Difluoroalkylation of Anilines via Photoinduced Methods DOI Creative Commons
Albert Gallego‐Gamo, Albert Granados, Roser Pleixats

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(17), P. 12585 - 12596

Published: Aug. 16, 2023

The development of sustainable and mild protocols for the fluoroalkylation organic backbones is current interest in chemical synthesis. Herein, we present operationally simple practical transition-metal-free methods preparation difluoroalkyl anilines. First, a visible-light organophotocatalytic system working via oxidative quenching described, providing access to wide range anilines under conditions. In addition, formation an unprecedented electron donor-acceptor (EDA) complex between ethyl difluoroiodoacetate reported exploited as alternative, efficient, straightforward strategy prepare derivatives.

Language: Английский

Synthetic Advantages of Defluorinative C−F Bond Functionalization DOI Creative Commons
Leidy V. Hooker, Jeffrey S. Bandar

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

Published: Aug. 22, 2023

Abstract Much progress has been made in the development of methods to both create compounds that contain C−F bonds and functionalize bonds. As such, are becoming common versatile synthetic functional handles. This review summarizes advantages defluorinative functionalization reactions for small molecule synthesis. The coverage is organized by type carbon framework fluorine attached mono‐ polyfluorinated motifs. main challenges, opportunities advances discussed each class organofluorine. Most text focuses on case studies illustrate how defluorofunctionalization can improve routes targets or properties enable unique mechanisms reactions. broader goal showcase incorporating exploiting design routes, improvement specific advent new methods.

Language: Английский

Citations

56
Bi-Catalyzed Trifluoromethylation of C(sp2)–H Bonds under Light DOI Creative Commons
Takuya Tsuruta, Davide Spinnato, Hye Won Moon

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(47), P. 25538 - 25544

Published: Nov. 14, 2023

We disclose a Bi-catalyzed C–H trifluoromethylation of (hetero)arenes using CF3SO2Cl under light irradiation. The catalytic method permits the direct functionalization various heterocycles bearing distinct functional groups. structural and computational studies suggest that process occurs through an open-shell redox manifold at bismuth, comprising three unusual elementary steps for main group element. cycle starts with rapid oxidative addition to low-valent Bi(I) catalyst, followed by light-induced homolysis Bi(III)–O bond generate trifluoromethyl radical upon extrusion SO2, is closed hydrogen-atom transfer Bi(II) intermediate.

Language: Английский

Citations

35
Nickel-Catalyzed Enantioconvergent and Diastereoselective Allenylation of Alkyl Electrophiles: Simultaneous Control of Central and Axial Chirality DOI
Asik Hossain, Robert L. Anderson,

Claudia S. Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7173 - 7177

Published: March 6, 2024

In recent years, remarkable progress has been described in the development of methods that simultaneously control vicinal stereochemistry, wherein both stereochemical elements are central chirality; contrast, and axial chirality comparatively rare. Herein we report a chiral nickel catalyst achieves enantioconvergent diastereoselective coupling racemic secondary alkyl electrophiles with prochiral 1,3-enynes (in presence hydrosilane) to generate tetrasubstituted allenes bear an adjacent stereogenic center. A carbon–carbon carbon–hydrogen bond formed this process, which provides good stereoselectivity is compatible array functional groups.

Language: Английский

Citations

12
9-(4-Halo-2,6-xylyl)-10-methylacridinium Ion as an Effective Photoredox Catalyst for Oxygenation and Trifluoromethylation of Toluene Derivatives DOI Creative Commons
Kei Ohkubo,

Soichiro Matsumoto,

Haruyasu Asahara

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2671 - 2684

Published: Feb. 6, 2024

9-(2,6-Dimethylphenyl)-10-methylacridinium perchlorate ([Acr+–Xyl]ClO4–), 9-(4-chloro-2,6-dimethylphenyl)-10-methylacridinium ([Acr+–XylCl]ClO4–), and 9-(4-fluoro-2,6-dimethylphenyl)-10-methylacridinium ([Acr+–XylF]ClO4–) were synthesized by the Grignard reaction. The one-electron reduction potentials (Ered vs SCE) of Acr+–Xyl, Acr+–XylCl, Acr+–XylF in deaerated acetonitrile (MeCN) determined cyclic voltammetry to be nearly same as −0.55, −0.53, −0.53 V, respectively. On other hand, oxidation (Eox Acr+–XylF, Acr+–XylCl second-harmonic alternative current voltammetric method +2.15, +2.20, +2.21 Eox value is higher than toluene (+2.20 V). Thus, photocatalytic oxygenation with oxygen occurs efficiently via electron transfer from XylCl•+ moiety triplet electron-transfer state under photoirradiation oxygen-saturated MeCN. By contrast, no occurred 9-mesityl-10-methylacridinium ion (Acr+–Mes) used a photocatalyst due lack oxidizing ability oxidize toluene. metal-free trifluoromethylation derivatives has also been made possible using S-(trifluoromethyl)dibenzothiophenium (CF3DBT+) trifluoromethyl source. reaction mechanism was clarified transient absorption electrochemical measurements.

Language: Английский

Citations

10
Construction of trifluoromethyl-containing heterocycles from trifluoroacetimidoyl chlorides and derivatives DOI

Zuguang Yang,

Guangming Wei,

Zhengkai Chen

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(33), P. 4872 - 4890

Published: Jan. 1, 2023

Recent advances in the direct synthesis of trifluoromethyl-containing heterocycles from trifluoroacetimidoyl chlorides (TFAICs) and derivatives, including trifluoroacetimidohydrazides (TFAIHs) CF3-imidoyl sulfoxonium ylides (TFISYs), are systematically summarized discussed. The cascade annulation reactions synthons with suitable coupling partners have emerged as a powerful promising tool for construction variety trifluoromethyl-substituted heterocycles. Compared other building blocks, TFAICs derivatives notable merits easy availability handling, relative stability safety, high reactivity.

Language: Английский

Citations

22
Selectively Tunable Synthesis of α-Trifluoromethyl Ketones DOI
Pan Zhou,

Shanya Lu,

Xiaoqiang Wu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(13), P. 2344 - 2348

Published: March 23, 2023

A cross-coupling of aldehydes and α-trifluoromethyl alkyl bromides was developed via dual nickel/photoredox catalysis system. wide variety substrates bearing a diverse set functional groups were compatible to afford ketones under very mild conditions (visible light, ambient temperature, no strong base). Selectively tunable access these with the trifluoromethyl group on any one side can be smoothly obtained by simply modulating different reagents. Meanwhile, asymmetric pattern also investigated.

Language: Английский

Citations

20
Synthesis of Trifluoromethyl-Substituted Allenols via Catalytic Trifluoromethylbenzoxylation of 1,3-Enynes DOI

Songrong Li,

Wenwen Yang,

Junjie Shi

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(3), P. 2142 - 2148

Published: Jan. 25, 2023

Allenol has been identified as a versatile building block for organic synthesis, and numerous efforts have made to synthesize apply allenol. However, limited obtain trifluoromethyl-substituted Here, by using readily available 1,3-enyne the starting material, copper-catalyzed trifluoromethylbenzoxylation process was developed efficient synthesis of allenols Togni-II reagent reaction partner. Triple roles reagent, including source trifluoromethyl group, hydroxyl oxidant, were elucidated in this transformation. Moreover, late-stage diversification performed, which revealed application potential preparation various compounds.

Language: Английский

Citations

19
Synthesis of Alkynylsilanes: A Review of the State of the Art DOI
Krzysztof Kuciński

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(11), P. 2382 - 2431

Published: April 12, 2024

Abstract This contribution offers a comprehensive overview of methods for forging sp C−Si bonds. Over time, alkynylsilanes (silylacetylenes), once considered mere byproducts hydrosilylation processes, have become essential building blocks in organic synthesis. literature review traces the evolution their synthesis, from traditional methodologies relying on organolithium and organomagnesium compounds to more advanced cross‐coupling reactions involving hydro‐ carbosilanes. Focused primarily past 25 years (2000–2024), it also extensively references significant historical breakthroughs. By analyzing synthetic methodologies, not only survey current state knowledge but identifies areas improvement. Furthermore, emphasize importance 1‐alkynylsilanes (1‐silyl‐1‐alkynes), selected applications these are highlighted, confirming potential

Language: Английский

Citations

6
EDA Complex-Enabled Annulation to Access CF2-Containing Tetralones and Quinazolinones Using Persulfates as Electron Donors DOI
Shupeng Zhang, Dawei Guo,

Mei-Ling Yang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(15), P. 10614 - 10623

Published: July 25, 2024

A photocatalyst-free and EDA complex-enabled radical cascade cyclization reaction of inactive alkenes with bromodifluoroacetamides was reported for the divergent synthesis fluorine-containing tetralones quinazolinones. In this transformation, persulfates as electron donors difluoro bromamide acceptors generate complex. This is a promising photochemical method advantages such mild conditions, simple operation, being metal-free, excellent functional group tolerance.

Language: Английский

Citations

6
Recent advances in the application of Langlois’ reagent in olefin difunctionalization DOI
Jiabin Shen, Lin Li, Jun Xu

et al.

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 21(10), P. 2046 - 2058

Published: Nov. 18, 2022

This review describes several key activation methods for Langlois' reagent in the difunctionalization of alkenes and could stimulate interest readers promoting wider development application reagent.

Language: Английский

Citations

27