A tandem non-aldol aldol Mukaiyama aldol reaction

[reaction: see text] A new one-pot tandem aldol process is described in which a secondary epoxy silyl ether is converted into the 1,5-bis-silyloxy-3-alkanone in good yield. Thus, treatment of the epoxy silyl ether 8 with TBSOTf and base affords the silyl enol ether 9 via non-aldol aldol rearrangement and addition of benzaldehyde and TBSOTf gives the ketone 10 with 4:1 syn selectivity. The diastereoselectivity changes to an anti preference for most aldehydes. This anti selectivity overwhelms the normal Felkin-Ahn preference; namely, the 1,5-anti isomer predominates even when it is anti-Felkin-Ahn.     

Platinum- and palladium-catalysed Kocheshkov redistribution of dialkyltin dichlorides or tetraalkyltins with tin tetrachloride

The Kocheshkov redistribution reaction of tetraalkyltin or dialkyltin dichlorides with tin tetrachloride is effectively catalysed by platinum(II) or palladium(II) phosphine complexes, yielding alkyltin trichlorides in high yield and with high selectivity.     

Detection of ppm quantities of gaseous SO2 by o9rganoplatinum dendritic sites immobilised on a quartz microbalance

Sensor devices for the detection of low quantities of SO2 gas have been constructed which comprise organoplatinum receptor sites for the selective recognition of SO2 and a quartz crystal microbalance for the detection of small mass changes at the receptor sites.     

The validation of Kayzero-assisted NAA in Budapest, Rez, and Ljubljana via the analysis of three BCR certified reference materials

After installation and calibration of k0-assisted NAA in three Central European research institutes (AEKI-Budapest, NPI-Rez, and IJS, Ljubljana), its validation was established via the analysis of three BCR certified reference materials. The matrices of choice were: CRM 277 estuarine sediment, CRM 038 coal fly ash from pulverized coal, and CRM 101 spruce needles. For some elements, e.g. Zn, Cd, and Hg, the analyses were not only performed instrumentally (INAA), but also in the radiochemical mode (RNAA). The work was performed in the framework of a European Copernicus Project.     

Palladium-catalyzed amination of aryl bromides and aryl triflates using diphosphane ligands: a kinetic study

[Pd(P-O-P)(Ar)]+ complexes with ligands that have wide bite angles are active catalysts for the coupling of aniline derivatives with aryl triflates. Kinetic studies show that for these systems a fast equilibrium that involves coordination of the amine precedes the deprotonation, which is the rate-limiting step of the reaction. This reaction is faster for compounds with a smaller P-Pd-P angle. When halide salts are present, the base sodium tert-butoxide is activated and adds to the palladium complex. This rate-limiting step is preceded by a fast equilibrium that involves decoordination of the halide. The initial reaction rate is faster for compounds with a larger P-Pd-P angle. This is due to the closer proximity of the oxygen to the Pd center, and this assists in the dissociation of the halide.     

Dissipative evolution of quantum statistical ensembles and nonlinear response to a time-periodic perturbation

We present a detailed discussion of the evolution of a statistical ensemble of quantum mechanical systems coupled weakly to a bath. The Hilbert space of the full system is given by the tensor product between the Hilbert spaces associated with the bath and the bathed system. The statistical states of the ensemble are described in terms of density matrices. Supposing the bath to be held at some - not necessarily thermal - statistical equilibrium and tracing over the bath degrees of freedom, we obtain reduced density matrices defining the statistical states of the bathed system. The master equations describing the evolution of these reduced density matrices are derived under the most general conditions. On time scales that are large with respect to the bath correlation time and with respect to the reciprocal transition frequencies of the bathed system, the resulting evolution of the reduced density matrix of the bathed system is of Markovian type. The detailed balance relations valid for a thermal equilibrium of the bath are derived and the conditions for the validity of the fluctuation-dissipation theorem are given. Based on the general approach, we investigate the non-linear response of the bathed subsystem to a time-periodic perturbation. Summing the perturbation series we obtain the coherences and the populations for arbitrary strengths of the perturbation.Received: 26 November 2003, Published online: 30 January 2004PACS: 05.30.-d Quantum statistical mechanics - 33.35. + r Electron resonance and relaxation - 33.25. + k Nuclear resonance and relaxation     

Expansion of derivatives in one-dimensional dynamics

We study the expansion of derivatives along orbits of real and complex one-dimensional mapsf, whose Julia setJ _f attracts a finite setCrit of non-flat critical points. Assuming that for eachcεCrit, either |D f ⁿ(f(c))|→∞ (iff is real) orb _n·|Df ⁿ(f(c))|→∞ for some summable sequence {b _n} (iff is complex; this is equivalent to summability of |D f ⁿ(f(c))|⁻¹), we show that for everyxεJ _f\U _i f ⁻ⁱ(Crit), there existℓ(x)≤max _c ℓ(c) andK′(x)>0