Wednesday, February 29, 2012

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

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

Abstract Image

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.

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