Halocyclocarbamation of benzyl N-(1-phenyl-3-butenyl)carbamates afforded 6-functionalized 4-aryl-1,3-oxazinan-2-ones with moderate to excellent diastereoselectivity depending on the N-substituent. Importantly, in contrast to reported cyclocarbamations of homoallylic carbamates, which are generally trans-diastereoselective, cyclization of N-unsubstituted Cbz-protected homoallylamines led to cis-1,3-oxazinan-2-ones, predominantly. The use of N-benzylated and in situ prepared N-silylated derivatives resulted however in trans-selectivity. Transition states are proposed to explain the stereochemical influence of the N-substituent on the cyclocarbamations. The functionalized 1,3-oxazinan-2-ones could be further elaborated towards biologically or synthetically important 6-arylpiperidine-2,4-diones and 3-aryl-1,3-aminoalcohols. 相似文献
Tactical forecasting in supply chain management supports planning for inventory, scheduling production, and raw material purchase, amongst other functions. It typically refers to forecasts up to 12 months ahead. Traditional forecasting models take into account univariate information extrapolating from the past, but cannot anticipate macroeconomic events, such as steep increases or declines in national economic activity. In practice this is countered by using managerial expert judgement, which is well known to suffer from various biases, is expensive and not scalable. This paper evaluates multiple approaches to improve tactical sales forecasting using macro-economic leading indicators. The proposed statistical forecast selects automatically both the type of leading indicators, as well as the order of the lead for each of the selected indicators. However as the future values of the leading indicators are unknown an additional uncertainty is introduced. This uncertainty is controlled in our methodology by restricting inputs to an unconditional forecasting setup. We compare this with the conditional setup, where future indicator values are assumed to be known and assess the theoretical loss of forecast accuracy. We also evaluate purely statistical model building against judgement aided models, where potential leading indicators are pre-filtered by experts, quantifying the accuracy-cost trade-off. The proposed framework improves on forecasting accuracy over established time series benchmarks, while providing useful insights about the key leading indicators. We evaluate the proposed approach on a real case study and find 18.8% accuracy gains over the current forecasting process. 相似文献
Existing research on price promotions typically investigates the effects of single-product promotions. However, brand managers often promote multiple items simultaneously to bolster the performance of a complete brand line. This paper investigates the brand performance implications of such multi-item promotions. We distinguish between two types of multi-item promotions: traditional, unconstrained multi-item promotions that grant a discount irrespective of the size or composition of the purchase set, and constrained multi-item promotions that require consumers to purchase specific quantities (self-bundling) or even predetermined combinations (fixed bundling) of promoted items. Using a normative consumer decision model, the authors analyze the relative effectiveness of these promotions in terms of unit sales and revenue impact and show that promotion performance is moderated by consumers’ preference for variety. The authors find that unconstrained multi-item promotions outperform single-item promotions, especially in markets without variety-seeking. In markets with variety seeking, unconstrained multi-item promotions are not as effective in stealing extra sales from competition because consumers prefer to spread their purchases across all items, including competitive ones. However, in those markets, self-bundling promotions are particularly effective because they force consumers to adopt larger amounts of the promoted items at the expense of competitors. Finally, in neither type of market does fixed bundling substantially improve promotion performance. 相似文献
Multicrystalline silicon wafer solar cells reveal performance‐ reducing defects by luminescence. X‐ray fluorescence spectra are used to investigate the elemental constituents from regions of solar cells yielding reverse‐bias or sub‐bandgap luminescence from defects. It is found that a higher concentration of metals is present in regions yielding reverse‐bias electroluminescence than in regions yielding sub‐bandgap electroluminescence. This suggests, dislocations do not create strong breakdown currents in the absence of impurity precipitates.
This paper studies and analyzes a preconditioned Krylov solver for Helmholtz problems that are formulated with absorbing boundary layers based on complex coordinate stretching. The preconditioner problem is a Helmholtz problem where not only the coordinates in the absorbing layer have an imaginary part, but also the coordinates in the interior region. This results into a preconditioner problem that is invertible with a multigrid cycle. We give a numerical analysis based on the eigenvalues and evaluate the performance with several numerical experiments. The method is an alternative to the complex shifted Laplacian and it gives a comparable performance for the studied model problems. 相似文献
We continue our study of the linear response of a nonequilibrium system. This Part II concentrates on models of open and driven
inertial dynamics but the structure and the interpretation of the result remain unchanged: the response can be expressed as
a sum of two temporal correlations in the unperturbed system, one entropic, the other frenetic. The decomposition arises from
the (anti)symmetry under time-reversal on the level of the nonequilibrium action. The response formula involves a statistical
averaging over explicitly known observables but, in contrast with the equilibrium situation, they depend on the model dynamics
in terms of an excess in dynamical activity. As an example, the Einstein relation between mobility and diffusion constant
is modified by a correlation term between the position and the momentum of the particle. 相似文献
[reaction: see text] Reaction of chiral alpha-chloro tert-butanesulfinyl aldimines with Grignard reagents efficiently afforded beta-chloro N-sulfinamides in high diastereomeric excess. The latter compounds were cyclized toward the corresponding chiral aziridines in a high-yielding one-pot reaction or after separate treatment with base. The diastereoselectivity obtained in the newly synthesized beta-chloro sulfinamides is explained via the coordinating ability of the alpha-chloro atom with magnesium resulting in the opposite stereochemical outcome as generally observed for nonfunctionalized N-sulfinyl imines. 相似文献
A one‐step synthetic procedure for the radical C?H alkylation of BODIPY dyes has been developed. This new reaction generates alkyl radicals through the oxidation of boronic acids or potassium trifluoroborates and allows the synthesis of mono‐, di‐, tri‐, and tetraalkylated fluorophores in a good to excellent yield for a broad range of organoboron compounds. Using this protocol, multiple bulky alkyl groups can be introduced onto the BODIPY core thus creating solid‐state emissive BODIPY dyes. 相似文献
The adsorption and self organization of phosphonic acids on oxidized aluminum surfaces has been investigated by surface sensible
techniques: ARXPS, AES and FTIR. The analysis has been performed on Al 99.999 samples and on surfaces of a technical alloy
whose surfaces contain iron inclusions. The results obtained lead to the conclusion that self organization is not only possible
on perfect defect free surfaces but also on inhomogeneous ones.
Received: 24 June 1996 / Accepted: 21 January 1997 相似文献