Alkylation of β-diketones through their co(II), co(III) and zn(II) complexes. 1-Bromoadamantane as alkylating agent.

α-(1-adamantyl)-β-diketones are now accessible by the alkylation of Co(II) complexes of β-diketones with 1-bromoadamantane. The intermediacy of adamantyl cation is proposed. Co(II), Co(III) and Zn(II) complexes of pentane-2,4-dione react with alkyl halides precursors of stabilized carbenium ions, to give 3-alkylpentane-2,4-diones.     

Crystal and Molecular Structure of (BzlMe3N) 2 + [Fe2OCl6]2-

The crystal and molecular structure of (BzlMe₃N) ₂ ⁺ [Fe₂OCl₆]^2- has been determined. The asymmetric unit contains two benzyltrimethylammonium cations and two half -oxo-bis(trichloro-iron(III)) anions. The bridging -oxygen atoms of these anions are located over crystallographic symmetry elements. Therefore, the two anions resulting from the symmetry operations correspond to two different conformers presenting angular and linear dispositions of the Fe-O-Fe bond angle. Mössbauer spectrum consists of two asymmetric lines that are adequately simulated by two equally populated quadrupole doublets associated with the two iron sites.     

Transition metal-mediated intramolecular [2+2+2] cycloisomerizations of cyclic triynes and enediynes

[reaction: see text] Nitrogen-containing 15-membered triacetylenic macrocycles known as 1,6,11-tris(arylsulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-triynes (1) and enediynic macrocycles called 1,6,11-tris(arylsulfonyl)-1,6,11-triazacyclopentadeca-3-ene-8,13-diynes (4 and 5) were satisfactorily prepared. [2+2+2] cycloisomerization processes catalyzed by transition metals were tested in the above-mentioned macrocycles. Readily available and familiar cyclotrimerization precatalysts were examined for efficiency. Among them, the RhCl(CO)(PPh(3))(2) complex was found to catalyze the cycloisomerization reaction giving the desired cycloadducts in high yields.     

An Improved Method for γ-Carboxylation of β-Diketones. Synthesis of 4-Alkyl-3,5-Dioxohexanoic Acids and 5-Alkyl Derivatives of Triacetic Acid Lactone

γ-Carboxylation of β-diketones, 1, can be improved using samples containing 100% of ketoenol tautomers, 3, prepared by mild hydrolysis of the corresponding copper(II) complexes 2. Cyclization of the so formed 4-alkyl-3,5-dioxohexanoic acids, 4, affords 5-alkyl-4-hydroxy-6-methyl-2-pyrones, 5.     

Palladium-Catalyzed Preparation of Dialkyl Allylphosphonates. A New Preparation of Diethyl 2-Oxoethylphosphonate

Palladium-catalyzed Michaelis-Arbuzov reaction of allyl acetates with trialkyl phosphites affords dialkyl allylphosphonates. Diethyl 2-oxoethylphosphonate is efficiently prepared by ozonization of diethyl allylphosphonate.     

Michael additions catalyzed by phosphines. An overlooked synthetic method

Triphenylphosphine and tributylphosphine are excellent catalysts for Michael additions. Many β-dicarbonyl compounds and electron-poor olefins, including sterically demanding partners, react successfully. The Michael addition catalyzed by phosphines deserves attention in its own right as a useful synthetic method.     

Test of right-handed currents in baryon semileptonic decays

The effect of a right-handed boson on baryon semileptonic decay is considered. The analysis of polarized and unpolarized decays is carried out and it is shown that the best place to look for a right-handed current (RHC) signature is in polarized baryon decay. However, our results are useful for high statistics experiments. In order to see the contribution of the right-handed currents in the case of unpolarized hyperon decay, the Cabibbo theory should be assumed.     

A nonlocal contact formulation for confined granular systems

We present a nonlocal formulation of contact mechanics that accounts for the interplay of deformations due to multiple contact forces acting on a single particle. The analytical formulation considers the effects of nonlocal mesoscopic deformations characteristic of confined granular systems and, therefore, removes the classical restriction of independent contacts. This is in sharp contrast to traditional contact mechanics theories, which are strictly local and assume that contacts are independent regardless the confinement of the particles. For definiteness, we restrict attention to elastic spheres in the absence of gravitational forces, adhesion or friction. Hence, a notable feature of the nonlocal formulation is that, when nonlocal effects are neglected, it reduces to Hertz theory. Furthermore, we show that, under the preceding assumptions and up to moderate macroscopic deformations, the predictions of the nonlocal contact formulation are in remarkable agreement with detailed finite-element simulations and experimental observations, and in large disagreement with Hertz theory predictions—supporting that the assumption of independent contacts only holds for small deformations. The discrepancy between the extended theory presented in this work and Hertz theory is borne out by studying periodic homogeneous systems and disordered heterogeneous systems.