α‐Thianthrenium Carbonyl Species: The Equivalent of an α‐Carbonyl Carbocation DOI Creative Commons
Hao Jia, Tobias Ritter

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(39)

Published: July 27, 2022

Abstract Here we report an α‐thianthrenium carbonyl species, as the equivalent of α‐carbonyl carbocation, which is generated by radical conjugate addition a trifluoromethyl thianthrenium salt to Michael acceptors. The reactivity allows for synthesis C α ‐tetrasubstituted α‐ and β‐amino acid analogues via Ritter reaction acetonitrile. Addition hydroxide, methoxide, even fluoride can afford α‐heteroatom substituted α‐phenylpropanoates.

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
α‐Thianthrenium Carbonyl Species: The Equivalent of an α‐Carbonyl Carbocation DOI Creative Commons
Hao Jia, Tobias Ritter

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(39)

Published: Aug. 9, 2022

Here we report an α-thianthrenium carbonyl species, as the equivalent of α-carbonyl carbocation, which is generated by radical conjugate addition a trifluoromethyl thianthrenium salt to Michael acceptors. The reactivity allows for synthesis C

Language: Английский

Citations

32
A sequential Au(i)/TBAF-promoted rapid and selective functionalization of heteroarene N-oxides with alkynes DOI

Mengfei Jiang,

Huilong Zhu, Lei Huang

et al.

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

Published: Jan. 1, 2025

We present a rapid Au( i )-catalyzed strategy for N -heteroarene functionalization using TBAF as nucleophile or base. The method provides excellent yields, broad substrate scope and functional group tolerance, enabling diverse transformations.

Language: Английский

Citations

0
Unified strategy for the α-functionalization of esters, imides, and ketones via enolonium species DOI Creative Commons

Raja Kapanaiah,

Bat‐El Oded,

Raz Strugano

et al.

Cell Reports Physical Science, Journal Year: 2025, Volume and Issue: unknown, P. 102460 - 102460

Published: March 1, 2025

Language: Английский

Citations

0
On-Water Accelerated Sulfenylation of Indole Derivatives under Visible Light Irradiation DOI Creative Commons

Jun Sup Lee,

Chulyong Lee,

Jiwon Jang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A visible-light promoted sulfenylation of N -carboxyindoles with thiols showed substantially higher rate and selectivity when conducted “on water”.

Language: Английский

Citations

0
Synthesis of α-heterofunctionalized carbonyl compounds via Brønsted acid-catalyzed oxygenative coupling of ynamides DOI
Tae‐Woong Um, Hyun‐Suk Yeom, Seunghoon Shin

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(6), P. 1790 - 1795

Published: Jan. 1, 2024

Brønsted acid-catalyzed addition of pyridine- N -oxides to ynamides forms -enoxypyridinium ions that are functionally equivalent α-carbonyl cations.

Language: Английский

Citations

1
Ortho-selective C–H arylation of phenols with N-carboxyindoles under Brønsted acid- or Cu(i)-catalysis DOI Creative Commons
Nguyen H. Nguyen, Soo Min Oh, Cheol‐Min Park

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 13(4), P. 1169 - 1176

Published: Dec. 27, 2021

Control over chemo- and regioselectivity is a critical issue in the heterobiaryl synthesis via C–H oxidative coupling. To address this challenge, strategy to invert normal polarity of indoles was developed.

Language: Английский

Citations

10
Umpolung Approach to Aldol Products via Isoxazoline N-Oxides as Intermediates DOI
Pavel Yu. Ushakov, Alexey Yu. Sukhorukov

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(21), P. 15590 - 15597

Published: Oct. 11, 2024

A two-step umpolung approach to the diastereoselective synthesis of aldols was developed, in which a conjugated nitroalkene is used as synthetic equivalent enolonium cation, while sulfur ylide acts α-carbinol anion. The resulting isoxazoline

Language: Английский

Citations

1
Reactivity Umpolung of Amides in Organic Synthesis DOI

Qiu Shi,

Wenbo Liu

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(12)

Published: Oct. 6, 2023

Abstract Amides are important carboxylic acid derivatives, having wide applications in chemistry, biochemistry, and material science. Due to the conjugation (n N ‐π* C=O ), carbonyl group of amides is least electrophilic C alpha −H bond acidic among thereby making it challenging develop highly efficient selective transformations based on amides. Reactivity umpolung refers reversion polarity a functional group. The idea inverting innate organic groups, initially introduced by Wittig later popularized Seebach, marks pivotal conceptual breakthrough synthesis. In contrast progress for aldehyde, has proved only recently made notable progress. Following elegant design, C1 amide can become nucleophilic, C2 be electrophilic. this review, we attempt summarize reported examples that broadly categorized as reactivity This review structured around through radical or carbanion reactions, well activation unique properties Weinreb amide.

Language: Английский

Citations

3
Catalyst‐Controlled Divergent Generations and Transformations of α‐Carbonyl Cations from Alkynes** DOI Open Access

Junrui Zhou,

Weilin Wang,

Fenfang Zuo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 19, 2023

α-Carbonyl cations are the umpolung forms of synthetically fundamental α-carbonyl carbanions. They highly reactive yet rarely studied and utilized species their precursors were rather limited. Herein, we report catalyst-controlled divergent generations from single alkyne functionalities interception them via Wagner-Meerwein rearrangement. Two chemodivergent catalytic systems have been established, leading to two different types and, eventually, products, i.e. α,β- β,γ-unsaturated carbonyl compounds. Broad spectrum alkynes including aryl alkyne, ynamide, alkynyl ether, sulfide could be migration priorities groups in rearrangement step was elucidated. Density functional theory calculations further supported intermediacy N-O bond cleavage both systems. Another key feature this methodology fragmentation inert tert-butyl into readily transformable olefin functionalities. The synthetic potential highlighted by scale-up reactions downstream diversifications formal synthesis nicotlactone B galbacin.

Language: Английский

Citations

3