Organoboron Reagent-Controlled Selective (Deutero)Hydrodefluorination

Review Chemistry, Applied

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Feng Zhao et al.

Summary: This review summarizes the recent developments of new methods for the synthesis of difluoromethyl motifs or difluoroalkenes from trifluoromethylated aromatic compounds or trifluoromethyl alkenes via single C(sp(3))-F bond cleavage.

ADVANCED SYNTHESIS & CATALYSIS (2022)

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Article Chemistry, Multidisciplinary

A Carbene Strategy for Progressive (Deutero)Hydrodefluorination of Fluoroalkyl Ketones

Xiaolong Zhang et al.

Summary: Hydrodefluorination is a promising chemical strategy for degrading perfluorochemicals into partially fluorinated compounds, but controlled progressive hydrodefluorination remains a challenge. The study describes a carbene strategy for sequential (deuterio)hydrodefluorination of perfluoroalkyl ketones under rhodium catalysis, allowing for the controllable preparation of difluoroalkyl- and monofluoroalkyl ketones with high yield and excellent functional group tolerance.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

Photoredox-Catalyzed Defluorinative Functionalizations of Polyfluorinated Aliphatic Amides and Esters

Jian-Heng Ye et al.

Summary: A new catalytic approach for the selective functionalization of strong C-F bonds in polyfluorinated aliphatic esters and amides has been reported, allowing access to important partially fluorinated motifs.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Multidisciplinary Sciences

Photocatalytic defluoroalkylation and hydrodefluorination of trifluoromethyls using o-phosphinophenolate

Can Liu et al.

Summary: The authors utilize o-phosphinophenolate as a photoredox catalyst to activate trifluoromethyl groups under visible light irradiation. This enables the selective defluoroalkylation and hydrodefluorination of trifluoroacetamides, trifluoroacetates, and trifluoromethyl (hetero)arenes, resulting in the formation of difluoromethyl radicals. The study provides a facile synthesis of difluoromethylene-incorporated carbonyl and (hetero)aromatic compounds, which are important intermediates in the pharmaceutical industry.

NATURE COMMUNICATIONS (2022)

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Article Chemistry, Multidisciplinary

C-F bond functionalizations of trifluoromethyl groups via radical intermediates

Tesfaye Tebeka Simur et al.

Summary: This review article provides a brief overview of recently reported methods used to functionalize C-F bonds in CF3 groups via radical intermediates, with an emphasis on the discussion of mechanistic aspects and synthetic applications.

CHINESE CHEMICAL LETTERS (2022)

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Article Chemistry, Physical

Defluorinative Carboimination of Trifluoromethyl Ketones

Xiaolong Zhang et al.

Summary: A silver-catalyzed rearrangement method for the defluorinative difunctionalization of trifluoromethyl ketones to synthesize α,α-difluoroimines has been reported. This approach involves the integration of successive C-F bond cleavage and C-C/C-N bond formation on a single molecule entity, different from the stepwise mechanism of previous carbodefluorination methods. The silver catalysis plays a critical role in the C-F bond cleavage and aza-Claisen rearrangement stages.

ACS CATALYSIS (2022)

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Article Chemistry, Multidisciplinary

Photochemical C-F Activation Enables Defluorinative Alkylation of Trifluoroacetates and -Acetamides

Mark W. Campbell et al.

Summary: A photochemically mediated method has been successfully developed for the defluorinative alkylation of ethyl trifluoroacetate, providing an efficient pathway for the synthesis of novel gem-difluoro analogs. This method can also be used for the hydroalkylation of a diverse suite of alkenes, expanding the range of substrates for the reaction.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (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

Bipyridinium and Phenanthrolinium Dications for Metal-Free Hydrodefluorination: Distinctive Carbon-Based Reactivity

Katherine I. Burton et al.

Summary: The development of novel Lewis acids derived from bipyridinium and phenanthrolinium dications has shown high carbon-based Lewis acidity, making them effective catalysts for hydrodefluorination reactions. These Lewis acids are capable of generating catalytically active silylium cations and have been successfully used for the initiation of deuterodefluorination reactions. Experimental and computational data support the role of these dications as initiators in the generation of silylium cations.

CHEMISTRY-A EUROPEAN JOURNAL (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

Nickel-catalyzed reductive monofluoroakylation of alkyl tosylate with bromofluoromethane to primary alkyl fluoride

Ru Cui et al.

Summary: A nickel-catalysed direct terminal monofluoromethylaion between alkyl tosylates and bromofluoromethane has been developed, demonstrating high efficiency, mild conditions, and good functional-group compatibility. The success of this transformation lies in the selection of ligand and mild base, ensuring the generation of various terminal monofluoromethylation products.

CHEMICAL COMMUNICATIONS (2021)

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Article Chemistry, Multidisciplinary

Direct electrochemical hydrodefluorination of trifluoromethylketones enabled by non-protic conditions

John R. Box et al.

Summary: CF2H groups are unique in their combination of lipophilic and hydrogen bonding properties, with the strength of hydrogen bonding determined by the attached group. Electrochemical hydrodefluorination has been developed as a method for the preparation of under-studied difluoromethyl ketones. Analysis has shown difluoromethyl ketones to potentially be highly useful as dual hydrogen bond donor/acceptor moieties.

CHEMICAL SCIENCE (2021)

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Article Chemistry, Multidisciplinary

Frustrated Lewis-Pair-Meditated Selective Single Fluoride Substitution in Trifluoromethyl Groups

Dipendu Mandal et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

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Article Chemistry, Organic

Direct and Chemoselective Electrophilic Monofluoromethylation of Heteroatoms (O-, S-, N-, P-, Se-) with Fluoroiodomethane

Raffaele Senatore et al.

ORGANIC LETTERS (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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Review Chemistry, Multidisciplinary

Contribution of Organofluorine Compounds to Pharmaceuticals

Munenori Inoue et al.

ACS OMEGA (2020)

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Review Chemistry, Multidisciplinary

Powering the Future: How Can Electrochemistry Make a Difference in Organic Synthesis?

Tjark H. Meyer et al.

CHEM (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

Isotope Effect in the Magneto-Optoelectronic Response of Organic Light-Emitting Diodes Based on Donor-Acceptor Exciplexes

Xiaojie Liu et al.

ADVANCED MATERIALS (2020)

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Review Chemistry, Multidisciplinary

Making electrochemistry easily accessible to the synthetic chemist

Christiane Schotten et al.

GREEN CHEMISTRY (2020)

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Article Chemistry, Organic

Palladium Catalyzed Hydrodefluorination of Fluoro-(hetero)arenes

Joseph J. Gair et al.

ORGANIC LETTERS (2019)

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Article Chemistry, Multidisciplinary

Hydrodifluoromethylation of Alkenes with Difluoroacetic Acid

Claudio F. Meyer et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

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Article Chemistry, Medicinal

CF2H, a Functional Group-Dependent Hydrogen-Bond Donor: Is It a More or Less Lipophilic Bioisostere of OH, SH, and CH3?

Yossi Zafrani et al.

JOURNAL OF MEDICINAL CHEMISTRY (2019)

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Article Chemistry, Physical

Visible-Light-Triggered Monofluoromethylation of Alkenes by Strongly Reducing 1,4-Bis(diphenylamino)naphthalene Photoredox Catalysis

Naoki Noto et al.

ACS CATALYSIS (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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Article Chemistry, Medicinal

Applications of Deuterium in Medicinal Chemistry

Tracey Pirali et al.

JOURNAL OF MEDICINAL CHEMISTRY (2019)

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Review Chemistry, Organic

Recent progress in photochemical radical di- and mono-fluoromethylation

Takashi Koike et al.

ORGANIC & BIOMOLECULAR CHEMISTRY (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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Review Chemistry, Multidisciplinary

Deuterium- and Tritium-Labelled Compounds: Applications in the Life Sciences

Jens Atzrodt et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

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Review Chemistry, Multidisciplinary

Picking One out of Three: Selective Single C-F Activation in Trifluoromethyl Groups

Florian Jaroschik

CHEMISTRY-A EUROPEAN JOURNAL (2018)

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Review Chemistry, Multidisciplinary

Use of Electrochemistry in the Synthesis of Heterocyclic Structures

Yangye Jiang et al.

CHEMICAL REVIEWS (2018)

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Article Chemistry, Medicinal

Difluoromethyl Bioisostere: Examining the Lipophilic Hydrogen Bond Donor Concept

Yossi Zafrani et al.

JOURNAL OF MEDICINAL CHEMISTRY (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

CF2H, a Hydrogen Bond Donor

Chanan D. Sessler et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2017)

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Article Biotechnology & Applied Microbiology

First deuterated drug approved

Charles Schmidt

NATURE BIOTECHNOLOGY (2017)

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Article Chemistry, Multidisciplinary

Chlorodifluoromethane-triggered formation of difluoromethylated arenes catalysed by palladium

Zhang Feng et al.

NATURE CHEMISTRY (2017)

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Article Multidisciplinary Sciences

Photoredox-catalyzed deuteration and tritiation of pharmaceutical compounds

Yong Yao Loh et al.

SCIENCE (2017)

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Review Chemistry, Organic

Metal-Catalyzed Direct Difluoromethylation Reactions

Jian Rong et al.

ASIAN JOURNAL OF ORGANIC CHEMISTRY (2017)

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Review Chemistry, Multidisciplinary

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

Ming Yan et al.

CHEMICAL REVIEWS (2017)

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Review Chemistry, Multidisciplinary

Difluoromethylation Reactions of Organic Compounds

Damian E. Yerien et al.

CHEMISTRY-A EUROPEAN JOURNAL (2017)

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Article Chemistry, Multidisciplinary

Monofluoromethyl-Substituted Sulfonium Ylides: Electrophilic Monofluoromethylating Reagents with Broad Substrate Scopes

Yafei Liu et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2017)

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Article Chemistry, Multidisciplinary

Visible-Light-Induced Hydrodifluoromethylation of Alkenes with a Bromodifluoromethylphosphonium Bromide

Qing-Yu Lin et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2016)

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Article Chemistry, Organic

Access to Difluoromethylated Arenes by Pd-Catalyzed Reaction of Arylboronic Acids with Bromodifluoroacetate

Zhang Feng et al.

ORGANIC LETTERS (2016)

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Article Chemistry, Multidisciplinary

Single C-F Bond Cleavage of Trifluoromethylarenes with an ortho-Silyl Group

Suguru Yoshida et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2016)

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Editorial Material Chemistry, Medicinal

Deuterium medicinal chemistry comes of age

Roger D. Tung

FUTURE MEDICINAL CHEMISTRY (2016)

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Article Chemistry, Multidisciplinary

Direct Difluoromethylation of Aryl Halides via Base Metal Catalysis at Room Temperature

Long Xu et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016)

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News Item Biotechnology & Applied Microbiology

Deuterated drugs draw heavier backing

Asher Mullard

NATURE REVIEWS DRUG DISCOVERY (2016)

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Article Chemistry, Multidisciplinary

Efficient Cu-catalyzed Atom Transfer Radical Addition Reactions of Fluoroalkylsulfonyl Chlorides with Electron-deficient Alkenes Induced by Visible Light

Xiao-Jun Tang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2015)

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Article Chemistry, Medicinal

Isotope chemistry; a useful tool in the drug discovery arsenal

Charles S. Elmore et al.

BIOORGANIC & MEDICINAL CHEMISTRY LETTERS (2015)

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Review Chemistry, Inorganic & Nuclear

Review of recent advances in C-F bond activation of aliphatic fluorides

Qian Shen et al.

JOURNAL OF FLUORINE CHEMISTRY (2015)

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Review Chemistry, Multidisciplinary

Functionalization of Fluorinated Molecules by Transition-Metal-Mediated C-F Bond Activation To Access Fluorinated Building Blocks

Theresia Ahrens et al.

CHEMICAL REVIEWS (2015)

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Review Chemistry, Multidisciplinary

Fluorine in Pharmaceutical Industry: Fluorine-Containing Drugs Introduced to the Market in the Last Decade (2001-2011)

Jiang Wang et al.

CHEMICAL REVIEWS (2014)

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Article Chemistry, Medicinal

Using Deuterium in Drug Discovery: Leaving the Label in the Drug

Thomas G. Gant

JOURNAL OF MEDICINAL CHEMISTRY (2014)

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Article Chemistry, Multidisciplinary

Direct monofluoromethylation of O-, S-, N-, and P-nucleophiles with PhSO(NTs) CH2F: the accelerating effect of alpha-fluorine substitution

Xiao Shen et al.

CHEMICAL SCIENCE (2014)

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Article Multidisciplinary Sciences

Cooperative dual palladium/silver catalyst for direct difluoromethylation of aryl bromides and iodides

Yang Gu et al.

NATURE COMMUNICATIONS (2014)

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Review Chemistry, Organic

Recent advances in transition metal-catalyzed Csp2-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

Gregory Landelle et al.

BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY (2013)

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News Item Biochemistry & Molecular Biology

Heavy drugs draw heavy interest from pharma backers

Alla Katsnelson

NATURE MEDICINE (2013)

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Article Chemistry, Medicinal

Deuterated Clopidogrel Analogues as a New Generation of Antiplatelet Agents

Yaoqiu Zhu et al.

ACS MEDICINAL CHEMISTRY LETTERS (2013)

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Article Chemistry, Multidisciplinary

On the Interpretation of Deuterium Kinetic Isotope Effects in C?H Bond Functionalizations by Transition-Metal Complexes

Eric M. Simmons et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2012)

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Article Chemistry, Multidisciplinary

Copper-Mediated Difluoromethylation of (Hetero)aryl Iodides and beta-Styryl Halides with Tributyl(difluoromethyl)stannane

G. K. Surya Prakash et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2012)

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Article Chemistry, Multidisciplinary

Copper-Mediated Difluoromethylation of Aryl and Vinyl Iodides

Patrick S. Fier et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2012)

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Article Multidisciplinary Sciences

Practical and innate carbon-hydrogen functionalization of heterocycles

Yuta Fujiwara et al.

NATURE (2012)

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Review Chemistry, Multidisciplinary

Kinetic Isotope Effects in the Study of Organometallic Reaction Mechanisms

Mar Gomez-Gallego et al.

CHEMICAL REVIEWS (2011)

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Article Chemistry, Multidisciplinary

Selective alpha-defluorination of polyfluorinated esters and amides using SmI2/Et3N/H2O

Jenny Wettergren et al.

CHEMICAL COMMUNICATIONS (2010)

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Review Chemistry, Multidisciplinary

Selective difluoromethylation and monofluoromethylation reactions

Jinbo Hu et al.

CHEMICAL COMMUNICATIONS (2009)

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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

Understanding organofluorine chemistry. An introduction to the C-F bond

David O'Hagan

CHEMICAL SOCIETY REVIEWS (2008)

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Review Chemistry, Multidisciplinary

Fluorine in medicinal chemistry

Sophie Purser et al.

CHEMICAL SOCIETY REVIEWS (2008)

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Article Chemistry, Organic

Direct electrophilic monofluoromethylation

G. K. Surya Prakash et al.

ORGANIC LETTERS (2008)

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Review Multidisciplinary Sciences

Fluorine in pharmaceuticals:: Looking beyond intuition

Klaus Mueller et al.

SCIENCE (2007)

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Review Chemistry, Multidisciplinary

The renaissance of H/D exchange

Jens Atzrodt et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2007)

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Review Biochemistry & Molecular Biology

Insights into enzyme structure and dynamics elucidated by amide H/D exchange mass spectrometry

LS Busenlehner et al.

ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS (2005)

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Article Chemistry, Inorganic & Nuclear

Nucleophilic trifluoromethylation tamed

GKS Prakash et al.

JOURNAL OF FLUORINE CHEMISTRY (2001)

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Article Chemistry, Multidisciplinary

A Base-Promoted Reductive Coupling Platform for the Divergent Defluorofunctionalization of Trifluoromethylarenes

Shawn E. Wright et al.

Summary: We reported a trifluoromethylarene reductive coupling method that expands the scope of difluorobenzylic substructures accessible, providing rapid access to over 20 unique difluoroalkylarene scaffolds.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

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Organoboron Reagent-Controlled Selective (Deutero)Hydrodefluorination

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