Low-valent niobium-mediated double activation of C-F/C-H bonds: fluorene synthesis from o-arylated alpha,alpha,alpha-trifluorotoluene derivatives

By the treatment of 0.3 molar amount of NbCl5 and LiAlH4, o-arylated alpha,alpha,alpha-trifluorotoluenes afforded fluorene derivatives in good yields. C-F bonds of the CF3 group and the neighboring ortho C-H bond were doubly activated to give the coupling products.     

Changes in thermodynamic quantities upon contact of two solutes in solvent under isochoric and isobaric conditions

The changes in excess thermodynamic quantities upon the contact of two solutes immersed in a solvent are analyzed using the radial-symmetric and three-dimensional versions of the integral equation theory. A simple model mimicking a solute in water is employed. The solute-solute interaction energy is not included in the calculations. Under the isochoric condition, the solute contact always leads to a positive entropy change irrespective of the solute solvophobicity or solvophilicity. The energy change is negative for solvophobic solutes while it is positive for solvophilic ones. Under the isobaric condition, the contact of solvophobic solutes results in system-volume compression but that of solvophilic ones gives rise to expansion. Effects of the compression and expansion on the changes in enthalpy and entropy are enlarged with rising temperature. When the solute solvophobicity is sufficiently high, the entropy change (multiplied by the absolute temperature) can become negative due to the compression, except at low temperatures with the result of an even larger, negative enthalpy change. The expansion in the case of solvophilic solutes leads to a large, positive entropy change accompanied by an even larger, positive enthalpy change. The changes in enthalpy and entropy are strongly dependent on the temperature. However, the changes in enthalpy and entropy are largely cancelled out and the temperature dependency of the free-energy change is much weaker. The authors also discuss possible relevance to the enthalpy-entropy compensation experimentally known for a variety of physicochemical processes in aqueous solution such as protein folding.     

New class of pyridine catalyst having a conformation switch system: asymmetric acylation of various sec-alcohols

We have developed a new class of pyridine catalyst for asymmetric acylation of sec-alcohols having a conformation switch system in which interconversion between self-complexation and uncomplexation is induced by acylation and deacylation steps, respectively. Kinetic resolution of various sec-alcohols is performed by the asymmetric acylation with isobutyric anhydride using 0.05 to 0.5 mol % catalyst 1a with s values of up to 30. In addition, dl-diols are also resolved in a similar manner in good selectivity. Moreover, asymmetric desymmetrization of meso-1,X-diols (X = 2-6) are achieved in the presence of 0.5-5 mol % catalyst 1a. A working model for the reaction mechanism is proposed on the basis of the (1)H NMR measurements, X-ray structural analyses, and AM1 and DFT calculations, where the conformation switch system governed by an intramolecular cation-pi interaction between a pyridinium ring and a thiocarbonyl group would play a key role to attain both good selectivity and high catalytic activity.     

Enantioselective Robinson‐Type Annulation Reaction Catalyzed by Chiral Phosphoric Acids

Let′s resolve our differences : Implementation of an enantioselective Michael addition followed by an intramolecular aldol reaction catalyzed by two phosphoric acids has enabled the synthesis of cyclohexenone derivatives with excellent enantioselectivities. Prominent kinetic resolution was observed in the latter reaction. Ar=aromatic group, X=H, halogen, Y=H, Me, halogen.

     

Search for Down-Type Fourth Generation Quarks with the ATLAS Detector in Events with One Lepton and Hadronically Decaying W Bosons

This Letter presents a search for pair production of heavy down-type quarks decaying via b^{'}→Wt in the lepton+jets channel, as b^{'}b[over ˉ]^{'}→W^{-}tW^{+}t[over ˉ]→bb[over ˉ]W^{+}W^{-}W^{+}W^{-}→l^{±}νbb[over ˉ]qq[over ˉ]qq[over ˉ]qq[over ˉ]. In addition to requiring exactly one lepton, large missing transverse momentum, and at least six jets, the invariant mass of nearby jet pairs is used to identify high transverse momentum W bosons. In data corresponding to an integrated luminosity of 1.04 fb^{-1} from pp collisions at sqrt[s]=7 TeV recorded with the ATLAS detector, a heavy down-type quark with mass less than 480?GeV can be excluded at the 95% confidence level.     

Synthesis and structure of bis(dialkylamino)carbeniumdithiocarboxylates

2-Chloro and 2-phenoxy substituted 1,1-bis(diethylamino)ethylenes ( 4a and 4c ) react with elemental sulfur at room temperature to give the inner salt, bis(diethylamino)carbeniumdithiocarboxylate ( 1a ), in excellent yields with extrusion of hydrogen chloride and phenol, respectively, thus providing a new and convenient synthesis of the structurally interesting inner salt. X-ray single crystal structure analysis of 1a reveals that the N C N and S C S planes are nearly vertical to each other with a dihedral angle of 82.0° and that the positive and negative charges are delocalized over the N C N and S C S moieties, respectively. Results of solid-state ¹³C NMR of 1a are also briefly described.     

Carrier Protein Mediated Formation of the Dihydropyridazinone Ring in Actinopyridazinone Biosynthesis

Heterocycles with nitrogen-nitrogen (N−N) bonds are privileged building blocks of synthetic drugs. They are also found in natural products, although the biosynthetic logic behind them is poorly understood. Actinopyridazinones produced by Streptomyces sp. MSD090630SC-05 possess unique dihydropyridazinone rings that have been studied as core nuclei in several approved synthetic therapeutics. Herein, we performed gene knockouts and in vitro biochemical experiments to elucidate the major steps in actinopyridazinone biosynthesis, including the unprecedented carrier protein mediated machinery for dihydropyridazinone formation.