Recent Advances in C–F Bond Activation of Acyl Fluorides Directed toward Catalytic Transformation by Transition Metals, N-Heterocyclic Carbenes, or Phosphines DOI
Yasushi Nishihara, Tian Tian, Qiang Chen

et al.

Synthesis, Journal Year: 2022, Volume and Issue: 54(17), P. 3667 - 3697

Published: May 6, 2022

Abstract Numerous studies on the activation of carbon–fluorine bonds have been reported in recent years. For example, acyl fluorides utilized as versatile reagents for acylation, arylation, and even fluorination. In this review, we focus compounds with bonds, highlight advances strategies their C–F via transition-metal catalysis, N-heterocyclic carbene (NHCs) organophosphine classical nucleophilic substitution reactions. 1 Introduction 2 Transition-Metal-Mediated Bond Activation 2.1 Acylation (Carbonyl-Retentive) Coupling Reactions 2.2 Decarbonylative 2.3 by Other Transition Metals 3 N-Heterocyclic Carbenes 3.1 NHC-Catalyzed Cycloaddition Acyl Fluorides 3.2 Radical Functionalization 3.3 Nucleophilic Fluorination (Hetero)aromatics 4 Phosphines 4.1 Phosphine-Catalyzed Direct 4.2 Indirect 5 Classical Substitution 6 Miscellaneous Examples 7 Summary Perspective

Language: Английский

Recent advances in visible-light-mediated organic transformations in water DOI
Kai Sun, Qi‐Yan Lv, Xiaolan Chen

et al.

Green Chemistry, Journal Year: 2020, Volume and Issue: 23(1), P. 232 - 248

Published: Dec. 11, 2020

Water is a green reaction medium, while visible light represents renewable, clean, and abundant energy source. The recent advances in visible-light-mediated organic transformations water are summarized.

Language: Английский

Citations

158
Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications DOI
Mingzhu Lu, Jeffrey Goh, Manikantha Maraswami

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(24), P. 17479 - 17646

Published: Oct. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

Language: Английский

Citations

150
Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups DOI
Feng Zhao, Wenlong Zhou,

Zuo Zuo

et al.

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 364(2), P. 234 - 267

Published: Nov. 29, 2021

Abstract Fluorine‐containing moieties are widely used in the pharmaceutical, agrochemical, and material fields. Thus, these structures of immense interest fields organic synthesis medicinal chemistry. Among various fluorinated groups, difluoromethyl unit has drawn increasing attention due to its unique pharmaceutical properties. In recent years, several methods for difluoromethylated compounds have been rapidly developed. However, most treat aromatic with excess difluoromethylating reagents, which often contain organometallic compounds, so transformations generally less environmentally friendly atom‐economical. this review, we summarize development new motifs or difluoroalkenes from trifluoromethylated trifluoromethyl alkenes via single C( sp 3 )−F bond cleavage. magnified image

Language: Английский

Citations

122
Photoredox-Catalyzed Defluorinative Carboxylation of gem-Difluorostyrenes with Formate Salt DOI
Chao Sun, Quan Zhou, Chuan‐Ying Li

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(4), P. 883 - 888

Published: Jan. 22, 2024

Herein, we present a transition-metal-free, easy handling protocol for regioselective carboxylation of gem-difluorostyrenes with sodium formate as the C1 source. 30 examples α-fluoracrylates were obtained in yields to 80% under these conditions. A defluorinative monofluorovinyl intermediate and consecutive photoinduced electron transfer mechanism proposed after investigation.

Language: Английский

Citations

26
Recent Advances in the Electrochemical Defluorinative Transformations of C—F Bonds DOI

Qinhui Wan,

Ruixue Liu, Zhongyi Zhang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(16), P. 1913 - 1928

Published: April 24, 2024

Comprehensive Summary Organic fluorine compounds are ubiquitous and pivotally important organic molecules, yet their activation transformation have long been a formidable challenge due to the high energy low reactivity of C—F bonds. electrosynthesis, an environmentally benign synthetic method in chemistry, enables myriad chemical transformations without need for external redox reagents. In recent years, electrochemistry has emerged as powerful tool achieving bonds fluorine‐containing compounds. This review aims succinctly recapitulate latest advancements electrochemical defluorinative delve into reaction design, mechanistic insights, developmental prospects these methods. Key Scientists 1959, Lund was first pioneer electroreduction CF 3 CH group. Electrochemistry lately provided new opportunities efficient conversion fluorides. 2020, Zhou coworkers discovered carboxylation α‐CF alkenes. Lambert colleagues reported electrophotocatalytic amination aryl Electrochemical hydrodefluorination trifluoromethylketones developed by Lennox 2021. same year, Wang Guo disclosed radical alkylation alkenes with Katritzky salts alkyl precursors. Subsequently, Wu Liao described transition‐metal‐free, site‐selective arylation polyfluoroarenes (het)arenes using paired electrophotocatalysis. 2023, numerous efforts were made achieve bond activation. Xia organoboron‐controlled chemoselective sequential (deutero)hydrodefluorination trifluoroacetamides.

Language: Английский

Citations

26
Photocatalytic Three-Component Reductive Coupling Synthesis of gem-Difluorohomoallyl Secondary Amines DOI

Bingbing Feng,

Meifang Tang,

Rui Xiao

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

gem-Difluorohomoallyl amines, an important class of gem-difluoroalkenes, are prevalent moieties in many bioactive compounds. However, limited methods suitable for the synthesis this type compound containing secondary amines. Here, we display a photocatalytic multicomponent protocol gem-difluoroalkenes which makes use readily available materials: arylamines, alkyl aldehydes, and α-trifluoromethyl alkenes. Moreover, ketones amines also substrates. Preliminary mechanistic experiments indicate that key α-amino radical was involved, generated from reduction situ-formed imines (or iminium ions) by reduced photocatalyst. Subsequent addition to alkenes β-F elimination deliver desired products.

Language: Английский

Citations

2
Highly Regio‐ and Enantioselective Hydrosilylation of gem‐Difluoroalkenes by Nickel Catalysis DOI
Dachang Bai, Fen Wu,

Lingna Chang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(10)

Published: Dec. 27, 2021

The synthesis of small organic molecules with a difluoromethylated stereocenter is particularly attractive in drug discovery. Herein, we have developed an efficient method for the direct generation stereocenters through Ni0 -catalyzed regio- and enantioselective hydrosilylation gem-difluoroalkenes. reaction also represents construction carbon(sp3 )-silicon bonds nickel catalysis, which provides atom- step-economical route high-value optically active α-difluoromethylsilanes. This protocol features readily available starting materials commercial chiral broad substrates spanning range functional groups high yield (up to 99 % yield) excellent enantioselectivity 96 ee). enantioenriched products undergo variety stereospecific transformations. Preliminary mechanistic studies were performed.

Language: Английский

Citations

63
Multiple-fold C–F bond functionalization for the synthesis of (hetero)cyclic compounds: fluorine as a detachable chemical handle DOI
Danhua Ge, Xue‐Qiang Chu

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(7), P. 2013 - 2055

Published: Jan. 1, 2022

We highlighted the recent advances in field of multiple-fold C–F bond functionalization for synthesis (hetero)cyclic compounds.

Language: Английский

Citations

47
Photoredox Metal-Free Allylic Defluorinative Silylation of α-Trifluoromethylstyrenes with Hydrosilanes DOI
Cong Luo, Yang Zhou, Hang Chen

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(23), P. 4286 - 4291

Published: June 8, 2022

We report an efficient strategy that combines organic photoredox and hydrogen atom transfer to deliver gem-difluoroallylsilanes via defluorinative silylation of α-trifluoromethylstyrenes using hydrosilanes as silicon sources. This protocol provides environmentally friendly approach for the preparation structurally diverse with excellent functional group compatibility renders it suitable late-stage modification bioactive complex molecules.

Language: Английский

Citations

45
Photoredox-Catalyzed Allylic Defluorinative Alkoxycarbonylation of Trifluoromethyl Alkenes through Intermolecular Alkoxycarbonyl Radical Addition DOI
Jiaxin Wang, Wei Ge, Ming‐Chen Fu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(7), P. 1471 - 1475

Published: Feb. 15, 2022

The gem-difluoroalkene moiety is an ideal carbonyl bioisostere in medicinal chemistry, but efficient synthesis of β-gem-difluoroalkene esters remains challenging so far. Herein, we disclose a photoredox-catalyzed allylic defluorinative alkoxycarbonylation trifluoromethyl alkenes enabled by intermolecular alkoxycarbonyl radical addition. A wide variety alcohol oxalate derivatives were amenable, affording various with excellent functional group tolerance. Notably, the potential synthetic value this method highlighted successful late-stage modification for bioactive molecules.

Language: Английский

Citations

40