С. 1708 - 1718

Опубликована: Янв. 20, 2023

The reactions leading to the formation of C-heteroatom bonds in coordination sphere Au(III) complexes are uncommon, and their mechanisms not well known. This work reports on synthesis reductive elimination a series methyl containing different Au-heteroatom bonds. Complexes [Au(CF3)(Me)(X)(PR3)] (R = Ph, X OTf, OClO3, ONO2, OC(O)CF3, F, Cl, Br; R Cy, Me, Br) were obtained by reaction trans-[Au(CF3)(Me)2(PR3)] Cy) with HX. cationic complex cis-[Au(CF3)(Me)(PPh3)2]OTf was [Au(CF3)(Me)(OTf)(PPh3)] PPh3. Heating these led MeX (X Ph3P+, Br). Mechanistic studies indicate that occur either through (a) tricoordinate intermediates phosphine dissociation, followed MeX, or (b) attack weakly coordinating anionic (TfO- ClO4-) neutral nucleophiles (PPh3 NEt3) Au-bound carbon. results show for first time nucleophilic substitution should be considered as likely pathway alkyl complexes.

Язык: Английский

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Multisubstituted Indoles by a Dual Gold/Silver-Catalyzed Aminoalkynylation of 2-Alkynylanilines

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 30, 2025

A straightforward and efficient method for the synthesis of multisubstituted indoles has been developed through a dual gold/silver-catalyzed aminoalkynylation 2-alkynylanilines using hypervalent iodine(III) reagents under open-air conditions. This approach features in situ generation alkynyl Au(III) species, which facilitates with excellent functional group tolerance high yields. Mechanistic studies reveal that gold(III) intermediate plays crucial role reaction pathway. Moreover, protocol is scalable to gram quantities offers potential further transformation into diverse functionalized compounds.

Язык: Английский

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Metal-free synthesis of dihydrofuran derivatives as anti-vicinal amino alcohol isosteres

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(5), С. 960 - 965

Опубликована: Янв. 1, 2023

Dihydrofuran cores are commonly incorporated into synthetically and pharmacologically significant scaffolds in natural product drug discovery chemistry. Herein, we report a concise practical strategy to construct spiro-dihydrofuran amino dihydrofuran as anti-vicinal alcohol isosteres. Hypervalent iodine (PhI(OAc)(NTs2))-mediated C-H activation of alkynes resulted two-bond formations with one pi bond cleavage: (i) C(sp2)-N(sp3) O(sp3)-C(sp2); (ii) C(sp3)-C(sp2). The metal-free 5-endo-dig oxidative cyclization provided versatile 2,3- 2,5-dihydrofurans bearing the C5 quaternary carbon. non-toxicity all synthesised dihydrofurans was verified via vitro cell viability assay.

Язык: Английский

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Atom-economic and stereoselective catalytic synthesis of fully substituted enol esters/carbonates of amides in acyclic systems enabled by boron Lewis acid catalysis

Chemical Science, Год журнала: 2023, Номер 14(21), С. 5608 - 5618

Опубликована: Янв. 1, 2023

A boron Lewis acid catalyzes trans-carboacyloxylations of ynamides with esters to afford fully substituted acyclic enol esters/carbonates in high yields and excellent stereocontrol.

Язык: Английский

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