Alkene versus Aryl Chlorination in Asymmetric Hypervalent Iodine Catalysis: A Case Study DOI
Tanja Gulder, Andreas M. Arnold, Julia Katharina Binder

et al.

Synlett, Journal Year: 2023, Volume and Issue: 35(09), P. 1001 - 1006

Published: Oct. 30, 2023

Abstract Hypervalent λ3-iodanes have become a prominent tool for halofunctionalizations of alkenes. Despite many examples asymmetric fluorinations reported lately, the corresponding enantioselective chlorination reactions using iodoresorcinol-based catalysts are significantly less developed, with only one example known to date. Here, we show how competing aromatic iodoarene catalyst is significant obstacle in these transformations, hinting towards conceptual issue this well-established class chlorinations. Consequently, reaction conditions and design must be adapted facilitate an effective chirality transfer. Hence, attention should paid when selecting oxidizing agent, stoichiometry, careful analysis conducted identify factual catalytically active species.

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
Electrochemical Oxidative Dibrominative Cyclization of 1,n-Enynes with Hypervalent Iodoarene Intermediates Utilizing Recyclable Bromine Ionic Liquids DOI
Longji Li, Xu Wang, Hui Jiang

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 5, 2025

An electrochemical approach with iodoarene as a mediator using recyclable ionic liquids to achieve dibromonative cyclization of 1,n-enynes has been reported. With bromine sources, in situ generation iodine(III) compounds through oxidation cyclization, variety heterocyclic frameworks containing both vinyl and alkyl bromide groups had obtained high yields good selectivity.

Language: Английский

Citations

0
A decade of lessons in the activation of ArIL2 species DOI Creative Commons

Tania Tania,

Marcus Sceney, Jason L. Dutton

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(11), P. 3784 - 3799

Published: Jan. 1, 2024

Developments in methods to increase the oxidative capacity of ArIL 2 reagents are discussed, with a focus on an understanding these species' behaviour from perspective iodine.

Language: Английский

Citations

2
Reduced estrogenic risks of a sunscreen additive: Theoretical design and evaluation of functionally improved salicylates DOI

Yuhan Cui,

Wei He, Zhonghe Wang

et al.

Journal of Hazardous Materials, Journal Year: 2024, Volume and Issue: 477, P. 135371 - 135371

Published: July 29, 2024

Language: Английский

Citations

2
Electrophilic activation of molecular bromine mediated by I(iii) DOI
Lachlan Sharp‐Bucknall,

Tania Tania,

Marcus Sceney

et al.

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(44), P. 16472 - 16479

Published: Jan. 1, 2023

In pursuit of a genuine bromo-λ3-iodane, it has been found that the combination Br2 and electron deficient λ3-iodanes can result in delivery both bromine atoms from to range aryl substrates, some highly deactivated. These brominations occur rapidly common chlorinated solvents at room temperature be achieved with catalytic activation commercially available PhI(OAc)2 PhI(OTFA)2. para-NO2 substituted derivatives are employed direct bromination towards more deactivated substrates. The mechanism is discussed insights being made, however remains unclear.

Language: Английский

Citations

2
ArI(NTf2)2: the boundary of oxidative capacity for ArIL2? DOI

Lachlan Barwise,

Jason D. Bennetts,

Keith F. White

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(89), P. 13340 - 13343

Published: Jan. 1, 2023

Synthesis and crystallographic characterization of NO2-C6H4-I(NTf2)2 (NTf2 = bistriflimide) is reported. Experimental results find that this compound can perform oxidation reactions ArI(OTf)2 unable to theoretical analysis indicates Ar-I(NTf2)2 the most oxidizing in ArIL2 class compounds known may also be practically possible.

Language: Английский

Citations

2
Structural verification and new reactivity for Stang's reagent, [PhI(CN)][OTf] DOI

Jason D. Bennetts,

Lachlan Barwise,

Lachlan Sharp‐Bucknall

et al.

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(25), P. 8536 - 8539

Published: Jan. 1, 2023

The structure of Stang's reagent [PhI(CN)][OTf] is confirmed by X-ray crystallography and determined to be best described as an ion-pair in organic solution. It found a strong Lewis acid, but reaction with pyridine ligands gives [Pyr-CN][OTf] salts via oxidation giving new derivative the CDAP widely used activation agent for polysaccharides.

Language: Английский

Citations

1
Alkene versus Aryl Chlorination in Asymmetric Hypervalent Iodine Catalysis: A Case Study DOI
Tanja Gulder, Andreas M. Arnold, Julia Katharina Binder

et al.

Synlett, Journal Year: 2023, Volume and Issue: 35(09), P. 1001 - 1006

Published: Oct. 30, 2023

Abstract Hypervalent λ3-iodanes have become a prominent tool for halofunctionalizations of alkenes. Despite many examples asymmetric fluorinations reported lately, the corresponding enantioselective chlorination reactions using iodoresorcinol-based catalysts are significantly less developed, with only one example known to date. Here, we show how competing aromatic iodoarene catalyst is significant obstacle in these transformations, hinting towards conceptual issue this well-established class chlorinations. Consequently, reaction conditions and design must be adapted facilitate an effective chirality transfer. Hence, attention should paid when selecting oxidizing agent, stoichiometry, careful analysis conducted identify factual catalytically active species.

Language: Английский

Citations

1