Catalytic enantioselective arylations: boron to zinc exchange as a powerful tool for the generation of transferable aryl groups

The transmetalation between boron and zinc is of great importance for application in organic synthesis, since it allows the formation of new carbon-carbon bonds between organometallic units and electrophiles. The direct arylation of aldehydes or more scarcely ketones, in a catalytic, enantioselective manner using chiral catalysts has been described recently. The enantiomerically enriched diarylmethanols obtained in these reactions are valuable precursors for important bioactive molecules. This review provides a synopsis of this ever-growing field and highlights some of the challenges that still remain.

Chemical and in vitro study of the potential of 3-(aryl)-2-sulfanylpropenoic acids and their Zn(II) complexes as protective agents against cadmium toxicity

The free H(2)xspa ligands [xspa = pspa, Clpspa, tspa or fspa where p = 3-(phenyl), Clp = 3-(2-chlorophenyl), t = 3-(2-thienyl), f = 3-(2-furyl) and spa = 2-sulfanylpropenoato], their Zn(II) complexes of formula [HQ](2)[Zn(xspa)(2)] (HQ=diisopropylammonium) and the Cd(II) equivalents were prepared and characterized by elemental analysis and by IR, Raman and NMR ((1)H, (13)C) spectroscopy. X-Ray studies of the crystal structures of [HQ](2)[Zn(pspa)(2)], [HQ](2)[Zn(Clpspa)2], [HQ](2)[Zn(tspa)(2)] and [HQ](2)[Zn(fspa)(2)] show that the zinc atom is coordinated to two O atoms and two S atoms of the ligands in a distorted tetrahedral ZnO(2)S(2) environment. In the structures of [HQ](2)[Cd(pspa)(2)] and [HQ](2)[Cd(Clpspa)(2)] the cadmium atom is coordinated to three S atoms and two carboxylato O atoms of the ligands in a distorted trigonal bipyramidal environment. The interchange of ligands between Zn( II) and Cd( II) was studied by (113)Cd NMR spectroscopy. The in vitro protective effect of H(2)xspa and their Zn( II) complexes against Cd toxicity was investigated using the human hepatocarcinoma HepG2 cell line and the pig renal proximal tubule LLC-PK1 cell line. The incorporation of Zn( II) was found to be relevant in the case of H(2)pspa, with an increase observed in the cell viability of the LCC-PK1 cells with respect to the value for the free ligand.

Highly efficient palladium-catalyzed Suzuki-Miyaura reactions of potassium aryltrifluoroborates with 5-iodo-1,3-dioxin-4-ones in water: an approach to alpha-aryl-beta-ketoesters

The high efficient palladium-catalyzed Suzuki-Miyaura reactions of potassium aryltrifluoroborates 3 with 5-iodo-1,3-dioxin-4-ones 2a-b in water as only solvent in the presence of n-Bu(4)NOH as base is reported. The respective 5-aryl-1,3-dioxin-4-ones 4a-n were obtained in good to excellent yields. The catalyst system provides high efficiency at low load using electronically diverse coupling partners. The obtained 2,2,6-trimethyl-5-aryl-1,3-dioxin-4-ones were transformed into corresponding alpha-aryl-beta-ketoesters 6 by reaction with an alcohol in the absence of solvent. (C) 2009 Elsevier Ltd. All rights reserved.

Ultrasound-Assisted Synthesis of Symmetrical Biaryls by Palladium-Catalyzed Homocoupling of Aryl n-Butyl Tellurides

An ultrasound-assisted synthesis of symmetrical biaryls with electron-withdrawing or -donating substituents is described and illustrated by palladium-catalyzed homocoupling reaction of aryl tellurides. This procedure offers easy access to biaryls in short reaction time, and the products are achieved in good to excellent yields.

Synthesis of 2-Aryl- and 2,5-Diarylfurans and Thiophenes by Suzuki-Miyaura Reactions Using Potassium Trifluoroborate Salts and Heteroaryltellurides

The Suzuki-Miyaura cross-coupling reaction of 2-(butyltellanyl) or 2,5-bis-(butyltellanyl)furans and thiophenes with potassium aryltrifluoroborate salts catalyzed by palladium afforded 2-aryl- or 2,5-diaryl-furans and thiophenes in moderate to good yields.

Negishi cross-coupling of organotellurium compounds: synthesis of biaryls, aryl-, and diaryl acetylenes

A functional group tolerant palladium-catalyzed Negishi coupling of diaryl tellurides with organozinc has been developed. This methodology permits efficient preparation of biaryls, aryl acetylenes and diaryl acetylenes in moderate to good yields. A preliminary study to gain further insight into the reaction was performed using in situ ReactIR technology. (C) 2011 Elsevier Ltd. All rights reserved.

Facile Synthesis of Koser`s Reagent and Derivatives from Iodine or Aryl Iodides

The first one-pot synthesis of neutral and electron-rich [hydroxy(tosyloxy)iodo]arenes (HTIBs) from iodine and arenes is presented, thereby avoiding the need for expensive iodine(III) precursors. A large set of including a polyfluorinated analogue, can be obtained from the corresponding aryl iodide under the same conditions. The reaction proceeds under mild conditions, without excess reagents, and is fast and high-yielding. Together, the two presented routes give access to a wide range of HTIBs, which are useful reagents in a variety of synthetic transformations.

Synthesis of alpha,beta-unsaturated aryl esters via Heck reaction of unsymmetrical aryl tellurides

A variety of alpha,beta-unsaturated aryl esters were prepared by the direct reaction of unsymmetrical aryltellurides and ethyl acrylate, catalyzed by PdCl(2) via a Heck cross-coupling reaction. (C) 2009 Elsevier Ltd. All rights reserved.

Antioxidant and antimicrobial properties of 2-(4,5-dihydro-1H-pyrazol-1-yl)-pyrimidine and 1-carboxamidino-1H-pyrazole derivatives

Five previously synthesized 4-trifluoromethyl-2-(5-aryl-3-styryl-1H-pyrazol-1yl)-pyrimidines and six 5-aryl-3-styryl-1-carboxamidino-1H-pyrazole derivatives were screened for their antioxidant proprieties. The antioxidant activities were evaluated by using the DPPH and the HRP/luminol/H2O2 chemiluminescence assay systems and for their antimicrobial activity (MIC). The results were good for those series in some concentration in comparison with the standards.

Searching for Moniliophthora perniciosa pathogenicity genes

The basidiomycete Moniliophthora perniciosa is the causal agent of witches` broom disease of Theobroma cacao (cacao). Pathogenesis mechanisms of this hemibiotrophic fungus are largely unknown. An approach to identify putative pathogenicity genes is searching for sequences induced in mycelia grown under in vitro conditions. Using this approach, genes from M. perniciosa induced under limiting nitrogen and light were identified from a cDNA library enriched by suppression subtractive hybridization as potential putative pathogenicity genes. From the 159 identified unique sequences, 59 were annotated and classified by gene ontology. Two sequences were categorized as ""Defence genes, Virulence, and Cell response"" presumably coding for allergenic proteins, whose homologues from other fungi are inducers of animal or plant defences. Differential gene expression was evaluated by quantitative amplification of reversed transcripts (RT-qPCR) of the putative identified genes coding for the two allergenic proteins (Aspf13 and 88KD), and for the enzymes Arylsulfatase (AS); Aryl-Alcohol Oxidase; Aldo-Keto Reductase (AK); Cytochrome P450 (P450); Phenylalanine Ammonia-Lyase; and Peroxidase from mycelia grown under contrasting N concentrations. All genes were validated for differential expression, except for the putative Peroxidase. The same eight genes were analysed for expression in susceptible plants inoculated with M. perniciosa, and six were induced during the early asymptomatic stage of the disease. In infected host tissues, transcripts of 88KD and AS were found more abundant at the biotrophic phase, while those from Aspf13, AK, PAL, and P450 accumulated at the necrotrophic phase, enabling to suggest that mycelia transition from biotrophic to necrotrophic might occur earlier than currently considered. These sequences appeared to be virulence life-style genes, which encode factors or enzymes that enable invasion, colonization or intracellular survival, or manipulate host factors to benefit the pathogen`s own survival in the hostile environment. (C) 2010 The British Mycological Society. Published by Elsevier Ltd. All rights reserved.

Technological advances and mechanistic basis for fungal biopulping

Biopulping fundamentals, technology and mechanisms are reviewed in this article. Mill evaluation of Eucalyptus grandis wood chips biotreated by Ceriporiopsis subvermispora on a 50-tonne pilot-plant demonstrated that equivalent energy savings can be obtained in lab- and mill-scale biopulping. Some drawbacks concerning limited improvements in pulp strength and contamination of the chip pile with opportunist fungi have been observed. The use of pre-cultured wood chips as inoculum seed for the biotreatment process minimized contamination problems related to the use of blended mycelium and corn-steep liquor in the inoculation step. Alkaline wash restored part of the brightness in biopulps and marketable brightness values were obtained by one-stage bleaching with 5% H2O2 when bio-TMP pulps were under evaluation. Considering the current scenario, the understanding of biopulping mechanisms has gained renewed attention because more resistant and competitive fungal species could be selected with basis on a function-directed screening project. A series of studies aimed to elucidate structural changes in lignin during wood biodegradation by C. subvermispora had indicated that lignin depolymerization occurs during initial stages of wood biotreatment. Aromatic hydroxyls did not increase with the split of aryl-ether linkages, suggesting that the ether-cleavage-products remain as quitione-type structures. On the other hand, cellulose is more resistant to the attack by C subvermispora. MnP-initiated lipid peroxidation reactions have been proposed to explain degradation of non-phenolic lignin substructures by C subvermispora, while the lack of cellobiohydrolases and the occurrence of systems able to suppress Fenton`s reaction in the cultures have explained non-efficient cellulose degradation by this biopulping fungus. (C) 2007 Elsevier Inc. All rights reserved.

Synthesis of seleno-carbohydrates derived from D-galactose

The synthesis of seleno-galactopyranosides in a short and efficient manner is described, starting from the parent carbohydrate D-galactose. The approach described allows the synthesis of small libraries of compounds with a number of structural variations at the group attached to selenium. Compounds with aryl, propargyl, allyl, acyl, and alkyl substituents are described. (C) 2010 Elsevier Ltd. All rights reserved.

Chiral Triphenylprolinol Ligands for the Efficient Catalytic Asymmetric Arylation of Aldehydes

The synthesis of new chiral amino alcohols by Heck arylation of an enecarbamate is described. These compounds were used as chiral ligands for the catalytic asymmetric arylation of aldehydes and can be easily recovered. Chiral, nonracemic diarylmethanols were obtained in high yields and enantioselectivities.

Enantioselective Arylations Catalyzed by Carbohydrate-Based Chiral Amino Alcohols

The application of carbohydrate-derived amino alcohols in the asymmetric arylation of aldehydes by using arylboronic acids as the source of transferable aryl groups is described. The best ligand is derived from the readily available sugar D-xylose and it mediates the addition of a range of arylboronic acids to various aromatic aldehydes in excellent yields and high enantiomeric excesses.

Ultrasound-assisted synthesis of symmetrical biaryls by palladium-catalyzed detelluration of 1,2-diaryiditellanes

An ultrasound-assisted synthesis of functionalized symmetrical biaryls with electron-withdrawing or electron-donating substituents is described and illustrated by the palladium-catalyzed detelluration of 1,2-diarylditellanes. This procedure offers easy access to symmetrical biaryls in short reaction time and the products are achieved in good to excellent yields. (c) 2009 Published by Elsevier Ltd.