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

peri-Fused polyaromatic molecular contacts for perovskite solar cells DOI
Ke Zhao, Qingqing Liu,

Libing Yao

et al.

Nature, Journal Year: 2024, Volume and Issue: 632(8024), P. 301 - 306

Published: July 24, 2024

Language: Английский

Citations

77
Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage DOI
Casey B. Roos, Chang-Hwa Chiang, Lauren A. M. Murray

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(17), P. 10641 - 10727

Published: Aug. 28, 2023

Enantiomers, where chirality arises from restricted rotation around a single bond, are atropisomers. Due to the unique nature of origins their chirality, synthetic strategies access these compounds in an enantioselective manner differ those used prepare enantioenriched containing point arising unsymmetrically substituted carbon center. In particular stereodynamic transformations, such as dynamic kinetic resolutions, thermodynamic and deracemizations, which rely on ability racemize or interconvert enantiomers, promising set transformations optically pure late stage sequence. Translation approaches with atropisomers requires expanded toolbox for epimerization/racemization provides opportunity develop new conceptual framework synthesis compounds.

Language: Английский

Citations

52
The chemistry of heterocycles in the 21st century DOI
Valery N. Charushin, Egor V. Verbitskiy, О. Н. Чупахин

et al.

Russian Chemical Reviews, Journal Year: 2024, Volume and Issue: 93(7), P. RCR5125 - RCR5125

Published: July 1, 2024

The chemistry of heterocyclic compounds has traditionally been and remains a bright area chemical science in Russia. This is due to the fact that many heterocycles find widest application. These are key structural fragments most drugs, plant protection agents. Many natural also derivatives heterocycles. At present, more than half hundreds millions known collective review devoted achievements Russian chemists this field over last 15–20 years. presents leading heterocyclists representing both RAS institutes university science. It worth noting wide scope review, terms geography author teams, covering whole our large country, diversity research areas. Practically all major types represented review. special attention focused on practical applications design new drugs biologically active compounds, high-energy molecules, materials for organic electronics photovoltaics, ligands coordination chemistry, other rapidly developing advances would not be possible without development fundamental transformations chemistry.<br> Bibliography — 2237 references.

Language: Английский

Citations

37
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
Amide C–N bonds activation by A new variant of bifunctional N-heterocyclic carbene DOI Creative Commons

Yuxing Cai,

Yuxin Zhao,

Kai Tang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 12, 2024

Abstract We report an organocatalyst that combines a triazolium N-heterocyclic carbene (NHC) with squaramide as hydrogen-bonding donor (HBD), which can effectively catalyze the atroposelective ring-opening of biaryl lactams via unique amide C–N bond cleavage mode. The free species attacks carbonyl, forming axially chiral acyl-azolium intermediate. Various amines be accessed by this methodology up to 99% ee and yield. By using mercaptan catalyst turnover agent, resulting thioester synthon transformed into several interesting atropisomers. Both control experiments theoretical calculations reveal crucial role hybrid NHC-HBD skeleton, activates H-bonding brings it spatially close centre. This discovery illustrates potential chimera demonstrates complementary strategy for activation manipulation.

Language: Английский

Citations

17
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

29
Atroposelective Synthesis of Axially Chiral Diaryl Ethers by Copper-Catalyzed Enantioselective Alkyne–Azide Cycloaddition DOI Creative Commons

Xuyao Han,

Lan Chen, Yong Yan

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3475 - 3481

Published: Feb. 21, 2024

Diaryl ethers are important structural motifs widely found in bioactive natural products, ligands, and catalysts. While there a variety of methods available to generate diaryl ethers, progress on the construction axially chiral has been slow. We report herein an atroposelective copper-catalyzed cycloaddition between bisalkynes azides. With indane-fused BOX ligand used, diverse array C–O atropisomers obtained with up 97% yield 99% ee. Control experiments showed that sequential enantioselective desymmetrization–kinetic resolution process is involved, former plays major role. In addition, asymmetric depletion observed for this catalytic synthesis by nonlinear effect studies. By thermal racemization experiments, rotational barrier axis 3aa calculated be 35.9 kcal/mol, which lays foundation its isolation, as well further applications.

Language: Английский

Citations

14
Diaryl hypervalent bromines and chlorines: synthesis, structures and reactivities DOI Creative Commons
Matteo Lanzi, Joanna Wencel‐Delord

Chemical Science, Journal Year: 2024, Volume and Issue: 15(5), P. 1557 - 1569

Published: Jan. 1, 2024

Diaryl hypervalent bromines and chlorines emerge as a novel foundation for advancing organic chemistry. This article provides an overview of the synthetic methodology, structural variations, latest transformations unearthed in this context.

Language: Английский

Citations

13
Transition-metal-catalyzed enantioselective C–N cross-coupling DOI
Jia Feng, Longlong Xi, Chuan‐Jun Lu

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(19), P. 9560 - 9581

Published: Jan. 1, 2024

Chiral amine scaffolds are among the most important building blocks in natural products, drug molecules, and functional materials, which have prompted chemists to focus more on their synthesis. Among accomplishments chiral synthesis, transition-metal-catalyzed enantioselective C-N cross-coupling is considered one of efficient protocols. This approach combines traditional C(sp

Language: Английский

Citations

10
Aryl-, Akynyl-, and Alkenylbenziodoxoles: Synthesis and Synthetic Applications DOI Creative Commons
Irina A. Mironova,

Dmitrii M. Noskov,

Akira Yoshimura

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(5), P. 2136 - 2136

Published: Feb. 24, 2023

Hypervalent iodine reagents are in high current demand due to their exceptional reactivity oxidative transformations, as well diverse umpolung functionalization reactions. Cyclic hypervalent compounds, known under the general name of benziodoxoles, possess improved thermal stability and synthetic versatility comparison with acyclic analogs. Aryl-, alkenyl-, alkynylbenziodoxoles have recently received wide applications efficient for direct arylation, alkenylation, alkynylation mild reaction conditions, including transition metal-free conditions photoredox metal catalysis. Using these reagents, a plethora valuable, hard-to-reach, structurally complex products can be synthesized by convenient procedures. The review covers main aspects chemistry benziodoxole-based aryl-, alkynyl-, alkenyl- transfer preparation applications.

Language: Английский

Citations

18