Synthesis of Highly Substituted γ‐Butyrolactones by a Gold‐Catalyzed Cascade Reaction of Benzyl Esters

Easily accessible benzylic esters of 3‐butynoic acids in a gold‐catalyzed cyclization/rearrangement cascade reaction provided 3‐propargyl γ‐butyrolactones with the alkene and the carbonyl group not being conjugated. Crossover experiments showed that the formation of the new C?C bond is an intermolecular process. Initially propargylic–benzylic esters were used, but alkyl‐substituted benzylic esters worked equally well. In the case of the propargylic–benzylic products, a simple treatment of the products with aluminum oxide initiated a twofold tautomerization to the allenyl‐substituted γ‐butyrolactones with conjugation of the carbonyl group, the olefin, and the allene. The synthetic sequence can be conducted stepwise or as a one‐pot cascade reaction with similar yields. Even in the presence of the gold catalyst the new allene remains intact.     

Remote stereocontrol by the sulfinyl group: Mukaiyama aldol reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde in the asymmetric synthesis of β-hydroxyacids and 1,3-diols

(S)-2-[2-(p-Tolylsulfinyl)phenyl]acetaldehyde reacts with different O-silylated ketenethioacetals in the presence of Yb(OTf)₃ yielding β-hydroxythioesters in high yields and diastereoselectivities. The obtained compounds were readily transformed into β-hydroxyacids and their corresponding diols. These Mukaiyama aldol reactions are a direct evidence of the ability of the sulfinyl group to control 1,5- and 1,6-asymmetric induction processes.     

Preparation of rhodium–phyllosilicate catalysts without leaching in liquid-phase 1-hexene hydrogenation

Rhodium catalysts have been prepared on palygorskite and montmorillonite (clay) supports by reduction with hydrogen (1 atmosphere) at room temperature of a cationic organometallic rhodium compound anchored to the support. The activity of these catalysts for the hydrogenation of liquid-phase 1-hexene remains constant with increase of prehydrogenation time and with re-use for several runs. No rhodium leaching is observed.     

Crystal field and magnetic properties of the tetragonal TbNi2Si2 compound

The magnetic properties of a TbNi₂Si₂ single crystal have been investigated experimentally by specific heat, anisotropy of the susceptibility and magnetization, and inelastic neutron scattering, leading to the determination of its fundamental coupling parameters. The lowest crystalline electric field states are two singlets close to each other, that explains the different magnetic structures evidenced in TbNi₂Si₂: an amplitude modulated structure, close to T _N , a simple antiferromagnetic one at low temperature and an antiphase one when an external magnetic field is applied along the c direction.     

Convergence of multistep discretizations of DAEs

Standard ODE methods such as linear multistep methods encounter difficulties when applied to differential-algebraic equations (DAEs) of index greater than 1. In particular, previous results for index 2 DAEs have practically ruled out the use of all explicit methods and of implicit multistep methods other than backward difference formulas (BDFs) because of stability considerations. In this paper we embed known results for semi-explicit index 1 and 2 DAEs in a more comprehensive theory based on compound multistep and one-leg discretizations. This explains and characterizes the necessary requirements that a method must fulfill in order to be applicable to semi-explicit DAEs. Thus we conclude that the most useful discretizations are those that avoid discretization of the constraint. A freer use of e.g. explicit methods for the non-stiff differential part of the DAE is then possible.Dedicated to Germund Dahlquist on the occasion of his 70th birthdayThis author thanks the Centro de Estadística y Software Matemático de la Universidad Simón Bolivar (CESMa) for permitting her free use of its research facilities.Partial support by the Swedish Research Council for Engineering Sciences TFR under contract no. 222/91-405.     

Theoretical study of cyclization of 2′-hydroxychalcone

The isomerization mechanism of 2′(OH)chalcone (1) in flavanone (2) was studied. The calculations were performed with the semiempirical method AM1, using totally optimized molecular geometries. A 6-step mechanism including several equilibrium states was proposed. It was concluded that: (a) At the conformational equilibrium of 1 there could be 43.9% of s-cis conformer; (b) The acid dissociation of 1 trans-s-trans is considerable; (c) The E_E, ΔH_f and net charges show that the rotation of ring A of 1 and the formation of ring C of 2 occurs without greater impairments; (d) Although the keto structure is the most stable one, the enolate of 2 is present in the reaction medium; (e) The conversion of enol of 2 in the keto form would be the limiting step of the analyzed isomerization rate.     

Production and characterization of refractive index gratings in high-birefringence fibre optics

In this work, we report production and modelling of both Bragg gratings and rocking filters in high birefringence fibre optics. Bragg gratings are produced by UV (257.0 nm) external interferometric exposition of a frequency-doubled Ar⁺ ion laser, whereas for rocking filters formation the visible Ar⁺ ion laser lines in 488.0 and 514.5 nm are used in an internal method. The spectral characteristics due to the birefringence properties are studied through numerical methods and experimental techniques. The spectral responsivity of the structures under temperature changes and stress application is presented.     

Micellar effect in hydroformylation of high olefin catalysed by water-soluble rhodium complexes associated with sulfonated diphosphines

High linear alkenes (1-octene and 1-decene) have been hydroformylated using water-soluble rhodium complexes associated with sulfonated diphosphines in the presence of ionic surfactants or methanol. In all cases, the hydroformylation activities were higher than in experiments without additives. The selectivity in aldehydes was higher when we used cetyltrimethylammonium hydrogensulfate (CTAHSO₄) as the surfactant or methanol as the co-solvent.