bluuebunny/crossref_metadata_2025 huggingface dataset:
The Pauson—Khand Reaction on Aromatic Substrates
Authors: Anorbe Loreto , Dominguez Gema , Perez‐Castells Javier
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
Asymmetric Desymmetrization‐Exploiting Symmetry to Expedite Organic Synthesis
Authors: Spivey Alan C. , Andrews Benjamin I. , Brown Alan D.
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
Supramolecular Chemistry
Authors: Gale Philip A.
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
Selective Aerobic Oxidation of Hydroxy Compounds Catalyzed by Photoactivated Ruthenium‐Salen Complexes (Selective Catalytic Aerobic Oxidation)
Authors: Irie Ryo , Katsuki Tsutomu
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
Thallium in Organic Synthesis
Authors: Uemura Sakae
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
Lithium in Organic Synthesis
Authors: Tomooka Katsuhiko , Ito Masato
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
Application of Hydrolytic Enzymes in the Synthesis of Chiral Heteroorganic Compounds
Authors: Kielbasinski Piotr , Mikolajczyk Marian
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
Heterocumulenes and Thioketenes from 1,2‐Dithiole Derivatives by Flash Vacuum Pyrolysis
Authors: Pedersen Carl Th.
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
Production of Cyclic Tetrasaccharide with 6‐α‐Glucosyltransferase and α‐Isomaltosyltransferase
Authors: Nishimoto Tomoyuki , Aga Hajime , Kubota Michio , Fukuda Shigeharu , Kurimoto Masashi , Tsujisaka Yoshio
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
Advances in Organic Chemistry over the Last 100 Years
Authors: Russell C. A.
Published: April 2005

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Synthesis and Reactivity of Thioaurones over the Past One Hundered Years
Authors: Konieczny Marek T. , Konieczny Wojciech
Published: April 2005

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The Tris(trimethylsilyl)silyl Group in Organic, Coordination and Organometallic Chemistry
Authors: Kornev A. N.
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
Pyrroloiminoquinone and Related Metabolites from Marine Sponges
Authors: Antunes Edith M. , Copp Brent R. , Davies‐Coleman Michael T. , Samaai Toufiek
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
Simple Indole Alkaloids and Those with a Non‐Rearranged Monoterpenoid Unit
Authors: Somei Masanori , Yamada Fumio
Published: April 2005

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Steroids: Reactions and Partial Synthesis
Authors: Hanson James R.
Published: April 2005

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Amaryllidaceae and Sceletium Alkaloids
Authors: Jin Zhong
Published: April 2005

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Photoactive Metallocyclodextrins: Sophisticated Supramolecular Arrays for the Construction of Light Activated Miniature Devices
Authors: Haider Johanna M. , Pikramenou Zoe
Published: April 2005

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Designing Tridentate Ligands for Ruthenium(II) Complexes with Prolonged Room Temperature Luminescence Lifetimes
Authors: Medlycott Elaine A. , Hanan Garry S.
Published: April 2005

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Progress of Understanding Liquid Crystals Made of Bent‐Shaped Molecules
Authors: Mieczkowski J. , Matraszek J.
Published: April 2005

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Organic Chemistry in 2004
Authors: Wuerthner Frank , Tschierske Carsten
Published: April 2005

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Flow Graphs in Chemical Kinetics. Part 1.
Authors: Socol Marius , Baldea Ioan
Published: April 2005

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Peptide—Lipid Interactions: Insights and Perspectives
Authors: Sanderson John M.
Published: April 2005

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Conformational Restriction of Sphingolipids
Authors: Kolter Thomas
Published: April 2005

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Engineering Aspects of Solid‐State Fermentation
Authors: Fernandez‐Fernandez Mario , Perez‐Correa Ricardo , Agosin Eduardo
Published: April 2005

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Solid‐State Fermentation for Bioconversion of Biomass Design of Bioreactors for Solid‐State Fermentation
Authors: Hardin Matt
Published: April 2005

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The Application of Micro Reactors for Organic Synthesis
Authors: Watts Paul , Haswell Stephan J.
Published: April 2005

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Process Reagents for the Enhanced Removal of Solids and Water from Oil Sand Froth
Authors: Madge D. N. , Romero J. , Strand W. L.
Published: April 2005

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Computer‐Aided Organic Synthesis
Authors: Todd Matthew H.
Published: April 2005

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Three‐Dimensional RISM Theory for Molecular Liquids and Solid—Liquid Interfaces
Authors: Kovalenko Andriy
Published: April 2005

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Effect of the Genetic Algorithm Parameters on the Optimization of Heterogeneous Catalysts
Authors: Pereira Silvia R. M. , Clerc Frederic , Farrusseng David , Van der Waal Jan C. , Maschmeyer Thomas , Mirodatos Claude
Published: April 2005

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Application of Data Mining and Evolutionary Optimization in Catalyst Discovery and High‐Throughput Experimentation: Techniques, Strategies, and Software
Authors: Ohrenberg Arne , Von Toerne Christian , Schuppert Andreas , Knab Bernhard
Published: April 2005

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A Semiclassical Quantum Simulation for Laser‐Induced Molecular Dynamics
Authors: Dou Yusheng
Published: April 2005

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High‐Throughput Gas Chromatography and Mass Spectrometry for Heterogeneous Catalysis: Screening of Catalytic Activities and Selectivities
Authors: Weiss Pierre‐Alain W. , Saalfrank Jens W. , Scheidtmann Jens , Schmidt Hans‐Werner , Maier Wilhelm F.
Published: April 2005

For Abstract see ChemInform Abstract in Full Text.
A Comparative Structural and Conformational Study of Some Aza‐, Diazabicyclic and Azatricyclic Systems
Authors: Iriepa Isabel , Villasante F. Javier , Galvez Enrique
Published: April 2005

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Ultraviolet—Visible Spectroscopy
Authors: Weckhuysen Bert M.
Published: April 2005

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Electron Paramagnetic Resonance
Authors: Brueckner Angelika
Published: April 2005

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Nuclear Magnetic Resonance
Authors: Hunger Michael , Weitkamp Jens
Published: April 2005

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Chiral recognition of cyclic α‐hydroxyketones by CD‐sensitive zinc tetraphenylporphyrin tweezer
Authors: Ishii Hideki , Chen Yihui , Miller Ross A. , Karady Sandor , Nakanishi Koji , Berova Nina
Published: April 2005

A combined chemical/chiroptical microscale protocol for the determination of absolute configurations of cyclic α‐hydroxyketones is described. The hydroxyl group in cyclic α‐hydroxyketones is converted into (3‐aminopropylamino)acetate (NH2CH2CH2CH2NHCH2COOR), or more generally, according to a newly developed protocol, into (3‐hydroxypropylamino)acetate group (HOCH2CH2CH2NHCH2COOR). The resultant conjugated compound forms a 1:1 host–guest complex with a dimeric zinc porphyrin tweezer, which exhibits exciton‐coupled bisignate CD spectrum centered around the 420‐nm porphyrin Soret band due to induced helicity between the two porphyrins in the complex. The absolute configurations of the α‐stereogenic center is then determined by comparison of the sign of the observed CD exciton couplet of the complex with that of the preferred porphyrin twist predicted by the Merck Molecular Force Field (MMFFs) method. Chirality 17:305–315, 2005. © 2005 Wiley‐Liss, Inc.
Epoetin‐α during radiotherapy for stage III esophageal carcinoma
Authors: Rades Dirk , Schild Steven E. , Yekebas Emre F. , Job Hendric , Schwarz Rudolf , Rudat Volker
Published: April 2005

BACKGROUND

It has been suggested that hemoglobin levels of 12–14 g/dL are optimal for tumor oxygenation, radiosensitivity, and prognosis. In this prospective study, the authors evaluated the effectiveness of epoetin‐α to maintain hemoglobin levels at 12–14 g/dL during radiotherapy (RT) for patients with UICC Stage III esophageal carcinoma, and they examined the impact of erythropoetin on overall survival (OS), metastatic‐free survival (MFS), and local control (LC).

METHODS

Sixty patients who received RT between March, 2001 and September, 2004, were included in this prospective, nonrandomized study. Thirty patients received epoetin‐α (150 IU/kg 3 times per week) during RT (Group A), and 30 patients did not receive epoetin‐α (Group B). Epoetin‐α was started at hemoglobin levels < 13 g/dL and was stopped at hemoglobin levels ≥ 14 g/dL. Hemoglobin was measured before RT and once weekly during RT.

RESULTS

Both patient groups were balanced for age, gender, performance status, tumor location/length, histology, grading, tumor classification, lymph node status, chemotherapy, treatment (45–50.4 grays [Gy] plus resection vs. 45.0–50.4 Gy vs. 59.4–66.0 Gy), and hemoglobin level before RT. In 20 of 30 patients (67%) from Group A and in 3 of 30 patients (10%) from Group B, ≥ 60% of hemoglobin levels during RT were 12–14 g/dL (P = 0.003). The median change in hemoglobin was + 0.4 g/dL per week in Group A and − 0.4 g/dL per week in Group B. LC was significantly better in Group A (66% vs. 38% at 1 year, respectively; P = 0.012), a trend was observed for OS (59% vs. 33%, respectively; P = 0.08), and MFS did not differ significantly (43% vs. 38%, respectively; P = 0.34). No epoetin‐α‐related toxicity was observed.

CONCLUSIONS

Epoetin‐α was effective in maintaining the hemoglobin levels at 12–14 g/dL during RT. The application of epoetin‐α significantly improved LC, and a trend was observed for OS. Cancer 2005. © 2005 American Cancer Society.
Women age ≤ 35 years with primary breast carcinoma
Authors: Gonzalez‐Angulo Ana M. , Broglio Kristine , Kau Shu‐Wan , Eralp Yesmin , Erlichman Julie , Valero Vicente , Theriault Richard , Booser Daniel , Buzdar Aman U. , Hortobagyi Gabriel N. , Arun Banu
Published: April 2005

BACKGROUND

The purpose of the current study was to describe a population of young patients with breast carcinoma, their characteristics at the time of diagnosis, and the association of these characteristics with disease recurrence and survival.

METHODS

Four hundred fifty‐two women age ≤ 35 years with breast carcinoma were registered at The University of Texas M. D. Anderson Cancer Center (Houston, TX) between 1990 and 2002. The relation between clinicopathologic factors and disease recurrence‐free survival (RFS) and overall survival (OS) was assessed. Cox regression analysis was used to identify independent survival predictors.

RESULTS

The median age of the patients was 32 years. Most of the patients were white, and 20% were obese. Approximately 50% reported oral contraceptive use, 34% reported a family history of breast carcinoma, and 5% reported a family history of ovarian carcinoma. Sixty‐nine percent of tumors were nuclear Grade 3 (using the modified Black's nuclear grading system), 52% had positive estrogen receptors, and 48% had positive progesterone receptors. HER‐2/neu status was available in 60% of tumor specimens and 34% were HER‐2/neu positive. The median follow‐up was 36 months. There were 185 disease recurrences and 84 deaths. RFS was significantly shorter in patients who reported a family history of ovarian carcinoma (P < 0.0001) and in those who had hormone receptor‐negative tumor specimens (P = 0.001). OS was significantly shorter in patients who reported a family history of ovarian carcinoma (P = 0.001), those who had hormone receptor‐negative tumor specimens (P < 0.0001), or those with > nuclear Grade 3 tumor specimens (P = 0.005).

CONCLUSIONS

This young population with breast carcinoma was found to have more aggressive biologic features. Hormone receptor negativity and a family history of ovarian carcinoma were associated with shorter RFS and OS. Cancer 2005. © 2005 American Cancer Society.
Platinum Nanoelectrodes Embedded in an Insulating Alumina Matrix: An Innovative Approach
Authors: Battiston G. A. , Daniele S. , Dluzewski P. , Gambirasi A. , Gerbasi R. , Rodriguez A. , Szczepanska A.
Published: April 2005

A novel strategy, based on MOCVD, has been employed for preparation of ensembles of platinum nanoelectrodes. Pt/Al2O3 films with different Pt loading were deposited in just one step on glass capillaries. Nanocomposite films with varying Pt/Al atomic ratios were investigated by both cyclic voltammetry and TEM. Ensembles of nanoelectrodes with either overlap or no overlap of the diffusion layers of each nanoelectrode are obtained, depending on the Pt loading. From TEM measurements average Pt particle size of 3 – 7 nm was determined (Figure).
Liquid‐Delivery MOCVD of Strontium Bismuth Tantalate Thin Films Using Sr[Ta(OC2H5)5(OCH2CH2OCH3)]2 and Liquid Bi(CH2CH=CH2)3 as Precursors
Authors: Hyeon J.‐Y. , Lisker M. , Silinskas M. , Burte E. , Edelmann F. T.
Published: April 2005

Thin films of BiOX, SrXTaYOZ, and strontium bismuth tantalate (SBT) were deposited by metal‐organic (MO)CVD on 150 mm silicon (100) wafers. Some of the wafers were pre‐deposited with Pt electrodes. The substrate temperature and the deposition pressure were varied from 300 °C to 600 °C and from 0.35 mbar to 7 mbar, respectively. Bi(CH2CH=CH2)3 (triallylbismuth) and Sr[Ta(OEt)5(OC2H4OMe)]2 (strontium‐bis[tantalum(pentaethoxide)(2‐methoxyethoxide)]) were used as Bi precursor and as Sr‐Ta precursor, respectively. A liquid delivery system was used to supply and to vaporize the precursors into the reactor. X‐ray photoelectron spectroscopy (XPS) and ellipsometry were carried out to characterize the film properties. The growth rate of the MOCVD of BiOX and SrXTaYOZ was compared to the growth rate of SBT to obtain information about mutual interaction between the precursors. The deposition rate of bismuth oxide thin films was low (∼10 nm h–1 at 0.35 mbar) and virtually independent of the temperature. On the contrary, the growth rate of strontium tantalate films depended strongly on the temperature. The deposition rate of the SBT films was similar to the bismuth oxide film deposition, which slightly increased with increasing substrate temperature. However, the deposition rate of SBT was always lower than deposition rate of the single precursors. The growth rate significantly depended on pressure. The decrease of the deposition pressure in the reactor chamber reduced the deposition rate of BiOX, SrXTaYOZ, and SBT but on the other hand, it improved the uniformity of the film thickness. XPS measurements showed a deficit of bismuth in the SBT films even though the concentration of the Bi precursor had been several times higher than the concentration of Sr‐Ta precursor. The XPS depth‐profiling by Ar+ ion sputtering indicated more metallic bond characteristics of Ti, Sr, and Bi after ion‐beam bombardment.
Deposition of Silver Thin Films Using the Pyrazolate Complex [Ag(3,5‐(CF3)2C3HN2)]3
Authors: Chi Y. , Lay E. , Chou T.‐Y. , Song Y.‐H. , Carty A. J.
Published: April 2005

The synthesis and characterization of a series of silver pyrazolate complexes [Ag(tfpz)]3 (1), [Ag(fbpz)]3 (2), [Ag(dbpz)]3 (3), and [(py)Ag(tfpz)]2 (4) are reported, for which tfpz, fbpz, dbpz are abbreviations for the pyrazolate ligands with formulae 3,5‐(CF3)2‐pz, 3‐tBu‐5‐(CF3)‐pz, and 3,5‐(tBu)2‐pz, respectively. These silver complexes were characterized by microanalysis and spectroscopic methods. The CF3‐substituted complex 1 possesses the highest volatility and stability against thermal decomposition. Low pressure CVD experiments were conducted over the temperature range 250–350 °C. Silver metal thin films were successfully obtained on silicon wafers using pure H2 as the carrier gas. Scanning electron microscopy (SEM) was used to reveal surface morphologies, while X‐ray photoelectron spectroscopy (XPS) and X‐ray diffraction (XRD) were utilized to determine the atomic composition of the as‐deposited thin films as well as the crystallite packing.
Synthesis, Molecular Structure and Reactivity of a Calix[4]arene Monomethyl Ether Supported Nitridomolybdenum Complex
Authors: Zeller Jürgen , Büschel Susanne , Reiser Benjamin K. H. , Begum Farida , Radius Udo
Published: April 2005

The calix[4]arene monomethyl ether supported nitridomolybdenum complex [MoN(MeCalix)] (1) was obtained in high yield from the reaction of [MoN(OtBu)3] and calix[4]arene methyl ether (H3MeCalix). Contrary to the calix[4]arene dimethyl ether supported dioxomolybdenum complex [MoO2(paco‐Me2Calix)] published earlier, the calix[4]arene ligand in 1 adopts a cone conformation. Complex 1 reacts smoothly with GaCl3 and GaEt3 to yield the compounds [Mo(NGaCl3)(MeCalix)] (2) and [Mo(NGaEt3)(MeCalix)] (3), respectively. Complex 2 is the first structurally characterized example of a nitrido‐bridged dinuclear compound of a group 6 metal and a group 13 halide (EX3). The [Mo≡N–GaCl3] unit, in which both metal atoms are unsymmetrically bridged with a short Mo≡N and a long Ga–N contact, shows significant bending at the nitrido bridge. This deviation from a linear alignment is attributed to packing forces. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Group II Intron Ribozymes and Metal Ions – A Delicate Relationship
Authors: Sigel Roland K. O.
Published: April 2005

Group II introns are naturally occurring ribozymes in plants, fungi, bacteria, and lower eukaryotes that undergo a fascinating array of reactions. These large molecular machines with a size ranging between 600 and 2500 nucleotides are self‐splicing introns also capable of reinserting themselves into RNA or DNA, thus making them mobile genetic elements. The structural information available on group II intron ribozymes is very scarce. So far, only one crystal structure and one NMR solution structure of two domains located in the catalytic core are available. For proper folding and function, each intron requires specific concentrations of monovalent and divalent metal ions. Although most of these metal ions are used for charge screening, some are bound to distinct sites as has been shown by hydrolytic cleavage experiments. These specifically bound ions are crucial for tertiary contact formation and catalysis. This review will discuss the different metal‐ion requirements of self‐splicing group II introns, the available structural data and information on the binding location and affinity of metal ions, as well as the methods applied to investigate the metal‐ion binding properties of these large RNAs. Due to the size of these introns, the richness of local structures, the catalytic versatility and the involvement of metal ions in all of the above‐mentioned aspects, group II introns are an ideal target to be studied by combined means from the fields of Biochemistry, Molecular Biology, Analytical, and (Bio)Inorganic Chemistry. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Molecular Recognition: Use of Metal‐Containing Molecular Clefts for Supramolecular Self‐Assembly and Host–Guest Formation
Authors: Crowley James D. , Bosnich Brice
Published: April 2005

Molecular clefts consisting of a rigid spacer linked to two parallel cofacially disposed terpy‐M–X (M = Pd2+, Pt2+) units, which can vary in separation from 6.6 to 7.2 Å, have been used as molecular receptors and for self‐assembly with linear and triangular linkers to produce rectangles and trigonal prisms, respectively. Aromatic molecules form multiple host–guest adducts with the molecular cleft receptors and with the rectangles and trigonal prisms. Planar complexes of Pt2+ also form host–guest adducts. The forces that control this molecular recognition, namely, π‐π interactions, charge‐induced dipole interactions, charge‐charge forces, weak metal‐metal interactions and solvation effects, are discussed and assigned to the various adducts. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
The Associative Properties of Some Amphiphilic Fullerene Derivatives
Authors: Angelini Guido , Cusan Claudia , De Maria Paolo , Fontana Antonella , Maggini Michele , Pierini Marco , Prato Maurizio , Schergna Stefano , Villani Claudio
Published: April 2005

The hydrophilic vs. hydrophobic balance for five C60 derivatives (FD1–5) bearing one hydrophilic addend has been evaluated by means of useful descriptors derived from (i) aggregation measurements in aqueous/organic mixtures, (ii) partition measurements between n‐octanol and water (log Pm/a), and (iii) retention factors in reverse‐phase chromatography (log kw). Aggregates of FD1–5 have been obtained both in water and in aqueous organic mixtures. The dimension of the aggregates has been estimated by gel‐permeation chromatography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Nucleophilic Reactivities of Silyl Ketene Acetals and Silyl Enol Ethers Containing (C6F5)3SiO and (C6H5)3SiO Groups
Authors: Dilman Alexander D. , Mayr Herbert
Published: April 2005

The kinetics of the reactions of tris(pentafluorophenyl)silyl and triphenylsilyl ketene acetals and enol ethers with benzhydrylium cations have been measured photometrically. The second‐order rate constants (log k2) have been used to determine the nucleophilicity parameters of these π systems, which provide a quantitative comparison of their reactivities with those of other types of nucleophiles. A change from trimethylsilyloxy to triphenylsilyloxy reduces reactivity by only a factor of ten, while replacement of triphenylsilyloxy with tris(pentafluorophenyl)silyloxy decreases the nucleophilicity of the enolate C=C double bond by three to four orders of magnitude. The cation‐stabilizing ability of the tris(pentafluorophenyl)silyloxy group is thus similar to that of a methyl group. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Asymmetric Cyanohydrin Synthesis Catalyzed by Al(salen)/Triphenylphosphane Oxide
Authors: Kim Sung Soo , Song Dae Ho
Published: April 2005

Various aldehydes undergo asymmetric trimethylsilylcyanation with (CH3)3SiCN (TMSCN) in the presence of a chiral Al(salen) complex and Ph3PO as the catalyst. This is a double activation where Al(salen) plays the role of Lewis acd and POPh3 acts as a Lewis base. Various kind of aldehydes were subjected to the enantioselective addition of (CH3)3SiCN at temperatures between –40 °C and –50 °C. Hydrolysis of the adducts gave cyanohydrins with over 90 % yield and 80 % ee in most cases. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Pyrimidine‐Annulated Pyrrolobenzodiazepines. A New Ring System Related to Aspergillus Alkaloids
Authors: Schmidt Andreas , Gholipour Shilabin Abbas , Christoph Namyslo Jan , Nieger Martin , Hemmen Sascha
Published: April 2005

Pyrrolo[2,1‐c][1,4]benzodiazepine‐5,11‐dione was converted into the corresponding C‐11‐monothiolactam and subsequently treated with amines to give cyclic amidines, which racemize due to the formation of tautomers (NMR, X‐ray analysis) under basic conditions. We treated these amidines with bis(trichlorophenyl) malonate esters. Formation of neutral tautomers of the 1,3,8‐triones of the new 4,7a,12b‐triaza‐dibenzo[e,g]azulene ring system gave a twisted molecule with both helical and chiral structure elements (NMR, X‐ray analysis), which caused a splitting of the NMR signals into two sets. Results of two X‐ray single crystal analyses are presented, together with an ab initio calculation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Studies Towards the Synthesis of Functionalized Medium‐Sized Carbocyclic and Fused Bicyclic Systems by Alkoxy Radical Fragmentation (ARF)
Authors: Ramesh Namakkal G. , Hassner Alfred
Published: April 2005

The stereoselective construction of polyfunctionalized medium‐sized carbocyclic and fused bicyclic systems from substituted bicyclo[3.n.1]alkanones has been studied; the strategy employed involved Suarez’s alkoxy radical fragmentation reaction (ARF) as the key step. The scope of the reaction was examined and this methodology was found to be especially useful for stereo‐ and regioselective construction of eight‐membered carbocycles including bicyclo[6.4.0]dodecane systems, a framework that is present in a variety of biologically active natural products. This reaction was also used successfully in the synthesis of seven‐membered carbocycles but with low selectivity. It was found that the presence of a hemiketal functionality in the molecule is essential for the ARF reaction to occur; hence nine‐ and ten‐membered ring analogs could not be attained since the precursor bicyclic ketones do not form the required hemiketals. This is borne out by MM calculations. Finally, a diquinane was also synthesized. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Phosphonate Modification for a Highly (Z)‐Selective Synthesis of Unsaturated Esters by Horner–Wadsworth–Emmons Olefination
Authors: Touchard François P.
Published: April 2005

The Horner–Wadsworth–Emmons (HWE) reaction of various ethyl diarylphosphonoacetates with benzaldehyde, cyclohexane carboxaldehyde and octanal is reported. Selectivities of up to 98 % at –78 °C are obtained with the three substrates. Among all the phosphonates prepared, the reagent based on 2‐tert‐butylphenol proved to be especially efficient, with Z/E ratios close to 95:5 at 0 °C. It appears thus to be the reagent of choice for the (Z)‐selective HWE reaction with both aromatic and aliphatic aldehydes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Preparation of 3‐(Fluoroalkyl)‐2‐azadienes and Its Application in the Synthesis of (Fluoroalkyl)isoquinoline and ‐pyridine Derivatives
Authors: Palacios Francisco , Alonso Concepción , Rodríguez Marta , Martínez de Marigorta Eduardo , Rubiales Gloria
Published: April 2005

A method for the preparation of 3‐(fluoroalkyl)‐substituted 2‐azabutadienes 5 by aza‐Wittig reaction of N‐vinylic 3‐(fluoroalkyl)phosphazenes 4 and aldehydes is reported. Thermal 6π‐electrocyclization of these azadienes gives 3‐(fluoroalkyl)‐substituted isoquinolines 6. Also [4+2] cycloaddition of these heterodienes 5 with enamine 8 gives fluoroalkyl‐substituted pyridine derivatives 10–16. However, the reaction of azadienes 17 with azo compound 18 affords bicyclic heterocycles 19. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Intramolecular Heck Reactions for the Synthesis of the Novel Antibiotic Mensacarcin: Investigation of Catalytic, Electronic and Conjugative Effects in the Preparation of the Hexahydroanthracene Core
Authors: Tietze Lutz F. , Stewart Scott G. , Polomska Marta E.
Published: April 2005

The intramolecular Heck reaction of the three complex diphenyl substrates rac‐2, 5 and rac‐6, containing substituents with different electronic and conjugative properties, were examined. The Pd compounds [Pd2(dba)3]/[(tBu)3PH]BF4, [Pd2(OAc)2{P(o‐Tol)3}2] (4), [PdCl2(PPh3)2] and Pd(OAc)2 were used as catalysts. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Further Synthetic Studies Towards the Austrodorane Skeleton: Synthesis of Austrodoral
Authors: Kulciţki Veaceslav , Ungur Nicon , Gavagnin Margherita , Carbone Marianna , Cimino Guido
Published: April 2005

The synthesis of austrodoral (1), a marine nor‐sesquiterpene that contains a unique bicyclic skeleton, has been achieved. The synthetic strategy is based on the ring contraction of a suitable optically active drimanic epoxy derivative, obtained from commercially available (+)‐sclareolide (4). Fluorosulfonic acid was found to promote the ring contraction efficiently. The nor‐sesquiterpene hydrocarbon 13, a key intermediate in the synthesis of sesquiterpene hydroquinones, has also been prepared in optically active form. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Facial Diastereoselectivity in Cationic Propargylations with Planar‐Chiral AreneCr(CO)3‐Substituted Propargyl Cations
Authors: Netz Astrid , Polborn Kurt , Nöth Heinrich , Müller Thomas J. J.
Published: April 2005

The planar‐chiral (o‐methoxyphenyl)chromium tricarbonyl‐substituted propargyl cation 4 reacts with silyl enol ether derivatives 5 with poor and with enamines 6 with good facial diastereoselectivity to give rise to the (arene)carbonylchromium‐substituted propargylated cyclohexan‐2‐ones 7 and 8, carboxylic acid 9, γ‐lactone 10, cyclopentan‐2‐one 11, and esters 16 and 17. Structural correlations were unambiguously deduced from X‐ray structure analyses of 7a, 9a, and 17a. The origin of facial diastereoselectivity with this class of organometallic electrophiles lies in steric and stereoelectronic biases rather than in purely electronic nucleophilicity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Silver(I)‐Catalysed Protiodesilylation of 1‐(Trimethylsilyl)‐1‐alkynes
Authors: Carpita Adriano , Mannocci Luca , Rossi Renzo
Published: April 2005

A procedure for protiodesilylation of 1‐(trimethylsilyl)‐1‐alkynes that involves the use of catalytic amounts of AgNO3 and does not require the employment of KCN is described. This procedure allows for chemoselective deprotection of 1‐(trimethylsilyl)‐1‐alkynes containing α‐(trimethylsilyl)benzyl moieties, tert‐butyldiphenylsilyl alkyl ethers or tert‐butyldimethylsilyl aryl ether groups. However, it causes complete desilylation of 1‐(trimethylsilyl)‐1‐alkynes characterised by a primary alcoholic group protected as a tert‐butyldimethylsilyl ether. Interestingly, compounds that contain this last functional group can also furnish the corresponding alcohols by treatment with a catalytic amount of aqueous HNO3. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Synthesis and Biological Evaluation of Apicularen A Analogues
Authors: Petri Andreas F. , Sasse Florenz , Maier Martin E.
Published: April 2005

Reactions between amide anions and propanal derivatives containing benzolactone components at their 3‐positions produced hemiaminals, which were dehydrated via the corresponding acetates to provide the apicularen A analogues 21, 29, 34, 38, and 41. Of these, 21 and 29 contain the intact enamide side chain of apicularen A but have modifications in the macrolactone core. On the other hand, compounds 34, 38, and 41 are characterized by the natural core structure but are modified in the enamide part. Biological studies showed that 21 and 29 are quite active but that the other three analogues show only minor activities. The 11‐deoxy analogue 21 turned out to be the most active compound against a mdr cell line. It can be concluded that the macrolactone part of apicularen A will tolerate modifications to some degree, whereas the enamide part is rather sensitive towards structural modifications. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Stereoselective Chloro‐Deboronation Reactions Induced by Substituted Pyridine–Iodine Chloride Complexes
Authors: Batsanov Andrei S. , Howard Judith A. K. , Lightfoot Andrew P. , Twiddle Steven J. R. , Whiting Andrew
Published: April 2005

A novel class of charge‐transfer complexes based on iodine chloride and substituted pyridines, which possess a number of interesting and unique structural features, can be employed to bring about a stereocontrolled chloro‐deboronation of certain vinyl boronates to generate the (1Z)‐alkenyl chlorides in good yields. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Preparation of Enantiomerically Pure [3]Ferrocenophane‐Based Chelate Bis‐Phosphane Ligands and Their Use in Asymmetric Alternating Carbon Monoxide/Propene Copolymerization
Authors: Liptau Patrick , Tebben Ludger , Kehr Gerald , Fröhlich Roland , Erker Gerhard , Hollmann Frank , Rieger Bernhard
Published: April 2005

An intramolecular Mannich reaction (HNMe2, TiCl4) was used to convert 1,1'‐diacetylferrocene to the unsaturated amino[3]ferrocenophane 2. Subsequent hydrogenation gave 3. To obtain enantiomerically pure chelate P,P‐[3]ferrocenophane ligands the readily available pure dimethylamino[3]ferrocenophane enantiomers (R,R)‐3 and (S,S)‐3 each were treated with butyllithium followed by chlorodiphenylphosphane to yield the chelate P,N‐[3]ferrocenophanes (R,R,Rpl)‐10 and (S,S,Spl)‐10, respectively. Their treatment with HPPh2 in glacial acetic acid resulted in substitution of the –NMe2 group by –PPh2 with overall retention of configuration to yield (R,R,Rpl)‐11 and (S,S,Spl)‐11, respectively (both characterized by X‐ray diffraction). Similarly, the reaction of (R,R,Rpl)‐10 or (S,S,Spl)‐10 with dicyclohexylphosphane/HOAc yielded the pure (R,R,Rpl)‐12 and (S,S,Spl)‐12 enantiomers, respectively. Both these compounds were also characterized by X‐ray crystal structure analyses. (R,R,Rpl)‐12 was employed in catalytic asymmetric hydrogenation and also in asymmetric alternating carbon monoxide/propene copolymerization. A catalyst that was generated in situ from the chelate P,P‐[3]ferrocenophane ligand and palladium acetate gave the CO/propene alternating copolymer with a good activity and high asymmetric induction. The catalyst derived from the reaction of (R,R,Rpl)‐11 with [Rh(cod)2]BF4 was employed in the enantioselective hydrogenation of dimethyl itaconate (DMI) (13, ca. 95 % ee, R‐configured product) and methyl α‐acetamidocinnamate (MAC) 14 (ca. 24 % ee, R‐configured product). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Elemental Fluorine and HOF·CH3CN in Service of General Organic Chemistry
Authors: Rozen Shlomo
Published: April 2005

At present, HOF·CH3CN complex is the best oxygen transfer agent that chemistry has to offer. It is readily made by passing dilute fluorine through aqueous acetonitrile and does not require any isolation or purification. It is stable in aqueous acetonitrile solution for a few hours at room temperature, providing ample opportunities for various reactions. Epoxidation of regular olefins as well as of very electron‐depleted ones proceeds smoothly. HOF·CH3CN transfer oxygen also to heteroatoms, especially sulfur and nitrogen. Even very electron‐depleted sulfides such as RfSAr that are very difficult to oxidize, are converted into the respective sulfones in a matter of minutes. On the other hand, since the reaction conditions are very mild, the reagent can oxidize various thiophenes and amino acids to the corresponding S,S‐dioxides and α‐nitro acid derivatives. HOF·CH3CN was also instrumental in ending the 50 years quest for making the elusive 1,10‐phenanthroline N,N‐dioxide and for the novel transformation of azides to nitro derivatives. The use of BrF3 for making symmetric esters and of tBuOF as an electrophilic tert‐butoxylation agent is also mentioned. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
A Highly Efficient Synthesis of Rocaglaols by a Novel α‐Arylation of Ketones
Authors: Diedrichs Nicole , Ragot Jacques P. , Thede Kai
Published: April 2005

Rocaglaols are natural products exhibiting a range of biological activities. A new synthetic method for the α‐arylation of ketones allows for the synthesis of previously inaccessible rocaglaol derivatives. The key sequence consists of a previously unreported Suzuki type reaction using brominated silyl enol ethers as substrates followed by deprotection of the arylated silyl enol ethers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Enantioselective Synthesis of Thiosulfinates and of Acyclic Alkylidenemethylene Sulfide Sulfoxides
Authors: Colonna Stefano , Pironti Vincenza , Drabowicz Jozef , Brebion Franck , Fensterbank Louis , Malacria Max
Published: April 2005

Enantioselectivities up to 75 % have been found in the catalytic mono‐oxidation of di‐tert‐butyl disulfide and related compounds as well as of ketene‐S,S‐acetals with an in situ generated chiral dioxirane. The effect of solvents on the enantiomeric excess has also been examined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
A New Glucose: Towards Conformationally Locked Hexoses through Annulation
Authors: Mehta Goverdhan , Ramesh Senaiar S.
Published: April 2005

A new family of surface‐modified carbohydrates with locked, axial‐rich conformations and bipolarofacial architectures has been developed with the aid of carbocyclic ring annulation. These novel trans‐decalin‐based carbohydrates have been synthesized, from simple aromatic precursors such as tetralin, through the ozonolysis of an appropriately protected allylic alcohol, followed by a cascade of intramolecular acetalizations to generate the sugar pyran moiety. The stereoselective synthesis of (racemic) cyclohexane‐annulated β‐glucopyranoside and α‐glucofuranoside from a common annulated trans‐cyclohexadiene diol (trans‐CHD) precursor underscores the versatility of our approach. The efficacy of the annulation stratagem in generating carbohydrate diversity has been demonstrated through the synthesis of two regioisomeric annulated gulose derivatives, which differ only in the site of ring annulation on the sugar moiety. The mapping of the MLP surface and solid‐state architecture of the new sugar shows that cycloalkane annulation results in surface modification and fine‐tuning of sugar hydrophilicity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Childhood conduct problems, stages of Alzheimer's disease, and physical aggression against caregivers
Authors: O'Leary Daniel , Jyringi Darlene , Sedler Mark
Published: April 2005

Objective

To assess the prevalence of physical aggression against caregivers by Alzheimer's patients.

Method

One hundred and ninety‐eight individuals with dementia, primarily Alzheimer's disease (AD) were evaluated with the Cohen‐Mansfield Agitation Inventory, the Mini Mental Status Examination, two measures of Activities of Daily Living, portions of the Conflict Tactics Scale to measure physical aggression against partner, questions about conduct problems during childhood/adolescence of the patients, and chart records of delusion and paranoia.

Results

25% of the patients engaged in physical aggression against their caregivers in the past year, and 33% of the patients engaged in some act of physical aggression against any individual in the past two weeks. Physical aggression against a caregiver was more likely in the middle (34%) than the early stage of AD (4%). Physical aggression against a partner and agitation were more likely if the patient had a history of symptoms of conduct disorder. Delusions and paranoia were both associated with general physical aggression and general verbal aggression but not physical aggression against a caretaker.

Conclusions

25% of Alzheimer's disease and Multi‐Infarct dementia patients engaged in acts of physical aggression against their caregivers. The rate of aggression seen in this clinical sample was much higher than the rate of physical aggression in a community sample of the elderly. Copyright © 2005 John Wiley & Sons, Ltd.
Does arm length indicate cognitive and functional reserve?
Authors: Jeong Seul‐Ki , Kim Jae‐Min , Kweon Sun‐Seog , Shin Min‐Ho , Seo Man‐Wook , Kim Young‐Hyun
Published: April 2005

Background

This study aimed to examine whether arm length and height were associated with cognitive and functional abilities.

Methods

Screening interviews were conducted in 235 community dwelling individuals aged 65 and over. The assessment scales included the Korean version of modified Mini‐Mental State Examination (K‐mMMSE) for cognition, and the Korean Instrumental Activities of Daily Living (K‐IADL) for functional ability. All the participants were examined clinically and a diagnosis of dementia was ascertained. Anthropometric measurements included total arm span and height.

Results

Both arm length and height correlated significantly with the cognitive and functional scales. In the multivariate regression models, their associations were significant, independent of age, sex, education, and other variables. Shorter arm length was also significantly associated with dementia; while, height lost significance after an adjustment for the potential confounders.

Conclusions

Arm length and height could indicate cognitive and functional ability. Arm length, which was known to be less prone to degenerative processes, might be more stable as an indicator for cognitive and functional reserve capacity than height. Copyright © 2005 John Wiley & Sons, Ltd.
Dementia in Parkinson's disease: a post‐mortem study in a population of brain donors
Authors: Papapetropoulos S. , Gonzalez J. , Lieberman A. , Villar J. M. , Mash D. C.
Published: April 2005

Objective

To identify factors associated with dementia in a cohort of Parkinson's disease (PD) brain donors and determine whether its presence may influence the clinical phenotype of the disease.

Methods

We included 67 consecutive patients with a clinical and pathological diagnosis of PD, who while alive, consented to donate their brains to the University of Miami Brain Endowment BankTM. Dementia and psychiatric complications of PD were diagnosed according to established criteria. Case histories were abstracted and reviewed and comparisons between PD patients with (PD‐D, n = 34) and without (PD, n = 33) dementia were made.

Results

Age at death, age at disease onset and disease duration did not differ significantly between PD‐D and PD patients. Other symptoms were similar in both groups. Visual hallucinations and bilateral symptoms at diagnosis were significantly higher in PD‐D patients. No association between dementia and overall survival duration was found. Although the frequency of depression and psychosis was higher in the PD patients with dementia no statistical significance was reached. The overall lifetime prevalence of dementia in our group was 50.7%.

Conclusions

Visual hallucinations and bilateral symptoms were associated with dementia in our cohort of PD brain donors. No association between dementia and survival duration was found. Understanding the influence of dementia on the clinical phenotype of the disease and predicting its development is essential for the successful management of PD. Copyright © 2005 John Wiley & Sons, Ltd.
A pilot study examining the effectiveness of maintenance Cognitive Stimulation Therapy (MCST) for people with dementia
Authors: Orrell Martin , Spector Aimee , Thorgrimsen Lene , Woods Bob
Published: April 2005

Background

A recent randomised controlled trial on Cognitive Stimulation Therapy (CST) identified the need to evaluate its more long‐term benefits for people with dementia. This study evaluates the effectiveness of a weekly maintenance CST programme for people with dementia in residential care.

Method

Thirty‐five people with dementia were included, following on from a seven‐week twice‐weekly study of CST. The maintenance CST sessions ran in two residential homes using a once a week programme of CST over an additional 16 weeks. Two control homes did not receive the maintenance intervention.

Results

Using repeated measures ANOVAS, there was a continuous, significant improvement in cognitive function (MMSE) for those receiving MCST (CST+maintenance CST sessions) as compared to CST alone or no treatment (p = 0.012). There were no effects on quality of life, behaviour or communication following maintenance sessions. The initial cognitive improvements following CST were only sustained at follow‐up when followed by the programme of maintenance CST sessions.

Conclusions

The cognitive benefits of CST can be maintained by weekly sessions for around 6 months. A large‐scale, multi‐centre maintenance CST trial is required to clarify potential longer‐term benefits of maintenance CST for dementia. Copyright © 2005 John Wiley & Sons, Ltd.
VITA: subtypes of mild cognitive impairment in a community‐based cohort at the age of 75 years
Authors: Jungwirth S. , Weissgram S. , Zehetmayer S. , Tragl K. H. , Fischer P.
Published: April 2005

Background

Mild cognitive impairment (MCI) is defined to diagnose prodromal dementia and prodromal Alzheimer dementia, in particular.

Objective

The main aim of this study is to identify subtypes of MCI in comparison to the frequency of Petersen's MCI‐amnestic in an elderly age‐cohort.

Participants

The study is based on the cross sectional data from the Vienna‐Transdanube‐Aging (VITA) study. The data refer to the age cohort of 592 individuals at age 75 to 76 years who completed extensive neuropsychological examination.

Results

Dementia was present in 15 subjects (2.5%, CI: 1.4–4.1). 141 subjects (23.8%, CI: 20.4–27.5) of the entire age cohort 75 (n = 592) showed cognitive impairment without dementia concerning one or more cognitive functions (1.5 SD paradigm). These subjects were assigned to three subtypes of MCI: Selective Memory Impairment: n = 22 (3.7%, CI: 2.3–5.6), Memory Impairment+Non‐Memory Impairment: n = 31 (5.2%, CI: 3.6–7.4) and Non‐Memory Impairment: n = 88 (14.9%, CI: 12.1–18.0).

Conclusions

The frequency of MCI‐amnestic, the so‐called prestage of AD according to Petersen, was very low (0.5%, CI: 0.1–1.5) compared to the estimated incidence rates of AD at this age. Established criteria of MCI could be modified in order to include a higher percentage of high‐risk subjects for later developing Alzheimer dementia. Copyright © 2005 John Wiley & Sons, Ltd.
The Center for Epidemiologic Studies Depression Scale in older Chinese: thresholds for long and short forms
Authors: Cheng Sheung‐Tak , Chan Alfred C. M.
Published: April 2005

Objective

No study has examined the diagnostic validity of the Center for Epidemiologic Studies Depression Scale (CES‐D) in the Chinese elderly. This study aims to determine appropriate cutoffs for the 20‐ (CESD‐20) as well as a ten‐item (CESD‐10) version of the instrument. Data were also provided, based on simulated scoring, for the diagnostic performance of the scales when using dichotomous instead of 4‐point rating scales.

Methods

Three hundred and ninety eight persons aged 60 +referred for psychiatric asssessment by a physician were administered the CES‐D as well as given an independent psychiatric assessment. A spectrum of depression diagnosis as the criterion was used to assess the diagnostic validity of the CES‐D.

Results

The ten and the 20‐item version of the CES‐D, regardless of scoring method, produced essentially identical performance indices. The optimal thresholds were 12 and 22 for CESD‐10 and CESD‐20 respectively, and based on these thresholds, sensitivity, specificity, positive predictive value and negative predictive value were 0.76, 0.55, 0.57 and 0.74 for CESD‐10, and 0.75, 0.51, 0.55 and 0.72 for CESD‐20. With both ends of the rating scale collapsed to create dichotomous items, the optimal thresholds became 4 for CESD‐10 and 7 for CESD‐20, and the correponding performance indices were 0.67, 0.58, 0.56 and 0.69 for CESD‐10, and 0.70, 0.58, 0.57 and 0.70 for CESD‐20.

Conclusions

The ten‐item version can be used in lieu of the 20‐item version, and a dichotomous response format would probably work as well as the original four‐point format, in order to simplify administration for elderly persons. Copyright © 2005 John Wiley & Sons, Ltd.