Synthesis of α-Diketones from Alkylaryl- and Diarylalkynes Using Mercuric Salts

Both alkylarylalkynes and diarylalkynes 1 are converted into the α-diketones 2 in good yield by the use of mercuric salts, e.g., mercuric nitrate hydrate or mercuric triflate, in the presence of water. Other mercuric salts, e.g., sulfate, chloride, acetate, or trifluoroacetate, do not provide the diketone product. A possible mechanism is proposed.

• Publication year

  2014

• Venue

  Organic Letters

• Publication date

  2014-04-01

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1021/ol500592mPMID 24684513PMCID 4316994
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Versatile Methodology to Hydrate Alkynes, in the Presence of a Wide Variety of Functional Groups, with Mercury(II) p-Toluensulfonamidate, Under Catalytic, Mild, and Neutral Conditions

  2013cited by this paper
• Ruthenium-catalyzed oxidation of alkynes to 1,2-diketones under room temperature and one-pot synthesis of quinoxalines

  2013cited by this paper
• Total Syntheses of Proposed (±)-Trichodermatides B and C.

  2013cited by this paper
• Photochromism of a naphthalene-bridged imidazole dimer constrained to the "anti" conformation.

  2013cited by this paper
• DBU-mediated regioselective intramolecular cyclization/dehydration of ortho diketo phenoxyethers: a synthesis of 2,3-substituted γ-benzopyranones

  2013cited by this paper
• Gold(I)-Catalyzed Diketonization of Alkynes and Its Application for the One-Pot Synthesis of Quinoxaline Derivatives

  2013cited by this paper
• Calculation of Free Energy Landscape in Multi-Dimensions with Hamiltonian-Exchange Umbrella Sampling on Petascale Supercomputer.

  2012cited by this paper
• Linking Crystallographic Model and Data Quality

  2012cited by this paper
• Synthesis of highly functionalized 9,10-phenanthrenequinones by oxidative coupling using MoCl5.

  2012cited by this paper
• Synthesis of electron-poor hexa-peri-hexabenzocoronenes.

  2012cited by this paper
• Pd/Cu-catalyzed oxidation of alkynes into 1,2-diketones using DMSO as the oxidant

  2012cited by this paper
• Gold-catalyzed stereoselective synthesis of azacyclic compounds through a redox/[2 + 2 + 1] cycloaddition cascade of nitroalkyne substrates.

  2011cited by this paper
• Making and breaking peptide bonds: protein engineering using sortase.

  2011cited by this paper
• Synthesis of novel twisted carbazole–quinoxaline derivatives with 1,3,5-benzene core: bipolar molecules as hosts for phosphorescent OLEDs

  2011cited by this paper
• Pyridine N‐Oxide Mediated Oxidation of Diarylalkynes with Palladium on Carbon

  2011cited by this paper
• The Iron‐Catalyzed Oxidation of Alkynes—1,2‐Dione Formation Versus Oxidative Cleavage—A Matter of Temperature

  2011cited by this paper
• Catalytic mechanism and roles of Arg197 and Thr183 in the Staphylococcus aureus sortase A enzyme.

  2011cited by this paper
• Elemental Iodine or Diphenyl Diselenide in the [Bis(trifluoroacetoxy)iodo]benzene‐Mediated Conversion of Alkynes into 1,2‐Diketones

  2011cited by this paper
• Gold-catalyzed synthesis of benzil derivatives and α-keto imides via oxidation of alkynes.

  2011cited by this paper
• Sortase enzymes in Gram‐positive bacteria

  2011cited by this paper
• Ruthenium‐Catalyzed Alkyne Oxidation with Part‐Per‐Million Catalyst Loadings

  2010cited by this paper
• Palladium on Carbon-Catalyzed Synthesis of Benzil Derivatives from 1,2-Diarylalkynes with DMSO and Molecular Oxygen as Dual Oxidants

  2010cited by this paper
• Improved side-chain torsion potentials for the Amber ff99SB protein force field

  2010cited by this paper
• Discovery and initial optimization of 5,5'-disubstituted aminohydantoins as potent beta-secretase (BACE1) inhibitors.

  2010cited by this paper
• Catalytic asymmetric synthesis of R207910.

  2010cited by this paper
• Sortase transpeptidases: insights into mechanism, substrate specificity, and inhibition.

  2010cited by this paper
• Solid-Phase Synthesis of 1,2-Diketonesvia Acetylene Oxidation: A Versatile Diversity Platform for theCombinatorial Synthesis of Heterocycles

  2010cited by this paper
• A Combined Experimental and Density Functional Theory Study on the Pd‐Mediated Cycloisomerization of o‐Alkynylnitrobenzenes – Synthesis of Isatogens and Their Evaluation as Modulators of ROS‐Mediated Cell Death

  2010cited by this paper
• The Listeria monocytogenes Sortase-B Recognizes Varied Amino Acids at Position 2 of the Sorting Motif*

  2009cited by this paper
• Wacker-type oxidation of alkynes into 1,2-diketones using molecular oxygen.

  2009cited by this paper
• Mutagenesis Studies of Substrate Recognition and Catalysis in the Sortase A Transpeptidase from Staphylococcus aureus*

  2008cited by this paper
• DMSO–PdI2 as a powerful oxidizing couple of alkynes into benzils: one-pot synthesis of nitrogen-containing five- or six-membered heterocycles

  2008cited by this paper
• Catalytic Hydration of Alkynes and Its Application in Synthesis

  2007cited by this paper
• Super radical stabilizers.

  2006cited by this paper
• Automatic atom type and bond type perception in molecular mechanical calculations.

  2006cited by this paper
• Practical Method for Transforming Alkynes into α-Diketones

  2006cited by this paper
• Practical method for transforming alkynes into alpha-diketones.

  2006cited by this paper
• Stereospecific synthesis of (+/-)-1,2-anhydro methyl rocaglate.

  2005cited by this paper
• Synthesis of (2R,3S) 3-amino-4-mercapto-2-butanol, a threonine analogue for covalent inhibition of sortases.

  2005cited by this paper
• Anchor Structure of Staphylococcal Surface Proteins

  2005cited by this paper
• Highly active, immobilized ruthenium catalysts for oxidation of alcohols to aldehydes and ketones. Preparation and use in both batch and flow systems.

  2005cited by this paper
• Intramolecular Oxygen Transfer from Nitro Groups to C⋮C Bonds Mediated by Iridium Hydrides

  2005cited by this paper
• Scalable molecular dynamics with NAMD

  2005cited by this paper
• Development of a high-performance liquid chromatography assay and revision of kinetic parameters for the Staphylococcus aureus sortase transpeptidase SrtA.

  2004cited by this paper
• Anchoring of Surface Proteins to the Cell Wall of Staphylococcus aureus

  2004cited by this paper
• A Comparative Genome Analysis Identifies Distinct Sorting Pathways in Gram-Positive Bacteria

  2004cited by this paper
• Structures of sortase B from Staphylococcus aureus and Bacillus anthracis reveal catalytic amino acid triad in the active site.

  2004cited by this paper
• The structure of sortase B, a cysteine transpeptidase that tethers surface protein to the Staphylococcus aureus cell wall.

  2004cited by this paper
• Kinetic mechanism of Staphylococcus aureus sortase SrtA.

  2003cited by this paper
• AuBr3-catalyzed cyclization of o-(alkynyl)nitrobenzenes. Efficient synthesis of isatogens and anthranils

  2003cited by this paper
• Passage of Heme-Iron Across the Envelope of Staphylococcus aureus

  2003cited by this paper
• Extension to the weighted histogram analysis method: combining umbrella sampling with free energy calculations

  2001cited by this paper
• A fast SHAKE algorithm to solve distance constraint equations for small molecules in molecular dynamics simulations

  2001cited by this paper
• Staphylococcus aureus sortase mutants defective in the display of surface proteins and in the pathogenesis of animal infections.

  2000cited by this paper
• Highly Diastereoselective Aldol Reactions with Camphor-Based Acetate Enolate Equivalents.

  1999cited by this paper
• Benzeneseleninic Anhydride Oxidation of 1,2-Diarylethanes and 1,2-Diarylethylenes to 1,2-Diaryldiketones.

  1998cited by this paper
• Constant pressure molecular dynamics simulation: The Langevin piston method

  1995cited by this paper
• Chemoselective Oxidation of Carbon-Carbon Double or Triple Bonds to 1,2-Diketones with DMSO-Based Reagents

  1995cited by this paper
• Oxidation of Alkynes by Hydrogen Peroxide Catalyzed by Methylrhenium Trioxide

  1995cited by this paper
• Constant pressure molecular dynamics algorithms

  1994cited by this paper
• Particle mesh Ewald: An N⋅log(N) method for Ewald sums in large systems

  1993cited by this paper
• Iodine in Dimethyl Sulfoxide as a New General Reagent for the Preparative Oxidation of 1,2-Diarylethenes and 1,2-Diarylethynes to Aromatic 1,2-Diketones

  1991cited by this paper
• Synthesis of 2-[[(p-nitrophenyl)sulfonyl]oxy] 3-keto esters from 3-keto esters and (p-nitrophenyl)sulfonyl peroxide

  1990cited by this paper
• Oxidation of alkynes catalyzed by molybdenum(VI) and tungsten(VI) polyoxometalates

  1989cited by this paper
• Studies on the synthesis of gloeosporone - synthesis of the proposed 2,8-disubstituted oxocane structure

  1986cited by this paper
• Stereoselective synthesis of an analog of podophyllotoxin by an intramolecular Diels-Alder reaction

  1985cited by this paper
• Carbocationic and related processes in reactions of .alpha.-keto mesylates and triflates

  1985cited by this paper
• Vinylene 1,2-bis(trifluoromethanesulfonates) from azibenzils and triflic anhydride

  1984cited by this paper
• Ru-Catalyzed Oxidation of Acetylenes to α-Diketones with Iodosylbenzene

  1981cited by this paper
• Reactions of pivaloin derivatives with lithium tetramethylpiperidide

  1980cited by this paper
• Oxidation of hydrocarbons. 9. The oxidation of alkynes by potassium permanganate

  1979cited by this paper
• Preparation of 1,2-diketones: oxidation of alkynes by potassium permanganate in aqueous acetone

  1979cited by this paper
• An Improved Procedure for the Conversion of Benzyl Halides into Benzaldehydes

  1975cited by this paper
• Reactions of 1,2-Dinitrophenylethanols. Intramolecular Participation by the Nitro Group.

  1975cited by this paper
• Ruthenium tetroxide oxidation of alkynes. A new one step synthesis of α-diketones

  1971cited by this paper
• N-Bromosuccinimide-Induced Dimethyl Sulfoxide Oxidation of Acetylenes

  1971cited by this paper
• The Synthesis of Diketones from Nitratoketones1

  1955cited by this paper
• OXIDATION OF ALKENES BY MERCURIC SALTS

  1955cited by this paper
• Über die Hydratation der Kohlenwasserstoffe der Acetylenreihe durch Cadmium‐, Zink‐ und Magnesiumsalze

  1909cited by this paper
• Ueber die Einwirkung der Kohlenwasserstoffe der Acetylenreihe auf Quecksilberoxyd und dessen Salze

  year unknowncited by this paper
• Ueber eine neue Methode direkter Addition von Wasser (Hydratation) an die Kohlenwasserstoffe der Acetylenreihe

  year unknowncited by this paper

• Functionalization of Internal Arylalkynes with Nitrosylsulfuric Acid: Access to Arylated 1,2-Diketones and 1,3-Oxazoles.

  2026cites this paper
• A Direct Oxidation of Diarylalkynes Containing Quinazolinones to 1,2-Diketone Derivatives with PIFA and PhSeSePh

  2025cites this paper
• Mimicking Ozonolysis via Mechanochemistry: Internal Alkynes to 1,2-Diketones using H5IO6.

  2024cites this paper
• Photoredox-Mediated Aerobic Oxidative Cleavage of 1,3-Diketones to Access 1,2-Diketones and (Z)-1,4-Enediones.

  2024cites this paper
• Oxidation of 1,2-diarylalkynes to 1,2-diketones on acidic mesoporous ZSM-5 supported palladium catalyst

  2023cites this paper
• Dual Oxidation of Epoxides with a High-Valent Cu(III)-CF3 Compound and DMSO to Access 1,2-Diketones.

  2023cites this paper
• Fe(III)-based Eutectic Mixtures as Multi-Task and Reusable Reaction Media for Efficient and Selective Conversion of Alkynes into Carbonyl Compounds.

  2023cites this paper
• Recent Developments on Photochemical Synthesis of 1,n-Dicarbonyls.

  2023cites this paper
• Co(II) and 2-Amino-perimidinium Based New Generation Hybrid Material Promoted Facile Dimerization of Aroyl chloride: A Route to α-Diketones

  2022cites this paper
• I2-Catalyzed Carbonylation of α-Methylene Ketones to Synthesize 1,2-Diaryl Diketones and Antiviral Quinoxalines in One Pot

  2021cites this paper
• Csp–Csp bond cleavage and fragment coupling: a transition metal-free “extrusion and recombination” approach towards synthesis of 1,2-diketones

  2021cites this paper
• Transition Metal‐Catalyzed Synthesis of 1,2‐Diketones: An Overview

  2021cites this paper
• Copper‐Catalyzed Coupling of Arylethynes and Aryltriazenes to Access Libraries of 1,2‐Diketones and Their Efficacy in Synthesis of Triaryloxazoles, Imidazoles and Diaryl‐Diazepines

  2021cites this paper
• Total Synthesis of Nortopsentin D via a Late-Stage Pinacol-like Rearrangement.

  2021cites this paper
• One-pot cascade synthesis of α-diketones from aldehydes and ketones in water by using a bifunctional iron nanocomposite catalyst

  2021cites this paper
• Synthesis of 2-Aryl Acetophenones via Hydrobromination and Oxy-isomerization of (o-Arylethynyl)benzyl Alcohols.

  2021cites this paper
• Visible-Light-Induced Photocatalytic Oxidative Decarboxylation of Cinnamic Acids to 1,2-Diketones.

  2021cites this paper
• Direct Metal-Free Transformation of Alkynes to Nitriles: Computational Evidence for the Precise Reaction Mechanism

  2021cites this paper
• Catalyst-Free and Transition-Metal-Free Approach to 1,2-Diketones via Aerobic Alkyne Oxidation.

  2021cites this paper
• N-Heterocyclic carbene (NHC)-catalyzed intramolecular benzoin condensation-oxidation.

  2021cites this paper
• Conversion of alkynes into 1,2-diketones using HFIP as sacrificial hydrogen donor and DMSO as dihydroxylating agent

  2020cites this paper
• Oxidation of Alkynyl Boronates to Carboxylic Acids, Esters and Amides.

  2020cites this paper
• Visible light-induced aerobic oxidation of diarylalkynes to α-diketones catalyzed by copper-superoxo at room temperature

  2020cites this paper
• Ozonolysis of Alkynes-A Flexible Route to Alpha-Diketones: Synthesis of AI-2.

  2020cites this paper
• ICl/AgNO3 Co-Catalyzed Radical Oxidation of Diaryl- and Alkylarylalkynes into 1,2-Diketones.

  2019cites this paper
• Substituent Effect in the Synthesis of α,α‐Dibromoketones, 1,2‐Dibromalkenes, and 1,2‐Diketones from the Reaction of Alkynes and Dibromoisocyanuric Acid

  2019cites this paper
• Gold-Catalyzed Oxidation of Internal Alkynes into Benzils and its Application for One-Pot Synthesis of Five-, Six-, and Seven-Membered Azaheterocycles

  2019cites this paper
• Highly Modular Synthesis of 1,2-Diketones via Multicomponent Coupling Reactions of Isocyanides as CO Equivalents

  2019cites this paper
• Selective synthesis of (1H-benzo[d]imidazol-2-yl)(phenyl)methanone and quinoxaline from aromatic aldehyde and o-phenylenediamine.

  2019cites this paper
• Efficient Total Synthesis of Lissodendrin B, 2-Aminoimidazole Marine Alkaloids Isolated from Lissodendoryx (Acanthodoryx) fibrosa

  2019cites this paper
• NH 4 I/EtOCS 2 K promoted synthesis of substituted benzils from diphenylacetylene derivatives

  2018cites this paper
• Two‐Step One‐Pot Synthesis of Unsymmetrical (Hetero)Aryl 1,2‐Diketones by Addition‐Oxygenation of Potassium Aryltrifluoroborates to (Hetero)Arylacetonitriles

  2018cites this paper
• KI‐I 2 ‐DMSO: An Improved Microwave‐Assisted Selective Oxidation of Alkenes into 1,2‐Diketones

  2018cites this paper
• Metal-Free Iodine-Catalyzed Oxidation of Ynamides and Diaryl Acetylenes into 1,2-Diketo Compounds.

  2018cites this paper
• Catalytic Oxidation of Alkynes into 1,2‐Diketone Derivatives by Using a PdII/Lewis‐Acid Catalyst

  2018cites this paper
• One-pot synthesis of 2-(quinoxalin-2-yl)benzoate through NBS-mediated sequential reaction of 2-alkynylbenozate and aryl-1,2-diamine

  2017cites this paper
• Synthesis of α-keto imides through copper-catalyzed oxidation of N-sulfonyl ynamides.

  2017cites this paper
• Sequential Silver‐Catalyzed Oxidative Cyclization Reactions of Unprotected 2‐Alkynylanilines to Anthranils

  2017cites this paper
• Aryl Nitriles from Alkynes Using tert-Butyl Nitrite: Metal-Free Approach to C≡C Bond Cleavage.

  2016cites this paper
• Synthesis of 1,2-Diketones via a Metal-Free, Visible-Light-Induced Aerobic Photooxidation of Alkynes.

  2016cites this paper
• Silver- versus gold-catalyzed sequential oxidative cyclization of unprotected 2-alkynylanilines with oxone.

  2016cites this paper
• Modular Synthesis of Diarylalkynes and Their Efficient Conversion into Luminescent Tetraarylbutadienes

  2016cites this paper
• Thiyl radical catalyzed oxidation of diarylalkynes to α-diketones by molecular oxygen under visible-light irradiation

  2016cites this paper
• Metal-free oxidative carbonylation on enaminone CC bond for the cascade synthesis of benzothiazole-containing vicinal diketones

  2016cites this paper
• Versatile Oxidation Methods for Organic and Inorganic Substrates Catalyzed by Platinum-Group Metals on Carbons.

  2016cites this paper
• Copper-catalyzed synthesis of 1,2-diketones via oxidation of alkynes

  2015cites this paper
• Copper-catalyzed base-accelerated direct oxidation of C–H bond to synthesize benzils, isatins, and quinoxalines with molecular oxygen as terminal oxidant

  2015cites this paper
• Nitroaldol (Henry) reaction of 2-oxoaldehydes with nitroalkanes as a strategic step for a useful, one-pot synthesis of 1,2-diketones

  2015cites this paper
• Novel SMAC Mimetics as Peptide-based Small Molecule Inhibitors of IAPs to Induce Apoptosis in Cancer Cells

  2015cites this paper
• Aminocatalytic cross-coupling approach via iminium ions to different C - C Bonds.

  2015cites this paper
• Selective oxygenation of alkynes: a direct approach to diketones and vinyl acetate.

  2014cites this paper
• Metal-free iodine(III)-promoted synthesis of isoquinolones.

  2014cites this paper