Structure and thermal stability of phosphorus-iodonium ylids DOI Creative Commons
Andrew Greener, Stephen P. Argent, Coby J. Clarke

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2931 - 2939

Published: Nov. 14, 2024

Hypervalent iodine(III) reagents have become indispensable tools in organic synthesis, but gaps remain the functionalities they can transfer. In this study, a fundamental understanding of thermal stability phosphorus-iodonium ylids is obtained through X-ray diffraction, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Insights into structural factors affecting potential decomposition pathways will enable future design development new reagents.

Language: Английский

Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents DOI Creative Commons
Akira Yoshimura, Viktor V. Zhdankin

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 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.

Language: Английский

Citations

28
Visible photons as ideal reagents for the activation of coloured organic compounds DOI Creative Commons
Lorenzo Di Terlizzi, Luca Nicchio,

Stefano Protti

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 4926 - 4975

Published: Jan. 1, 2024

In search for the perfect wave(length). This review is dedicated to recent efforts in development of visible light driven photochemical strategies occurring coloured organic compounds.

Language: Английский

Citations

11
Aliphatic Sulfonyl Fluoride Synthesis via Decarboxylative Fluorosulfonylation of Hypervalent Iodine(III) Carboxylates DOI

Caiyun Ou,

Yinxia Cai,

Yuyang Ma

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(36), P. 6751 - 6756

Published: Sept. 1, 2023

We disclose herein a photocatalytic decarboxylative fluorosulfonylation reaction of various hypervalent iodine(III) carboxylates in combination with 1,4-diazabicyclo[2.2.2]octane–bis(sulfur dioxide) adduct as sulfonyl source and KHF2 desirable fluorine via radical sulfur dioxide insertion fluorination strategy. A one-pot carboxylic acids mediated by PhI(OAc)2 was realized, well. Notably, this transformation can be performed under heating conditions without the need for catalysts.

Language: Английский

Citations

15
Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer DOI Creative Commons
Jiale Xie, Jiayu Zhang, Sitthichok Kasemthaveechok

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(8), P. 1021 - 1030

Published: July 1, 2024

Abstract Intramolecular amination of remote aliphatic C–H bonds via hydrogen-atom transfer reactions has become a powerful tool for accessing saturated nitrogen-containing heterocycles. However, the formation six-membered rings or oxa-heterocycles remains formidable challenge Hofmann–Löffler–Freytag reactions. Here we show how by simply combining bench-stable (bis(trifluoroacetoxy)iodo)benzene and hexafluoroisopropanol (HFIP) can switch from well-established mechanism to different versatile reaction pathway that enables selective C( sp 3 )–H bond functionalization. We have exploited facile radical cations single-electron transfer, in presence absence light, synthesize pyrrolidines piperidines, including drug-type molecules, along with O-heterocycles. Experimental computational mechanistic studies support two distinct pathways, depending on electron density substrate, which HFIP plays multifunctional role.

Language: Английский

Citations

5
Iodine(III)-Mediated Trifluoroacetylation of a C(sp2)–H or C(sp)–H Bond with Masked Trifluoroacyl Reagents DOI

Zhipeng Ye,

Meng Guo,

Yong-Qing Ye

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(24), P. 5196 - 5201

Published: June 10, 2024

A novel strategy for incorporating a trifluoroacetyl functionality into range of structurally varied unsaturated bonds was developed by using PhI(OCOMe)2 as an oxidant with masked trifluoroacyl reagent radical precursor. The oxidative decarboxylation the precursor followed tandem process provides versatile access to 5-exo-trig cyclization N-arylacrylamides, direct C(sp2)–H trifluoroacetylation quinolines, isoquinoline, 2H-indazole, and quinoxalin-2(1H)-ones, C(sp)–H alkynes. This protocol is characterized mild reaction conditions, operational simplicity, broad functional group compatibility.

Language: Английский

Citations

4
Advances in Catalytic Enantioselective Transformations Using Diaryliodonium Reagents DOI

Prasoon Raj Singh,

Arijit Banerjee,

Amit Kumar Simlandy

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3096 - 3115

Published: Feb. 5, 2025

Language: Английский

Citations

0
Iodoarene Activation: Take a Leap Forward toward Green and Sustainable Transformations DOI Creative Commons
Toshifumi Dohi, Elghareeb E. Elboray, Kotaro Kikushima

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Constructing chemical bonds under green sustainable conditions has drawn attention from environmental and economic perspectives. The dissociation of (hetero)aryl-halide is a crucial step most arylations affording (hetero)arene derivatives. Herein, we summarize the (hetero)aryl halides activation enabling direct (hetero)arylation trapping reagents construction highly functionalized (hetero)arenes benign conditions. strategies for aryl iodides are classified into (a) hypervalent iodoarene followed by functionalization thermal/photochemical conditions, (b) aryl-I bond in presence bases with/without organic catalysts promoters, (c) photoinduced presence/absence organophotocatalysts, (d) electrochemical direct/indirect electrolysis mediated organocatalysts mediators acting as electron shuttles, (e) electrophotochemical redox-active organocatalysts. These modes result exhibiting diverse reactivity formal cations/radicals/anions aryne precursors. coupling these reactive intermediates with leads to facile selective formation C-C C-heteroatom bonds. ecofriendly, inexpensive, functional group-tolerant offer alternatives transition metal-based catalysis.

Language: Английский

Citations

0
Halogen Bonds Formed by Halogen’s p/π-Hole in Molecules Help Shape Crystalline Materials DOI
Pradeep R. Varadwaj, Helder M. Marques, Ireneusz Grabowski

et al.

Crystal Growth & Design, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Language: Английский

Citations

0
Triplet Energy Transfer Mechanism in Copper Photocatalytic N‐ and O‐Methylation DOI Creative Commons
Martijn Hoving, Jacob‐Jan Haaksma, Anne Stoppel

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(22)

Published: Feb. 16, 2024

Abstract Methylation reactions are chemically simple but challenging to perform under mild and non‐toxic conditions. A photochemical energy transfer strategy was merged with copper catalysis enable fast reaction times of minutes broad applicability N ‐heterocycles, (hetero−)aromatic carboxylic acids, drug‐like molecules in high yields good functional group tolerance. Detailed mechanistic investigations, using kinetic analysis, aprotic MS, UV/Vis, luminescence quenching experiments revealed a triplet‐triplet mechanism between hypervalent iodine(III) reagents readily available photosensitizers.

Language: Английский

Citations

1
Structure and thermal stability of phosphorus-iodonium ylids DOI Creative Commons
Andrew Greener, Stephen P. Argent, Coby J. Clarke

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2931 - 2939

Published: Nov. 14, 2024

Hypervalent iodine(III) reagents have become indispensable tools in organic synthesis, but gaps remain the functionalities they can transfer. In this study, a fundamental understanding of thermal stability phosphorus-iodonium ylids is obtained through X-ray diffraction, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Insights into structural factors affecting potential decomposition pathways will enable future design development new reagents.

Language: Английский

Citations

0