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Wednesday, February 29, 2012

Tuesday, February 28, 2012

Synthesis of Olefin-Oxazoline Ligands (OlefOx) by Rhodium(III)-Catalyzed Oxidative Olefination



ASC, 2012, DOI: 10.1002/adsc.201100711

Iron-Catalyzed Nitrogen-Directed Coupling of Arene and Aryl Bromides Mediated by Metallic Magnesium


ASC, 2012, DOI: 10.1002/adsc.201100791

Rh-catalyzed intramolecular sp2 C–H bond difluoromethylenation

Graphical abstract: Rh-catalyzed intramolecular sp2 C–H bond difluoromethylenation

Chem. Commun., 2012, 48, 3136-3138

Practical synthesis of aromatic nitriles via gallium-catalysed electrophilic cyanation of aromatic C–H bonds

Graphical abstract: Practical synthesis of aromatic nitriles via gallium-catalysed electrophilic cyanation of aromatic C–H bonds

Chem. Commun., 2012, 48, 3127-3129

Aza-oxindole synthesis by oxidative coupling of Csp2–H and Csp3–H centers

Graphical abstract: Aza-oxindole synthesis by oxidative coupling of Csp2–H and Csp3–H centers

Chem. Commun., 2012, 48, 3064-3066

Friday, February 24, 2012

Palladium-Catalyzed Direct Hydroxymethylation of Aryl Halides and Triflates with Potassium Acetoxymethyltrifluoroborate

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Org. Lett., 2012, DOI: 10.1021/ol300149b

Synthesis of Densely Substituted α,β,γ,δ-Dienones via the PdII-Catalyzed Allylation, H-Migration, and Aerobic Oxidative δ-Hydride Elimination Cascade

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Org. Lett., 2012, DOI: 10.1021/ol203444g

Nickel-Catalyzed Intermolecular Insertion of Aryl Iodides to Nitriles: A Novel Method to Synthesize Arylketones

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Org. Lett., 2012, DOI: 10.1021/ol300153f

Nickel(0)-Catalyzed Heck Cross-Coupling via Activation of Aryl C–OPiv Bonds

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Org. Lett., 2012, DOI: 10.1021/ol203322v

Pd-Catalyzed Arylation/Oxidation of Benzylic C–H Bond

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Org. Lett., 2012, DOI: 10.1021/ol300037p

Intramolecular Pd(II)-Catalyzed Aerobic Oxidative Amination of Alkenes: Synthesis of Six-Membered N-Heterocycles

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Org. Lett., DOI: 10.1021/ol300030w

Thursday, February 23, 2012

Synthesis of Pyridines from Ketoximes and Terminal Alkynes via C–H Bond Functionalization

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JOC, 2012, DOI: 10.1021/jo202280e

Synthesis of Benzisoxazolines by the Coupling of Arynes with Nitrones

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JOC, 2012, DOI: 10.1021/jo2025064 

4-Aryl-2-quinolones from 3,3-Diarylacrylamides through Intramolecular Copper-Catalyzed C–H Functionalization/C–N Bond Formation

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JOC, 2012, DOI: 10.1021/jo202427m

Expedient Synthesis of Highly Substituted Pyrroles via Tandem Rearrangement of α-Diazo Oxime Ethers

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JACS, DOI: 10.1021/ja300552c 

Highly Diastereoselective Synthesis of Tetrahydropyridines by a C–H Activation–Cyclization–Reduction Cascade - Journal of the American Chemical Society (ACS Publications)

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JACS, DOI: 10.1021/ja2119833

Fluorine Transfer to Alkyl Radicals

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JACS, DOI: 10.1021/ja211679v

Silver-Catalyzed Decarboxylative Chlorination of Aliphatic Carboxylic Acids

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JACS, DOI: 10.1021/ja210361z

Double 1,4-rhodium migration cascade in rhodium-catalysed arylative ring-opening/spirocyclisation of (3-arylcyclobutylidene)acetates

Graphical abstract: Double 1,4-rhodium migration cascade in rhodium-catalysed arylative ring-opening/spirocyclisation of (3-arylcyclobutylidene)acetates

Takanori Matsuda  Yuya Suda and Akira Takahashi
Chem. Commun., 2012, 48, 2988-2990

A facile route to flavone and neoflavone backbones via a regioselective palladium catalyzed oxidative Heck reaction

Graphical abstract: A facile route to flavone and neoflavone backbones via a regioselective palladium catalyzed oxidative Heck reaction

Chem. Commun., 2012, 48, 2985-2987

Transition metal catalysis and nucleophilic fluorination

Graphical abstract: Transition metal catalysis and nucleophilic fluorination

Chem. Commun., 2012, 48, 2929-2942

Tuesday, February 14, 2012

Efficient Iron-Catalyzed Direct β-Alkylation of Secondary Alcohols with Primary Alcohols

Copper-Catalyzed Domino Synthesis of Benzimidazo[2,1-b]quin- azolin-12(6H)-ones Using Cyanamide as a Building Block

A general and selective copper-catalyzed reduction of secondary amides

Graphical abstract: A general and selective copper-catalyzed reduction of secondary amides

Ortho-Trifluoromethylation of Functionalized Aromatic Triazenes

Iron-Catalyzed Synthesis of β-Chlorovinyl and α,β-Alkynyl Ketones from Terminal and Silylated Alkynes with Acid Chlorides - Gandeepan - 2012 - Advanced Synthesis & Catalysis - Wiley Online Library



Abstract
A simple efficient method for the iron(III)-catalyzed synthesis of substituted β-chlorovinyl ketones and α,β-alkynyl ketones from terminal and silyl-substituted alkynes with acid chlorides, respectively, is described. This method features easily available starting materials, a cheap and non-toxic catalyst, simple manipulation and mild reaction conditions. Evidence shows that the catalytic addition of the acid chloride to a terminal alkyne to give (Z)-β-chlorovinyl ketones favours a concerted pathway via a four-membered ring transition state between the two alkyne carbons and the carbon-chloride bond of the acid chloride.


  1. Parthasarathy Gandeepan, 
  2. Kanniyappan Parthasarathy, 
  3. Tsu-Hui Su, 
  4. Chien-Hong Cheng
DOI: 10.1002/adsc.201100670

Tuesday, February 7, 2012

An Alternative Approach to para-C–H Arylation of Phenol: Palladium-Catalyzed Tandem γ-Arylation/Aromatization of 2-Cyclohexen-1-one Derivatives - Organic Letters (ACS Publications)

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Palladium-Catalyzed Oxidative Heck Coupling Reaction for Direct Synthesis of 4-Arylcoumarins Using Coumarins and Arylboronic Acids

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Synthesis of δ-Bromo γ,δ-Unsaturated Carbonyl Compounds via Palladium-Catalyzed Bromoalkylation of Alkynoates

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Palladium-catalyzed regio- and stereoselective intermolecular tandem reaction of electron-deficient alkynes, CuBr2, and allylic alcohol to synthesize δ-bromo-γ,δ-unsaturated carbonyls was developed. A mechanism involving bromopalladation of alkyne, followed by insertion of allylic alcohol and allylic hydrogen shift, is proposed. The shift of allylic hydrogen is the rate-limiting step in this reaction.

Allenes in Molecular Materials - Rivera-Fuentes - 2012 - Angewandte Chemie International Edition - Wiley Online Library


This Minireview provides a critical account of the development of allene-containing advanced functional materials, starting with the design and synthesis of stable and enantiopure building blocks. A variety of systems, including shape-persistent macrocycles, foldamers, polymers, charge-transfer chromophores, dendrimers, liquid crystals, and redox-switchable chiral chromophores are discussed from the viewpoint of their syntheses, properties, and potential applications. The goal of this Minireview is to inspire new uses of enantiopure allenes for the rational design of advanced materials.

Chiral Monodentate Phosphines and Bulky Carboxylic Acids: Cooperative Effects in Palladium-Catalyzed Enantioselective C(sp3)–H Functionalization


Teaming up: The important indoline scaffold is provided with enantiomeric ratios of up to 98:2 in palladium(0)-catalyzed C(sp3)–H activations of aryl triflates. The key is the combination of the electron-rich monodentate Sagephos and the bulky 9H-xanthene-9-carboxylic acid. Both participate in a highly cooperative manner in the enantiodetermining concerted-deprotonation-metalation step (see scheme, Tf=triflate).

Palladium-Catalyzed Amidation by Chemoselective C(sp3)[BOND]H Activation: Concise Route to Oxindoles Using a Carbamoyl Chloride Precursor


Quite select: A new strategy was developed for the synthesis of various oxindoles from carbamoyl chlorides. Under the optimum reaction conditions, with Ad2PBu as a ligand, tBuCONHOH as an additive, and a CO atmosphere, selective C(sp3)H activation proceeded in the presence of a C(sp2)H bond. Ad=adamantyl.

Extrusion of CO from Aryl Ketones: Rhodium(I)-Catalyzed C[BOND]C Bond Cleavage Directed by a Pyridine Group - Lei - 2012 - Angewandte Chemie International Edition - Wiley Online Library


Snipping tool: The rhodium(I)-catalyzed extrusion of carbon monoxide from biaryl ketones and alkyl/alkenyl aryl ketones was developed to produce biaryls and alkyl/alkenyl arenes, respectively, in high yields (see scheme). A wide range of functionalities are tolerated. Not only does this method provide an alternative pathway to construct useful scaffolds, but also offers a new strategy for C-C bond activation.

Palladium-Catalyzed Intermolecular C(sp3)[BOND]H Amidation



Dual capacity: A new palladium-catalyzed intermolecular sequence consisting of the CH activation and amidation of methyl groups relies on N-fluorobis(phenylsulfonyl)imide (NFSI) as both the oxidant and the nitrogen source. The reaction provides the corresponding arylamines as bissulfonimides along with HF as the only by-product. Both experimental and computational results suggest the involvement of a monomeric palladium(IV) intermediate.

Copper-Catalyzed Cross-Coupling Interrupted by an Opportunistic Smiles Rearrangement: An Efficient Domino Approach to Dibenzoxazepinones

Synthesis of 3-Fluoro-3-aryl Oxindoles: Direct Enantioselective α Arylation of Amides



Modus operandi: Catalytic access to the title compounds through a new asymmetric α-arylation protocol is reported (see scheme). These products are formed in good yields and excellent enantioselectivities using a new and easily synthesized chiral N-heterocyclic carbene (NHC) ligand. Advanced DFT calculations reveal the properties of the NHC ligand and the mode of operation of the catalyst.

DOI: 10.1002/anie.201200206

Gold-Catalyzed Oxidative Cyclizations of cis-3-En-1-ynes to Form Cyclopentenone Derivatives - Bhunia - 2012 - Angewandte Chemie International Edition - Wiley Online Library


Golden tendencies: The title reaction for synthesizing cyclopentenone derivatives utilizes a gold complex and 8-methylquinoline oxide as catalytic system (see scheme; IPr=1,3-bis(diisopropylphenyl)imidazol-2-ylidene). Such products are not attainable using diazocarbonyl reagents as the gold carbenoids tend towards reacting with C-H bonds.

DOI: 10.1002/anie.201108027


Amine Synthesis through Mild Catalytic Hydrosilylation of Imines using Polymethylhydroxysiloxane and [RuCl2(arene)]2 Catalysts



DOI: 10.1002/cssc.201100585

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