Halogenation
View article: Synthesis of Aryl Difluoroalkyl Ethers by Deprotonative Functionalization of the Difluoromethoxy (OCHF <sub>2</sub> ) Moiety
Synthesis of Aryl Difluoroalkyl Ethers by Deprotonative Functionalization of the Difluoromethoxy (OCHF <sub>2</sub> ) Moiety Open
An unprecedented deprotonative functionalization of difluoromethoxylated compounds is described herein using a lithiated base under in situ trapping conditions. Aryl α , α ‐difluoroalkyl ethers could be obtained in a two‐step process via d…
View article: Harnessing Radical Polarity Effects for Hydroalkylation of Unactivated Alkenes with Amides
Harnessing Radical Polarity Effects for Hydroalkylation of Unactivated Alkenes with Amides Open
View article: Preparation of Se(IV) Aryltrifluoromethylselenide Dichlorides
Preparation of Se(IV) Aryltrifluoromethylselenide Dichlorides Open
Trifluoromethylselenide dichlorides are rare selenium(IV) derivatives that have received limited attention despite their potential in organoselenium chemistry. We report a straightforward and efficient synthesis of dichloro(aryl)(trifluoro…
View article: Assessing the role of iodination degree on biodegradation kinetics and transformation pathways of iodinated contrast media and derivatives
Assessing the role of iodination degree on biodegradation kinetics and transformation pathways of iodinated contrast media and derivatives Open
Triiodinated aromatic compounds used as iodinated contrast media in medical imaging are poorly biodegradable. Reductive dehalogenation enhances biotransformation, but the specific influence of iodination degree on biodegradation remains un…
View article: Photostable π-Expanded Furans via Base-Mediated Quinone Oxygen-Annulation
Photostable π-Expanded Furans via Base-Mediated Quinone Oxygen-Annulation Open
A one-pot O-annulation couples chloroquinones with aromatic alcohols to efficiently construct π-expanded furans in yields up to 91%. Subsequent TIPS-acetylene functionalization and reductive aromatization enhance solubility and furnish ben…
View article: Halogens On, H-Bonds Off—Insights into Structure Control of Dihalogenated Imidazole Derivatives
Halogens On, H-Bonds Off—Insights into Structure Control of Dihalogenated Imidazole Derivatives Open
Halogen bonds play an important role in the targeted generation of solid-state structures, with polyhalogenated compounds enabling the simultaneous formation of various interactions. In this manuscript, we investigate the interactions of d…
View article: Anion Transfer Reactions from Chiral Hypervalent Iodine Macrocycles
Anion Transfer Reactions from Chiral Hypervalent Iodine Macrocycles Open
The direct chlorination, bromination and azidation of beta keto esters, 2-acetyl-1-tetralone and methyl 1-oxo-2,3-dihydro-1H-indene-2-carboxylate is achieved utilizing anion-coordinated hypervalent iodine benziodazoles derived from hyperva…
View article: Bifunctional Aziridines from Photochemically Generated FSO <sub>2</sub> NH <sub>2</sub> for SuFEx Diversification of Alkenes
Bifunctional Aziridines from Photochemically Generated FSO <sub>2</sub> NH <sub>2</sub> for SuFEx Diversification of Alkenes Open
Sulfonyl fluorides have emerged as ubiquitous reactive motifs in fields ranging from medicinal chemistry to materials science, with applications as chemical warheads and as clickable units via Sulfur(VI) Fluoride Exchange (SuFEx). However,…
View article: Bifunctional Aziridines from Photochemically Generated FSO <sub>2</sub> NH <sub>2</sub> for SuFEx Diversification of Alkenes
Bifunctional Aziridines from Photochemically Generated FSO <sub>2</sub> NH <sub>2</sub> for SuFEx Diversification of Alkenes Open
Sulfonyl fluorides have emerged as ubiquitous reactive motifs in fields ranging from medicinal chemistry to materials science, with applications as chemical warheads and as clickable units via Sulfur(VI) Fluoride Exchange (SuFEx). However,…
View article: On the reaction mechanism of a colour test for uracil detection
On the reaction mechanism of a colour test for uracil detection Open
When uracil is dissolved in bromine water and excess of a solution of barium hydroxide is added, a purple precipitate or colour is developed. It was found that iso-dialuric and dialuric acid form purple precipitates with barium hydroxide. …
View article: Experimental and Computational Analysis of the Inability of an Iron(II)- and 2-Oxoglutarate-Dependent Aliphatic Halogenase to Mediate Fluorination
Experimental and Computational Analysis of the Inability of an Iron(II)- and 2-Oxoglutarate-Dependent Aliphatic Halogenase to Mediate Fluorination Open
Incorporation of fluorine into pharmaceuticals, agrochemicals, and molecular-imaging agents is of growing importance. Multiple synthetic fluorination methods have recently emerged, and metalloenzymes that are potentially capable of even C(…
View article: CF and CH Bond Activation Reactions of Fluorinated Molecules at Rhodium Pincer Complexes
CF and CH Bond Activation Reactions of Fluorinated Molecules at Rhodium Pincer Complexes Open
The pyridine‐based pincer complexes [Rh(P H NNNP t Bu )H] ( 2a ) (P H NNNP t Bu = {2,6‐( t Bu 2 P NH)( t Bu 2 P NH)(C 5 N H 3 )‐ κ 3 P,N,P}) and [Rh(P H NNOP t Bu )H] ( 2b ) (P H NNOP t Bu = {2‐( t Bu 2 P O)‐6‐( t Bu 2 P NH)(C 5 N H 3 )‐ κ…
View article: Palladium‐Catalyzed Chemoselective Direct Arylation of Polyfluoroarenes With Chloroaryl Triflates at the C–Cl Bond
Palladium‐Catalyzed Chemoselective Direct Arylation of Polyfluoroarenes With Chloroaryl Triflates at the C–Cl Bond Open
This study describes a palladium‐catalyzed chemoselective direct arylation of polyfluoroarenes with chloro(hetero)aryl triflates, achieving site‐selective functionalization at the C–Cl bond for the first time. The recently developed alkyl‐…
View article: A Telescopic, Sustainable Synthesis of the Key Starting Materials of Antipsychotic Drugs Quetiapine and Loxapine via Reductive Amidation
A Telescopic, Sustainable Synthesis of the Key Starting Materials of Antipsychotic Drugs Quetiapine and Loxapine via Reductive Amidation Open
Quetiapine, a dibenzothiazepine derivative, is an antagonist of serotonin and dopamine. It was approved by the Food Drug and Administration for the treatment of schizophrenia in 1997 and has been used as a commonly prescribed second-genera…
View article: Photochemical Macrolactonization of Hydroxyaldehydes via C–H Bromination
Photochemical Macrolactonization of Hydroxyaldehydes via C–H Bromination Open
View article: Enabling regiospecific di-halogenation in one-pot reactions using an engineered single-component flavin-dependent tryptophan halogenase
Enabling regiospecific di-halogenation in one-pot reactions using an engineered single-component flavin-dependent tryptophan halogenase Open
Installation of halogen atoms to organic compounds through flavin-dependent halogenases (FDHs) catalyzed reactions has emerged as an attractive strategy in organic biochemistry and synthetic biology. A cyanobacterial FDH termed AetF that c…
View article: Préparation de nanocristaux de cellulose amphiphiles par polymérisation radicalaire par transfert d’atome initiée en surface (SI-ATRP) de particules immobilisées à l'interface d’émulsions de Pickering
Préparation de nanocristaux de cellulose amphiphiles par polymérisation radicalaire par transfert d’atome initiée en surface (SI-ATRP) de particules immobilisées à l'interface d’émulsions de Pickering Open
In this work, we investigated an original method to prepare amphiphilic cellulose nanocrystals (CNCs) by interfacial surface-initiated atom transfer radical polymerization (SI-ATRP) of Pickering emulsions stabilized by CNCs bearing bromina…
View article: Organic Halogenation using Inorganic Halides and Visible-Light Photocatalyst Perylenediimide
Organic Halogenation using Inorganic Halides and Visible-Light Photocatalyst Perylenediimide Open
Halogenation reactions are fundamental in organic synthesis. While halogenation with fragile N-X (nitrogen-halogen) bonds is well-known in the literature, metal halide salts often require electrolysis. In this study, we unveil a novel and …
View article: A Broadly Applicable Strategy to Aminate Azines Enabled by Electronically Tuned Phosphine Reagents
A Broadly Applicable Strategy to Aminate Azines Enabled by Electronically Tuned Phosphine Reagents Open
We describe a strategy for aminating pyridines and other azines via phosphonium salt intermediates. Precisely tuning the electronic properties of the phosphonium ion was key for C─N bond formation via an S N Ar‐halogenation, S N Ar‐aminati…
View article: Peptidic Tryptophan Halogenation by a Promiscuous Flavin‐Dependent Enzyme
Peptidic Tryptophan Halogenation by a Promiscuous Flavin‐Dependent Enzyme Open
Amino acids undergo numerous enzymatic modifications. However, the broad applicability of amino acid‐modifying enzymes for synthetic purposes is limited by narrow substrate scope and often unknown regulatory or accessory factor requirement…
View article: Synthesis of active pharmaceutical ingredient atomoxetine via desulfurative halogenation
Synthesis of active pharmaceutical ingredient atomoxetine via desulfurative halogenation Open
View article: Peptidic Tryptophan Halogenation by a Promiscuous Flavin‐Dependent Enzyme
Peptidic Tryptophan Halogenation by a Promiscuous Flavin‐Dependent Enzyme Open
Amino acids undergo numerous enzymatic modifications. However, the broad applicability of amino acid‐modifying enzymes for synthetic purposes is limited by narrow substrate scope and often unknown regulatory or accessory factor requirement…
View article: Scalable Reductive Deuteration of (Hetero)Aryl Chlorides with D2O
Scalable Reductive Deuteration of (Hetero)Aryl Chlorides with D2O Open
Deuterated compounds serve as powerful tools for investigating reaction mechanisms, tracing molecular pathways, as well as enhancing properties in medicinal and materials science. Herein, we reported a nickel-catalyzed deutero-dehalogenati…
View article: The Atroposelective Iodination of 2-Amino-6-arylpyridines Catalyzed by Chiral Disulfonimides Actually Proceeds via Brønsted Base Catalysis: A Combined Experimental and Computational Study
The Atroposelective Iodination of 2-Amino-6-arylpyridines Catalyzed by Chiral Disulfonimides Actually Proceeds via Brønsted Base Catalysis: A Combined Experimental and Computational Study Open
A thorough mechanistic investigation into the disulfonimide (DSI)-catalyzed atroposelective iodination of 2-amino-6-arylpyridines with N-iodosuccinimide is described. While initially hypothesized to proceed via Brønsted-acid catalysis thro…
View article: A concise synthesis of pyrrolo[2,3-d]pyrimidine through I2/DMSO promoted cascade annulation
A concise synthesis of pyrrolo[2,3-d]pyrimidine through I2/DMSO promoted cascade annulation Open
An attractive approach for the preparation of pyrrolo[2,3-d]pyrimidines has been developed via I2/DMSO promoted cascade annulation of 6-amino-1,3-dimethyluracil with aurones. The reaction involves Michael addition, iodination, i…
View article: Trisubstituted Alkenes as Valuable Building Blocks
Trisubstituted Alkenes as Valuable Building Blocks Open
The stereoselective synthesis of trisubstituted alkenes has become a key topic in modern organic chemistry. At the same time, trisubstituted alkenes also serve as valuable starting materials for a wide range of transformations. However, it…
View article: Unveiling an Alternative Mechanism for Lewis Basic Selenium as a C─H Hydrogen Bond Catalyst and Its Application in the Halogenation of Arenes
Unveiling an Alternative Mechanism for Lewis Basic Selenium as a C─H Hydrogen Bond Catalyst and Its Application in the Halogenation of Arenes Open
Electrophilic halogenation is a fundamentally useful transformation, and Lewis basic selenium catalysts together with N ‐haloimides are known to promote the reaction under mild conditions. Selenourea is a frequently used platform for the L…
View article: Unveiling an Alternative Mechanism for Lewis Basic Selenium as a C─H Hydrogen Bond Catalyst and Its Application in the Halogenation of Arenes
Unveiling an Alternative Mechanism for Lewis Basic Selenium as a C─H Hydrogen Bond Catalyst and Its Application in the Halogenation of Arenes Open
Electrophilic halogenation is a fundamentally useful transformation, and Lewis basic selenium catalysts together with N ‐haloimides are known to promote the reaction under mild conditions. Selenourea is a frequently used platform for the L…
View article: Selective Bromination of p-Xylene via Homogeneous Catalysis: Influence of Reaction Parameters on 2,5-Dibromo- p-Xylene Formation
Selective Bromination of p-Xylene via Homogeneous Catalysis: Influence of Reaction Parameters on 2,5-Dibromo- p-Xylene Formation Open
In general, homogeneous catalysis signifies reactions with soluble catalysts that are of the same phase as of the reactants in order to decrease the activation energy and increase the reaction rate. The aromatic halogenation substitution r…
View article: Covalent halogenation of polyethylene glycol-based flame-retardant phase change materials for safe energy storage
Covalent halogenation of polyethylene glycol-based flame-retardant phase change materials for safe energy storage Open
To address the synergistic challenge of regulating phase change properties and optimizing flame-retardant performance in phase change materials (PCMs), this study uses a brominated molecular engineering approach to concurrently regulate ph…