Palladium-catalyzed cascade reaction of alpha,beta-unsaturated sulfones with aryl iodides

Unlike traditionally used acyclic 1,2-disubstituted alkenes, the reaction of alpha,beta-unsaturated phenyl sulfones with aryl iodides under Heck reaction conditions (Pd(OAc)(2) as catalyst, Ag(2)CO(3) as base in DMF at 120 (0)C) takes place mainly by a cascade process, involving one unit of the alkene and three units of the aryl iodide, to afford a substituted 9-phenylsulfonyl-9,10-dihydrophenanthrene. The dominant formation of this 3:1 coupling product, instead of the Heck trisubstituted olefin, shows that aromatic C-H bond activation processes can compete with the usually fast syn beta-hydrogen elimination step in the Heck arylation of an acyclic olefin. The structural scope of this palladium-catalyzed cascade arylation of alpha,beta-unsaturated sulfones has proved to be wide with regard to substitution at the beta-position (alkyl, aryl, or alkenyl substitution), substitution at the sulfone unit (alkyl or phenyl sulfones), and configuration at the CdoublebondC bond (trans or cis). Moreover, although less favored than in the case of the arylation of alpha,beta-unsaturated sulfones, similarly substituted 9,10-dihydrophenanthrenes have also been obtained in the case of alpha,beta-unsaturated phosphine oxides and alpha,beta-unsaturated phosphonate esters. A Pd(0)-Pd(II)-Pd(IV) mechanistic pathway involving the successive formation of highly electrophilic sigma-alkylpalladium intermediates and palladacycles is proposed for this multicomponent arylation.     

2',7'-Difluorofluorescein excited-state proton reactions: correlation between time-resolved emission and steady-state fluorescence intensity

The presence of excited-state buffer-mediated proton exchange reactions influences the steady-state fluorescence signals from dyes in solution. Since biomolecules in general have some chemical groups that can act as proton acceptors/donors and are usually dissolved in buffer solutions which can also behave as appropriate proton acceptors/donors, the excited-state proton exchange reactions may result in distorted steady-state fluorescence signals. In a previous paper (J. Phys. Chem. A 2005, 109, 734-747), we evaluated kinetic and other pertinent parameters for the excited-state proton reactions of the prototropic forms of 2',7'-difluorofluorescein (Oregon Green 488, OG488), recording a fluorescence decay surface at different pH values and acetate buffer concentrations, analyzed by means of global compartmental analysis. In this article we use the rate constants and the corrected pre-exponential factors from the previously recorded fluorescence decay traces to simulate the decay times and associated pre-exponentials at different acetate buffer concentrations and constant pH and compare these theoretically calculated values with new experimental data. We also calculate the steady-state fluorescence intensity vs pH and vs acetate buffer concentration (at constant pH) and compare these calculated emission values with the experimental data previously published. The agreement between the experimental and simulated data is excellent.     

Modular bis(oxazoline) ligands for palladium catalyzed allylic alkylation: unprecedented conformational behaviour of a bis(oxazoline) palladium eta3-1,3-diphenylallyl complex

New families of enantiopure bis(oxazolines) with 4,5-trans (5 a-g) or 4,5-cis (6 c) stereochemistry at the individual rings have been prepared in high yield. Their eta(3)-allyl palladium complexes (8 a-g, 9 c and 10) have been used as catalytic precursors in allylic alkylation reactions with excellent enantioselectivities (up to 96 %) for the trans oxazoline derivatives, while Pd/6 c system was inactive. NMR studies on palladium eta(3)-1,3-diphenylallyl intermediates (11 a, c and e) showed the presence of syn/syn- and syn/anti-allyl isomers in solution; this resembles the first example of eta(3)-eta(1)-eta(3) isomerism in Pd allylic complexes containing bis(oxazolines) derived from malonic acid.     

Structural model of glassy CdGeAs2

Attempts to construct structural models of glassy CdGeAs₂ are described. Microcrystal models with normal and appropriately distorted crystallites gave poor fits with the experiment. Relaxed random network models, in which force constants and equilibrium distances and angles obtained by an energy relaxation of the crystal were used to minimize their free energy, provided excellent agreement with experiment if only even-numbered rings and, therefore, no wrong bonds were allowed to form.     

Abelian varieties with finite abelian group action

An automorphism of an abelian variety induces a decomposition of the variety up to isogeny. There are two such results, namely the isotypical decomposition and Roan’s decomposition theorem. We show that they are essentially the same. Moreover, we generalize in a sense this result to abelian varieties with action of an arbitrary finite abelian group. An early version of this article was inadvertently published before all the revisions had been completed and then retracted [https://doi.org/10.1007/s00013-018-1244-3]. This article is the final peer reviewed version.

     

SALS,WAXS and mechanical properties of heat‐treated thermotropic polymers

The influence of heat treatment on the texture, microstructure and tensile mechanical properties of extruded thin films of a series of high‐performance thermotropic liquid crystal polymers (LCPs) was investigated. LCPs based on random units of hydroxybenzoic acid (B), hydroxynaphthoic acid (N), terephthalic acid (TA) and biphenol (BP) were kindly supplied by the former Hoechst Celanese Corp as 50 µm thick extruded tapes. The LCPs, denoted B‐N, COTBP and RD1000, have B and N as common comonomers and vary the other comonomers. Thus, this study also enables the investigation of the influence of monomer composition on microstructure and mechanical properties. Heat treatments were carried out at temperatures close to the solid‐to‐nematic transition (T_s→n) for periods up to 5 h, under dry air conditions. The thermal treatment produced either two endotherms or a small increase of T_s→n (B‐N and RD1000), or increased significantly T_s→n (COTBP). Moreover, when heat treatment was carried out approximately 40°C below the respective T_s→n, the mechanical Young's modulus, E, along the extrusion axis, increased for all LCPs. Strikingly, for COTBP, E increased over 100% relative to the as‐extruded film. The results also showed that the optimum treatment time for improving the Young modulus, under dry air atmosphere, was between 3 and 4 h. Wide‐angle X‐ray scattering showed a significant sharpening of crystalline reflections and concentration of the 002 meridional reflection as a result of thermal treatment, suggesting the elimination of defects and a better alignment of the molecular chains along the extrusion axis. This would explain the increase in tensile modulus. Copyright © 2013 John Wiley & Sons, Ltd.     

The Preparation Of 2-[4,5-Dihydro-3-Aryl-5-Isoxazolyl]-Phenols From C(α),O-Dilithiooximes and Lithiated Hydroxyaryl Aldehydes

C(a), O-Oximes were dilithiated in excess lithium diisopropylamide, and the resulting intermediates were condensed with lithiated hydroxyphenyl aldehydes and related materials and cyclized with acid to afford 2-[4,5-dihydro-3-aryl-5-isoxazolyl]phenols, substituted 4,5-dihydroisoxazoles (2-isoxazolines).     

A Convenient Method for the Phosphorylation of Phenols with Diethyl Cyanophosphonate

Phosphorylation of phenols with diethyl cyanophosphonate in methylene chloride solution at 0°C is an easy, rapid and good yielding reaction.     

Regiospecific synthesis of 1-acetamide-5-methoxy-2-oxindoles in two steps: (Ugi-SN2)/xanthate mediated free radical cyclization

A series of twelve novel 1-acetamide-5-methoxy-2-oxindoles were prepared in moderate to good yields (30–88%) by an Ugi-S_N2 one pot process with a xanthate mediated free radical cyclization. Additionally, Density Functional Theory (DFT) based calculations were performed at UB3LYP/6-311G(d) level in order to rationalize the energy profile of the xanthate mediated free radical cyclization because the benzo-fused γ-lactams (ortho products) were obtained as sole regioisomers over the spiro β-lactams (ipso products).