Synthesis of (-)-centrolobine by Prins cyclizations that avoid racemization

[formula: see text] The segment-coupling Prins cyclization avoids two of the problems common to other Prins cyclization protocols: side-chain exchange and partial racemization by reversible 2-oxonia Cope rearrangement. Model studies demonstrate the stereochemical fidelity of Prins cyclizations using alpha-acetoxy ethers compared with direct aldehyde-alcohol Prins reactions. Furthermore, we propose a mechanism for the racemization observed in some intermolecular Prins cyclizations. Two straightforward syntheses of optically pure (-)-centrolobine highlight the utility of Prins cyclizations.     

Kluyveromyces marxianus CBS 6556 growing cells as a new biocatalyst in the asymmetric reduction of substituted acetophenones

The use of microorganism growing cells is a well recognized methodology in biocatalyzed organic reactions. A non-conventional thermotolerant Kluyveromyces marxianus yeast strain was used for the bio-reduction of different arylketones. Differently substituted ketones were converted into the corresponding (S)-alcohols with up to 96% enantiomeric excess under very mild reaction conditions. Kluyveromyces marxianus represents a promising biocatalyst for the production of optically active 1-arylethanols.     

Optical characterization of the recombination process in silicon wafers, epilayers and devices

In this paper we present various approaches to the measurement of recombinative parameters in silicon wafers, epitaxial layers and solar cells. In particular our techniques are able to measure the bulk lifetime and the surface recombination velocity at low injection levels. We also show that the techniques presented are a reliable tool to monitor the fabrication process of a standard crystalline silicon solar cell. In all the methodologies presented there are no stringent requirements concerning the state of wafer surface.     

Critical exponents of the Gross-Neveu model from the effective average action

The phase transition of the Gross-Neveu model with N fermions is investigated by means of a nonperturbative evolution equation for the scale dependence of the effective average action. The critical exponents and scaling amplitudes are calculated for various values of N in d = 3. It is also explicitly verified that the Neveu-Yukawa model belongs to the same universality class as the Gross-Neveu model.     

Asymptotic Behavior of a Set-Statistic

The existence theorem of Minkowski for a polytope with given facet normals and areas is adapted to a data-analytic context. More precisely, we show that a centered, random point sample arising from an absolutely continuous distribution in R ^d can be uniquely mapped into such a polytope almost surely. With increasing sample size, the sequence of (scaled) polytopes converges almost surely to a limiting convex body that is associated with the underlying distribution. An accompanying central limit theorem is proved using methods from the theory of empirical processes. Received January 28, 1999, and in revised form April 12, 1999.     

Azumaya Categories

We define the notions of Azumaya category and Brauer group in category theory enriched over some very general base category V. We prove the equivalence of various definitions, in particular in terms of separable categories or progenerating bimodules. When V is the category of modules over a commutative ring R with unit, we recapture the classical notions of Azumaya algebra and Brauer group and provide an alternative, purely categorical treatment of those theories. But our theory applies as well to the cases of topological, metric or Banach modules, to the sheaves of such structures or graded such structures, and many other examples.     

Thermal decomposition of n-alkyl[bis(triphenylphosphine)](carbonyl)iridium(I) complex

The decomposition of L₂Ir(CO)R, R = n-alkyl) prepared in situ by the reacton of n-alkyllithium or -magnesium reagents with L₂Ir(CO)Cl(2) produces a mixture of n-alkane and isomerized alkene, the ratio of which is strongly dependent on the concentration [L] of triphenylphosphine as well as certain other additives. When [L] = 0, positional isomerism and isotope scrabling are extensive as is the isomerism of added olefin, suggesting that β-hydride elimination is rapid and reversible and that any olefins participating in an iridium hydride addition-elimination sequence are also capable of exchange with free olefin in solution. When [Ph₃P]/[2] >/ 1, the principal product (>90%) is the 1-alkene. No positional isomerism or isotope scrambling is observed only a minor amount of alkane is produced. A mechanistic scheme consistent these observations is proposed.