Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(8), P. 2141 - 2148
Published: Jan. 1, 2022
The first approach of photoredox catalyzed radical–radical cross-coupling difluoromethylation C(sp 3 )−H bond was reported, featuring transition metal-free, good functional group tolerance, broad substrate scope and mild reaction conditions.
Language: Английский
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
60
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
53
Science, Journal Year: 2023, Volume and Issue: 381(6655), P. 302 - 306
Published: July 20, 2023
All fluorochemicals—including elemental fluorine and nucleophilic, electrophilic, radical fluorinating reagents—are prepared from hydrogen fluoride (HF). This highly toxic corrosive gas is produced by the reaction of acid-grade fluorspar (>97% CaF 2 ) with sulfuric acid under harsh conditions. The use to produce fluorochemicals via a process that bypasses HF desirable but remains an unsolved problem because prohibitive insolubility . Inspired calcium phosphate biomineralization, we herein disclose protocol treating dipotassium (K HPO 4 mechanochemical affords solid composed crystalline K 3 (HPO )F 2− x Ca y (PO F) b , which found suitable for forging sulfur-fluorine carbon-fluorine bonds.
Language: Английский
Citations
52
Chemical Papers, Journal Year: 2023, Volume and Issue: 77(8), P. 4085 - 4106
Published: April 13, 2023
Language: Английский
Citations
50
Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(15), P. 9397 - 9446
Published: July 7, 2023
The proportion of approved chiral drugs and drug candidates under medical studies has surged dramatically over the past two decades. As a consequence, efficient synthesis enantiopure pharmaceuticals or their synthetic intermediates poses profound challenge to medicinal process chemists. significant advancement in asymmetric catalysis provided an effective reliable solution this challenge. successful application transition metal catalysis, organocatalysis, biocatalysis pharmaceutical industries promoted discovery by precise preparation enantio-enriched therapeutic agents, facilitated industrial production active ingredient economic environmentally friendly fashion. present review summarizes most recent applications (2008–2022) industry ranging from scales pilot levels. It also showcases latest achievements trends agents with state art technologies catalysis.
Language: Английский
Citations
45
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 4026 - 4035
Published: Feb. 1, 2024
Herein, we report a divergent synthesis of fluoroalkyl ketones through visible-light-induced reactions between readily available organoboronic esters and acylsilanes. Selective control the reactivity in situ generated organoboronate complexes is key to achieving transformations. Under basic conditions, undergo deboronative fluoride elimination, resulting formation enol silyl ethers as intermediates that react with various electrophiles generate defluorinated products. Moreover, combination peroxide, 1,2-shift group favored over elimination ketal intermediates, leading This transition-metal-free reaction operationally simple, aryl, alkenyl, alkyl boronic are all suitable substrates. The synthetic potential has been demonstrated by gram-scale facile bioactive molecules including zifrosilone its analogs.
Language: Английский
Citations
31
Science, Journal Year: 2024, Volume and Issue: 384(6696), P. 670 - 676
Published: May 9, 2024
Electrochemistry offers a sustainable synthesis route to value-added fine chemicals but is often constrained by competing electron transfer between the electrode and redox-sensitive functionalities distinct from target site. Here, we describe an ion-shielding heterogeneous photoelectrocatalysis strategy impose mass-transfer limitations that invert thermodynamically determined order of transfer. This showcased enable decarboxylative trifluoromethylation sensitive (hetero)arenes using trifluoroacetate, inexpensive yet relatively inert trifluoromethyl group (CF
Language: Английский
Citations
28
Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(8), P. 958 - 966
Published: March 28, 2024
Language: Английский
Citations
25
Pharmaceuticals, Journal Year: 2024, Volume and Issue: 17(3), P. 281 - 281
Published: Feb. 22, 2024
The fluorine atom possesses many intrinsic properties that can be beneficial when incorporated into small molecules. These include the atom’s size, electronegativity, and ability to block metabolic oxidation sites. Substituents feature fluorine-containing groups are currently prevalent in drugs lower cholesterol, relieve asthma, treat anxiety disorders, as well improve chemical of various medications imaging agents. dye scaffolds (fluorescein/rhodamine, coumarin, BODIPY, carbocyanine, squaraine dyes) reported will address incorporation scaffold contribution it provides its application an agent. It is also important recognize radiolabeled atoms used for PET early detection diseases. This review discuss benefits incorporating molecules give examples fluorinated pharmaceutical industry techniques.
Language: Английский
Citations
21
Chemical Science, Journal Year: 2024, Volume and Issue: 15(8), P. 2712 - 2724
Published: Jan. 1, 2024
Frustrated Lewis pair (FLP) bond activation chemistry has greatly developed over the last two decades since seminal report of metal-free reversible hydrogen activation. Recently, FLP systems have been utilized to allow monoselective C-F (at equivalent sites) in polyfluoroalkanes. The problem 'over-defluorination' functionalization polyfluoroalkanes (where multiple fluoro-positions are uncontrollably functionalized) a long-standing chemical fluorocarbon for 80 years. mediated is complementary other solutions address and offers several advantages unique opportunities. This perspective highlights some these opportunities places development into context wider effort overcome 'over-defluorination'.
Language: Английский
Citations
20