Synthesis of perfluoroaryl sulfides at electron-poor arenes via an S Ar step with an unexpected mechanism DOI
Hsuan‐Hung Liao, Shao‐Chi Lee,

Hsin Kao

et al.

Cell Reports Physical Science, Journal Year: 2022, Volume and Issue: 3(8), P. 101010 - 101010

Published: Aug. 1, 2022

Language: Английский

Strategies for Nucleophilic C(sp3)–(Radio)Fluorination DOI
Isabelle Nathalie-Marie Leibler, Shivaani Gandhi, Makeda A. Tekle‐Smith

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(18), P. 9928 - 9950

Published: April 24, 2023

This Perspective surveys the progress and current limitations of nucleophilic fluorination methodologies. Despite long rich history C(sp3)–F bond construction in chemical research, inherent challenges associated with this transformation have largely constrained to a privileged reaction platform. In recent years, Doyle group─along many others─has pursued study development intent generating deeper mechanistic understanding, developing user-friendly reagents, contributing invention synthetic methods capable enabling radiofluorination. Studies from our laboratory are discussed along developments others field. Fluoride reagent implications identity highlighted. We also outline space inaccessible by technologies series future directions field that can potentially fill existing dark spaces.

Language: Английский

Citations

51
Enantioconvergent nucleophilic substitution via synergistic phase-transfer catalysis DOI Creative Commons
C. J. Dooley, Francesco Ibba, Bence B. Botlik

et al.

Nature Catalysis, Journal Year: 2025, Volume and Issue: 8(2), P. 107 - 115

Published: Feb. 13, 2025

Language: Английский

Citations

2
Electron-Transfer-Enabled Concerted Nucleophilic Fluorination of Azaarenes: Selective C–H Fluorination of Quinolines DOI Creative Commons
Li Zhang, Jiyao Yan, Dilgam Ahmadli

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(37), P. 20182 - 20188

Published: Sept. 11, 2023

Direct C-H fluorination is an efficient strategy to construct aromatic C-F bonds, but the cleavage of specific bonds in presence other functional groups and high barrier bond formation make transformation challenging. Progress for electrophilic arenes has been reported, a similar electron-deficient azaarenes remained elusive due energy corresponding Wheland intermediates. Nucleophilic difficult owing identity Meisenheimer intermediate after fluoride attack, from which elimination regenerate substrate favored over hydride form product. Herein, we report new concept nucleophilic without azaarene intermediates through chain process with asynchronous concerted F--e--H+ transfer. The substitution allows first successful oxidative quinolines.

Language: Английский

Citations

20
Tetramethylammonium Fluoride Alcohol Adducts for SNAr Fluorination DOI
María T. Morales-Colón, Yi Yang See, So Jeong Lee

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(11), P. 4493 - 4498

Published: May 24, 2021

Nucleophilic aromatic fluorination (SNAr) is among the most common methods for formation of C(sp2)–F bonds. Despite many recent advances, a long-standing limitation these transformations requirement rigorously dry, aprotic conditions to maintain nucleophilicity fluoride and suppress generation side products. This report addresses this challenge by leveraging tetramethylammonium alcohol adducts (Me4NF·ROH) as sources SNAr fluorination. Through systematic tuning substituent (R), tert-amyl (Me4NF·t-AmylOH) was identified an inexpensive, practical, bench-stable reagent under mild convenient (80 °C in DMSO, without drying reagents or solvent). A substrate scope more than 50 (hetero) aryl halides nitroarene electrophiles demonstrated.

Language: Английский

Citations

33
Direct Synthesis of α‐Aryl‐α‐Trifluoromethyl Alcohols via Nickel Catalyzed Cross‐Electrophile Coupling DOI Creative Commons
Lorenzo Lombardi,

Alessandro Cerveri,

Riccardo Giovanelli

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(47)

Published: Sept. 26, 2022

A nickel-catalyzed reductive cross-electrophile coupling between the redox-active N-trifluoroethoxyphthalimide and iodoarenes is documented. The protocol reproduces a formal arylation of trifluoroacetaldehyde under mild conditions in high yields (up to 88 %) with large functional group tolerance (30 examples). combined computational experimental investigation revealed pivotal solvent assisted 1,2-Hydrogen Atom Transfer (HAT) process generate nucleophilic α-hydroxy-α-trifluoromethyl C-centered radical for Csp

Language: Английский

Citations

26
A broadly applicable quantitative relative reactivity model for nucleophilic aromatic substitution (SNAr) using simple descriptors DOI Creative Commons

Jingru Lu,

Irina Paci, David C. Leitch

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(43), P. 12681 - 12695

Published: Jan. 1, 2022

A model for S N Ar reactivity is reported, built from relative rate data obtained by competition studies. Based only on molecular descriptors of the electrophile, predicts and site selectivity many complex substrates.

Language: Английский

Citations

24
Tetramethylammonium Fluoride: Fundamental Properties and Applications in C-F Bond-Forming Reactions and as a Base DOI Open Access
Vladimir Iashin, Tom Wirtanen, Jesús E. Perea‐Buceta

et al.

Catalysts, Journal Year: 2022, Volume and Issue: 12(2), P. 233 - 233

Published: Feb. 18, 2022

Nucleophilic ionic sources of fluoride are essential reagents in the synthetic toolbox to access high added-value fluorinated building blocks unattainable by other means. In this review, we provide a concise description and rationale outstanding features one these reagents, tetramethylammonium (TMAF), as well disclosing different methods for its preparation, how physicochemical properties solvation effects solvents intimately associated with reactivity. Furthermore, herein also comprehensively describe historic recent utilization, up December 2021, C-F bond-forming reactions special emphasis on nucleophilic aromatic substitution fluorinations potential sustainable application industrial settings, use base capable rendering unprecedented transformations.

Language: Английский

Citations

23
One‐Carbon Ring Expansion of Indoles and Pyrroles: A Straightforward Access to 3‐Fluorinated Quinolines and Pyridines DOI Open Access

Huaixuan Guo,

Shiqin Qiu,

Peng Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(5)

Published: Dec. 12, 2023

Abstract 3‐Fluorinated quinolines and pyridines are prevalent pharmacophores, yet their synthesis is often challenging. Herein, we demonstrate that dibromofluoromethane as bromofluorocarbene source enables the one‐carbon ring expansion of readily available indoles pyrroles to structurally diverse 3‐fluorinated pyridines. This straightforward protocol requires only a short reaction time ten minutes can be performed under air atmosphere. Preliminary investigations reveal this strategy also applied other valuable azines by using different 1,1‐dibromoalkanes bromocarbene sources.

Language: Английский

Citations

15
Three-component aminofluorination of alkenes with electronically rich amino sources DOI Creative Commons
Yang Li,

Jiamin Bao,

Yu Zhang

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(4), P. 1147 - 1163

Published: March 18, 2022

Language: Английский

Citations

21
Recent progress on radiofluorination using metals: strategies for generation of C–18F bonds DOI
Truong Giang Luu, Hee‐Kwon Kim

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(22), P. 5746 - 5781

Published: Jan. 1, 2023

This review summarizes recent progress in metal-mediated radiofluorination studies for C– 18 F bond formation to provide organofluorine-18 compounds.

Language: Английский

Citations

11