Recent advances in radical enabled selective Csp3-F bond activation of multifluorinated compounds

Article Chemistry, Organic

Photoredox-Catalyzed Difunctionalization of Unactivated Olefins for Synthesizing Lactam-Substituted gem-Difluoroalkenes

Jie Shi et al.

Summary: A photoredox-catalyzed radical cascade reaction has been developed for the synthesis of lactam-substituted gem-difluoroalkenes, providing a simple method with good functional group tolerance and high yields.

ORGANIC LETTERS (2021)

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Article Chemistry, Organic

Photoredox/Hydrogen Atom Transfer Cocatalyzed C-H Difluoroallylation of Amides, Ethers, and Alkyl Aldehydes

Yuan-Qiang Guo et al.

Summary: This study introduces a method that combines hydrogen atom transfer and photoredox catalysis to achieve the dehydrogenative difluoroallylation of amides, ethers, and alkyl aldehydes. The method transforms a wide range of substrates into gem-difluoroalkenes via the construction of C(sp(3))-C(sp(3)) or C(sp(3))-C(sp(2)) bonds, with excellent functional group compatibility and high selectivity. It is suitable for late-stage modification of pharmaceutical intermediates due to its versatility in substrate types.

ORGANIC LETTERS (2021)

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Article Multidisciplinary Sciences

Sequential C-F bond functionalizations of trifluoroacetamides and acetates via spin-center shifts

You-Jie Yu et al.

Summary: A general strategy for sequential carbon-fluorine (C-F) bond functionalizations of trifluoroacetamides and trifluoroacetates has been described, enabling the sequential generation of difluoro- and monofluoroalkyl radicals for diverse fluorinated products. The reaction mechanism and chemoselectivity were established through experimental and computational approaches.

SCIENCE (2021)

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Article Chemistry, Multidisciplinary

Site-Selective Defluorinative sp3 C-H Alkylation of Secondary Amides

Wen-Jun Yue et al.

Summary: This new method features mild conditions, wide applicability, and exquisite site-selectivity, allowing for the rapid and reliable incorporation of gemdifluoroalkene motifs into previously unfunctionalized sp(3) sites, thus providing a new platform for introducing carbonyl isosteres at saturated hydrocarbon sites.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Chromium-Catalyzed Allylic Defluorinative Ketyl Olefin Coupling

Chang Zhang et al.

Summary: A novel chromium-catalyzed reaction was reported for the efficient synthesis of gem-difluorohomoallylic alcohols, with high chemoselectivity towards formyl moiety conversion in the presence of other functionalities. Simple derivatizations of the hydroxyl group of the coupling products demonstrate the utility of this method.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Photoredox-Catalyzed C-F Bond Allylation of Perfluoroalkylarenes at the Benzylic Position

Naoki Sugihara et al.

Summary: Site-selective and direct C-F bond transformation of perfluoroalkylarenes was achieved using an iridium photoredox catalyst system with allylic stannanes. The defluoroallylation process exclusively occurs at the benzylic position through perfluoroalkyl radicals generated by a single-electron transfer. Different perfluoroalkyl groups are applicable, and the utility of this reaction was demonstrated through the synthesis of a specific compound.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Visible-Light-Induced Palladium-Catalyzed Selective Defluoroarylation of Trifluoromethylarenes with Arylboronic Acids

Yun-Cheng Luo et al.

Summary: Selective functionalization of inactive C(sp(3))-F bonds to prepare medicinally interesting aryldifluoromethylated compounds remains challenging. One promising route is the transition-metal-catalyzed cross-coupling through oxidative addition of the C(sp(3))-F bond in trifluoromethylarenes (ArCF3), which are ideal precursors for this process due to their ready availability and low cost. Here, we report an unprecedented excited-state palladium catalysis strategy for selective defluoroarylation of trifluoromethylarenes with arylboronic acids. This visible-light-induced palladium-catalyzed cross-coupling proceeds under mild reaction conditions and allows transformation of a variety of arylboronic acids and ArCF3. Preliminary mechanistic studies reveal that the oxidative addition of the C(sp(3))-F bond in ArCF3 to excited-state palladium(0) via a single electron transfer pathway is responsible for the C(sp(3))-F bond activation.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Visible-light photoredox-catalyzed selective carboxylation of C(sp3)-F bonds with CO2

Si-Shun Yan et al.

Summary: This study demonstrates the dual role of CO2 as both an electron carrier and an electrophile, enabling selective carboxylation of C(sp(3))-F bonds to construct various alpha-fluorocarboxylic acids via visible-light photoredox catalysis. The fluorinated substrates undergo reduction by CO2 radical anions generated from sequential hydride-transfer reduction and hydrogen-atom transfer processes. This methodology shows promise for the late-stage functionalization of complex molecules.

CHEM (2021)

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Review Chemistry, Multidisciplinary

Radical trifluoromethylation

Haiwen Xiao et al.

Summary: The trifluoromethyl group is becoming increasingly important in various fields such as pharmaceuticals, agrochemicals, and materials, with recent advances in trifluoromethylation of carbon-centered radical intermediates being discussed in this tutorial.

CHEMICAL SOCIETY REVIEWS (2021)

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Article Chemistry, Multidisciplinary

NiH-Catalyzed Migratory Defluorinative Olefin Cross-Coupling: Trifluoromethyl-Substituted Alkenes as Acceptor Olefins to Form gem-Difluoroalkenes

Fenglin Chen et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Multidisciplinary

Visible-Light-Induced Selective Defluoroborylation of Polyfluoroarenes, gem-Difluoroalkenes, and Trifluoromethylalkenes

Wengang Xu et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Multidisciplinary

Photoinduced Single-Electron Transfer as an Enabling Principle in the Radical Borylation of Alkenes with NHC-Borane

Peng-Ju Xia et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Organic

Visible-Light-Mediated β-C-H gem-Difluoroallylation of Aldehydes and Cyclic eKetones through C-F Bond Cleavage of 1-Trifluoromethyl Alkenes

Devireddy Anand et al.

ORGANIC LETTERS (2020)

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Article Chemistry, Organic

Visible-Light-Induced Deoxygenation/Defluorination Protocol for Synthesis of γ,γ-Difluoroallylic Ketones

Yuan-Qiang Guo et al.

ORGANIC LETTERS (2020)

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Article Chemistry, Multidisciplinary

New Radical Borylation Pathways for Organoboron Synthesis Enabled by Photoredox Catalysis

Jing Qi et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Multidisciplinary

Organophotoredox Hydrodefluorination of Trifluoromethylarenes with Translational Applicability to Drug Discovery

Jeroen B. Sap et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

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Article Multidisciplinary Sciences

Manganese-mediated reductive functionalization of activated aliphatic acids and primary amines

Zhan Li et al.

NATURE COMMUNICATIONS (2020)

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Article Chemistry, Organic

Synthesis of gem-Difluoroalkenes via Zn-Mediated Decarboxylative/Defluorinative Cross-Coupling

Hai-Wu Du et al.

ORGANIC LETTERS (2020)

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Review Chemistry, Multidisciplinary

Recent progress on selective deconstructive modes of halodifluoromethyl and trifluoromethyl-containing reagents

Xingxing Ma et al.

CHEMICAL SOCIETY REVIEWS (2020)

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Article Chemistry, Multidisciplinary

Direct electrochemical defluorinative carboxylation of α-CF3 alkenes with carbon dioxide

Xiao-Tong Gao et al.

CHEMICAL SCIENCE (2020)

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Article Chemistry, Organic

Visible-Light-Promoted Redox Neutral γ,γ-Difluoroallylation of Cycloketone Oxime Ethers with Trifluoromethyl Alkenes via C-C and C-F Bond Cleavage

Yuwei He et al.

ORGANIC LETTERS (2019)

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Article Chemistry, Organic

Photocatalytic, Phosphoranyl Radical-Mediated N-O Cleavage of Strained Cycloketone Oximes

Peng-Ju Xia et al.

ORGANIC LETTERS (2019)

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Article Chemistry, Multidisciplinary

Selective Defluoroallylation of Trifluoromethylarenes

Chaosheng Luo et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

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Article Chemistry, Multidisciplinary

Selective C-F Functionalization of Unactivated Trifluoromethylarenes

David B. Vogt et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

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Editorial Material Multidisciplinary Sciences

Fluorine and amide groups together at last

Jonathan Clayden

NATURE (2019)

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Article Chemistry, Physical

Synthesis of gem-Difluoroalkenes via Nickel-Catalyzed Reductive C-F and C-O Bond Cleavage

Zhiyang Lin et al.

ACS CATALYSIS (2019)

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Article Chemistry, Multidisciplinary

Nickel-catalyzed allylic defluorinative alkylation of trifluoromethyl alkenes with reductive decarboxylation of redox-active esters

Xi Lu et al.

CHEMICAL SCIENCE (2019)

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Review Chemistry, Multidisciplinary

Recent advances in the synthesis and applications of α-(trifluoromethyl)styrenes in organic synthesis

Feitao Tian et al.

CHEMICAL COMMUNICATIONS (2019)

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Article Chemistry, Multidisciplinary

Catalytic Defluoroalkylation of Trifluoromethylaromatics with Unactivated Alkenes

Hengbin Wang et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2018)

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Article Chemistry, Medicinal

Fluorine and Fluorinated Motifs in the Design and Application of Bioisosteres for Drug Design

Nicholas A. Meanwell

JOURNAL OF MEDICINAL CHEMISTRY (2018)

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Article Chemistry, Physical

Synthesis of gem-Difluoroalkenes via Nickel-Catalyzed Allylic Defluorinative Reductive Cross-Coupling

Yun Lan et al.

ACS CATALYSIS (2018)

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Article Chemistry, Organic

A photocatalytic decarboxylative/defluorinative [4+3] annulation of o-hydroxyphenylacetic acids and trifluoromethyl alkenes: synthesis of fluorinated dihydrobenzoxepines

Haoguo Chen et al.

ORGANIC CHEMISTRY FRONTIERS (2018)

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Review Chemistry, Organic

Selective Late-Stage Hydrodefluorination of Trifluoromethylarenes: A Facile Access to Difluoromethylarenes

Socrates B. Munoz et al.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2017)

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Article Chemistry, Multidisciplinary

Cooperative Al-H Bond Activation in DIBAL-H: Catalytic Generation of an Alumenium-Ion-Like Lewis Acid for Hydrodefluorinative Friedel-Crafts Alkylation

Francis Forster et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2017)

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Article Chemistry, Multidisciplinary

Selective Single C(sp3)-F Bond Cleavage in Trifluoromethylarenes: Merging Visible-Light Catalysis with Lewis Acid Activation

Kang Chen et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2017)

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Article Chemistry, Multidisciplinary

Photoredox Generation of Carbon-Centered Radicals Enables the Construction of 1,1-Difluoroalkene Carbonyl Mimics

Simon B. Lang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2017)

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Article Chemistry, Multidisciplinary

Visible-Light-Mediated Two-Fold Unsymmetrical C(sp3)-H Functionalization and Double C-F Substitution

Linyong Li et al.

CHEMISTRY-A EUROPEAN JOURNAL (2017)

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Review Chemistry, Multidisciplinary

The unique fluorine effects in organic reactions: recent facts and insights into fluoroalkylations

Chuanfa Ni et al.

CHEMICAL SOCIETY REVIEWS (2016)

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Article Chemistry, Organic

Synthesis of Functionalized gem-Difluoroalkenes via a Photocatalytic Decarboxylative/Defluorinative Reaction

Tiebo Xiao et al.

JOURNAL OF ORGANIC CHEMISTRY (2016)

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Article Chemistry, Medicinal

Applications of Fluorine in Medicinal Chemistry

Eric P. Gillis et al.

JOURNAL OF MEDICINAL CHEMISTRY (2015)

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Article Chemistry, Organic

An overview of reductive trifluoromethylation reactions using electrophilic '+CF3' reagents

Shi-Meng Wang et al.

TETRAHEDRON (2015)

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Review Chemistry, Multidisciplinary

Addition of CF3 across unsaturated moieties: a powerful functionalization tool

Estibaliz Merino et al.

CHEMICAL SOCIETY REVIEWS (2014)

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Article Chemistry, Physical

Main-Group Lewis Acids for C-F Bond Activation

Timo Stahl et al.

ACS CATALYSIS (2013)

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Review Chemistry, Multidisciplinary

C-F Bond Activation in Organic Synthesis

Hideki Amii et al.

CHEMICAL REVIEWS (2009)

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Review Chemistry, Multidisciplinary

Fluorine in medicinal chemistry

Sophie Purser et al.

CHEMICAL SOCIETY REVIEWS (2008)

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Review Multidisciplinary Sciences

Fluorine in pharmaceuticals:: Looking beyond intuition

Klaus Mueller et al.

SCIENCE (2007)

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Article Chemistry, Organic

Low-valent niobium-catalyzed reduction of α,α,α-trifluorotoluenes

Kohei Fuchibe et al.

ORGANIC LETTERS (2007)

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Article Chemistry, Multidisciplinary

Room-temperature catalytic hydrodefluorination of C(sp3)-F bonds

VJ Scott et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2005)

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Article Chemistry, Inorganic & Nuclear

A review of Mg metal-promoted C-F bond activation; a reliable synthetic approach to difluorinated organic compounds

K Uneyama et al.

JOURNAL OF FLUORINE CHEMISTRY (2002)

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Recent advances in radical enabled selective Csp3-F bond activation of multifluorinated compounds

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