Synthesis of Closed‐Heterohelicenes Interconvertible between Their Monomeric and Dimeric Forms DOI

Yusuke Matsuo,

Chihiro Maeda, Yusuke Tsutsui

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(50)

Published: Oct. 26, 2023

Abstract Oxidative fusion reaction of cyclic heteroaromatic pentads consisting pyrrole and thiophene gave closed‐heterohelicene monomers dimers depending on the oxidation conditions. Specifically, with [bis(trifluoroacetoxy)iodo]benzene (PIFA) closed‐[7]helicene connected at β‐position one units remarkably elongated C−C bonds about 1.60 Å. Although this bond was intact against thermal physical activations, homolytic dissociation took place in DMSO upon irradiation UV light to give corresponding monomers. Thus, interconversion between closed‐helicene monomer dimer achieved. The optically pure photo‐dissociated into associated a turn‐on circularly polarized luminescence (CPL).

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

33
Mn(III) Catalyzed Cascade Cross-coupling / Annulation / C(O)-C Bond Insertion / Rearrangement: Access to Multi-substituted Indolenines in Water DOI Creative Commons
Huimin Qian, Shuai Jiang, You Zi

et al.

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

Citations

0
Synthesis of Closed‐Heterohelicenes Interconvertible between Their Monomeric and Dimeric Forms DOI

Yusuke Matsuo,

Chihiro Maeda, Yusuke Tsutsui

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(50)

Published: Oct. 26, 2023

Oxidative fusion reaction of cyclic heteroaromatic pentads consisting pyrrole and thiophene gave closed-heterohelicene monomers dimers depending on the oxidation conditions. Specifically, with [bis(trifluoroacetoxy)iodo]benzene (PIFA) closed-[7]helicene connected at β-position one units remarkably elongated C-C bonds about 1.60 Å. Although this bond was intact against thermal physical activations, homolytic dissociation took place in DMSO upon irradiation UV light to give corresponding monomers. Thus, interconversion between closed-helicene monomer dimer achieved. The optically pure photo-dissociated into associated a turn-on circularly polarized luminescence (CPL).

Language: Английский

Citations

6
Synthesis of [4.6] Spirocarbocycles: A Base-promoted Ring-Expansion and Subsequent I2-mediated Regioselective Spirocyclization Protocol DOI
Nana Fei, Zongkang Wang, Peng He

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(23), P. 6797 - 6803

Published: Jan. 1, 2024

An efficient protocol for the synthesis of [4.6] spirocarbocycles by reacting cyclic β-ketoesters with aryl-fused 1,6-diyn-3-ones has been developed.

Language: Английский

Citations

0
Five-membered ring systems: Pyrroles and benzo analogs DOI
Chuan Shan, Justin M. Lopchuk

Progress in heterocyclic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 123 - 173

Published: Jan. 1, 2024

Language: Английский

Citations

0
Hypervalent Iodine Catalyzed Cascade C–H Functionalization: An Atom‐Economical Strategy to Access Diverse 2‐Substituted Benzothiazoles DOI
Santhosh Kumar Alla, Kotari Shakeena,

Bokka Srinivas

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 10, 2024

Abstract A metal‐free 4,5‐difluoro‐2‐iodobenzoic acid catalyzed C−H functionalization strategy has been developed for the synthesis of 2‐(hetero)aryl benzothiazoles from aryl isothiocyanates and unfunctionalized arenes/thiophenes/furans at room temperature. The procedure entails one‐pot cascade carbon−carbon carbon−sulfur bond formation facilitated by triflic acid, which serves as both a Brønsted ligand source in situ generated I(III) center. This process is atom‐economical offers benefits over existing protocols synthesizing terms ease use, eco‐friendliness, not requiring typical use aldehyde/carboxylic precursors. Mechanistic studies were carried out, synthetic utility protocol was demonstrated benzothiazole‐based antitumor drug GW‐610.

Language: Английский

Citations

0
Dearomative Spirocyclization of Ynamides DOI Creative Commons

Mohamed Agbaria,

Nwar Egbaria,

Zackaria Nairoukh

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(45), P. 19136 - 19141

Published: Jan. 1, 2024

Spiro N-heterocycles, particularly aza-spiro piperidines, have shown significant promise in pharmaceutical applications due to their ability enhance physicochemical properties. Despite potential, the preparation of these complex structures poses challenges. To address this, we propose a one-pot dearomative spirocyclization reaction ynamides. This method involves copper-catalyzed carbomagnesiation reaction, achieving chemo-, regio-, and stereoselective formation vinyl metal intermediates. Upon addition Lewis acid, intermediates undergo regioselective nucleophilic dearomatization event, facilitating synthesis diverse dihydropyridine scaffolds with multiple functional handles. Various Grignard reagents, ynamides, acylating reagents been explored. A subsequent hydrogenation provides access both partially fully reduced spirocyclic frameworks, broadening scope potential medicinal applications.

Language: Английский

Citations

0
Synthesis of Closed‐Heterohelicenes Interconvertible between Their Monomeric and Dimeric Forms DOI

Yusuke Matsuo,

Chihiro Maeda, Yusuke Tsutsui

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(50)

Published: Oct. 26, 2023

Abstract Oxidative fusion reaction of cyclic heteroaromatic pentads consisting pyrrole and thiophene gave closed‐heterohelicene monomers dimers depending on the oxidation conditions. Specifically, with [bis(trifluoroacetoxy)iodo]benzene (PIFA) closed‐[7]helicene connected at β‐position one units remarkably elongated C−C bonds about 1.60 Å. Although this bond was intact against thermal physical activations, homolytic dissociation took place in DMSO upon irradiation UV light to give corresponding monomers. Thus, interconversion between closed‐helicene monomer dimer achieved. The optically pure photo‐dissociated into associated a turn‐on circularly polarized luminescence (CPL).

Language: Английский

Citations

0