Reactivity of hypervalent iodine(III) reagents bearing a benzylamine with sulfenate salts DOI Creative Commons
Beatriz Dedeiras,

Catarina Caldeira,

José Cunha

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 3281 - 3289

Published: Dec. 19, 2024

The reactivity of our recently disclosed hypervalent iodine reagents (HIRs) bearing a benzylamine with in situ-generated sulfenate salts was investigated. Under the studied conditions sulfonamides have been obtained up to 52% yield. This reaction has extended variety HIRs and explore different these new reagents. A plausible mechanism is proposed, suggesting possible radical pathway.

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

34
Recent Progress in Synthetic Applications of Cyclic Hypervalent Iodine(III) Reagents DOI Creative Commons
Akira Yoshimura, Akio Saito, Viktor V. Zhdankin

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(16), P. 2653 - 2675

Published: April 21, 2023

Abstract Hypervalent iodine compounds have found broad application in modern organic chemistry as reagents and catalysts. Cyclic hypervalent based on the benziodoxole heterocyclic system higher stability compared to their acyclic analogues, which makes possible preparation safe handling of with special ligands such azido, cyano, trifluoromethyl groups. Numerous iodine‐substituted derivatives been prepared utilized for transfer substituent substrate. Reactions these substrates can be performed under metal‐free conditions, presence transition metal catalysts, or using photocatalysts photoirradiation conditions. In this review, we focus most recent synthetic applications cyclic iodine(III) following ligands: N 3 , NHR, CN, CF SCF OR, OAc, ONO 2 C(=N )CO R. The review covers literature published mainly last 5 years.

Language: Английский

Citations

30
Organohypervalent heterocycles DOI
Ravi Kumar, Toshifumi Dohi, Viktor V. Zhdankin

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4786 - 4827

Published: Jan. 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.

Language: Английский

Citations

8
Visible‐Light‐Induced C−H Amidation of (Hetero)arenes with Hypervalent Iodine(III) Reagents DOI Open Access
Xiaojuan Wang, He Wang, Zhenkun Ma

et al.

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

Published: March 10, 2025

Abstract A visible‐light‐promoted C−H amidation of (hetero)arenes with hypervalent iodine reagents has been successfully achieved good yields. The high efficiency, broad substrate range and functional group compatibility demonstrated the utility method. Moreover, this protocol was suitable for late‐stage functionalization natural products. Mechanistic studies have shown that N‐centred saccharin radical mediates arenes.

Language: Английский

Citations

0
Iodine-Mediated α-C–H Amination of Carbonyl Compounds via Nitrogen-Directed Oxidative Umpolung DOI

Manman Wang,

Xiaofei Yi, Wenjun Ye

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 8751 - 8760

Published: June 12, 2023

A new synthetic strategy for direct C(sp3)–H amination of carbonyl compounds at their α-carbon has been established employing molecular iodine and nitrogen-directed oxidative umpolung. In this transformation, acts not only as an iodinating reagent but also a Lewis acid catalyst, both the nitrogen-containing moiety group in substrate play important roles. This approach is applicable to broad variety substrates, including esters, ketones, amides. Its features include no requirement transition metals, mild reaction conditions, short times, gram-scale synthesis.

Language: Английский

Citations

7
Photoexcitation of (diarylmethylene)amino benziodoxolones for alkylamination of styrene derivatives with carboxylic acids DOI Creative Commons

Daichi Okumatsu,

Kensuke Kiyokawa,

Linh Tran Bao Nguyen

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 15(3), P. 1068 - 1076

Published: Dec. 12, 2023

The alkylamination of alkenes using pristine carboxylic acids was achieved by the photoexcitation (diarylmethylene)amino benziodoxolones (DABXs), which serve as both an oxidant and aminating reagent (an iminyl radical precursor). developed method is a simple photochemical reaction without need for external photosensitizers shows broad substrate scope aliphatic leading to formation primary, secondary, tertiary alkyl radicals, thus enabling facile synthesis various structurally complex amines. Mechanistic investigations including transient absorption spectroscopy measurements laser flash photolysis (LFP) disclosed unique reactivity DABXs, undergoes homolysis their I-N bonds give

Language: Английский

Citations

6
Amino‐ and Alkoxybenziodoxoles: Facile Preparation and Use as Arynophiles DOI Creative Commons
Kazuya Kanemoto,

Ken Yoshimura,

Koki Ono

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(29)

Published: March 18, 2024

Abstract We report here on the facile synthesis of amino‐ and alkoxy‐λ 3 ‐iodanes supported by a benziodoxole (BX) template their use as arynophiles. The alkoxy‐BX derivatives can be readily synthesized reacting respective amines or alcohols with chlorobenziodoxole in presence suitable base. Unlike previously known nitrogen‐ oxygen‐bound iodane compounds, which have primarily been employed electrophilic group transfer agents oxidants, present reagents manifest themselves nucleophilic amino alkoxy toward arynes. This reactivity leads to aryne insertion into N−I(III) O−I(III) bond afford ortho ‐amino‐ ‐alkoxy‐arylbenziodoxoles, compounds nontrivial procure existing methods. BX these products exhibits excellent leaving ability, enabling diverse downstream transformations.

Language: Английский

Citations

2
Reactivity of hypervalent iodine(III) reagents bearing a benzylamine with sulfenate salts DOI Creative Commons
Beatriz Dedeiras,

Catarina Caldeira,

José Cunha

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 3281 - 3289

Published: Dec. 19, 2024

The reactivity of our recently disclosed hypervalent iodine reagents (HIRs) bearing a benzylamine with in situ-generated sulfenate salts was investigated. Under the studied conditions sulfonamides have been obtained up to 52% yield. This reaction has extended variety HIRs and explore different these new reagents. A plausible mechanism is proposed, suggesting possible radical pathway.

Language: Английский

Citations

0