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.     

Fast and efficient preparation of Baylis-Hillman-derived (E)-allylic azides and related compounds in aqueous medium

A practical access to alkyl- and aryl-substituted (E)-2-(azidomethyl)alkenoates and related azido compounds from the corresponding allylic bromides in aqueous acetone is described. An alternative method to obtain the starting bromides based on heterogeneous catalysis under mild conditions was also investigated.     

Stereoselective total synthesis of (±)-α-vetispirene, (±)-hinesol, and (±)-β-vetivone based on a Claisen rearrangement

The stereoselective total syntheses of (±)-α-vetispirene, (±)-hinesol, and (±)-β-vetivone were accomplished based on a Claisen rearrangement in an alkenyl bicyclic dihydropyran system. The most striking feature of this approach is that the Claisen rearrangement of bicyclic dihydropyran proceeds stereoselectively to provide a multi-functionalized spiro[4.5]decane, which is an efficient precursor for the synthesis of the vetivane sesquiterpenes.     

Enantiodiscrimination of racemic electrophiles by diketopiperazine enolates: asymmetric synthesis of methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates

Enolates of (S)-N,N′-bis-(p-methoxybenzyl)-3-iso-propylpiperazine-2,5-dione exhibit high levels of enantiodiscrimination in alkylations with (RS)-1-aryl-1-bromoethanes and (RS)-2-bromoesters, affording substituted diketopiperazines containing two new stereogenic centres in high de. Deprotection and hydrolysis of the resultant substituted diketopiperazines provides a route to the asymmetric synthesis of homochiral methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates in high de and ee.     

Large set of P3‐decompositions

Let G=(V(G),E(G)) be a graph. A (n,G, λ)‐GD is a partition of the edges of λK_n into subgraphs (G‐blocks), each of which is isomorphic to G. The (n,G,λ)‐GD is named as graph design for G or G‐decomposition. The large set of (n,G,λ)‐GD is denoted by (n,G,λ)‐LGD. In this work, we obtain the existence spectrum of (n,P₃,λ)‐LGD. © 2002 Wiley Periodicals, Inc. J Combin Designs 10: 151–159, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/jcd.10008     

Luminescent properties of Ce in MSO4 (M: Ca, Sr and Ba) and the effect of Na co-doping

The optical properties of Ce³⁺ in CaSO₄, SrSO₄ and BaSO₄ are reported. The Ce³⁺ ion shows 4f⁰5d¹→²F_5/2,²F_7/2 luminescence in all three sulphates. Co-doping with Na⁺ does not change the local surrounding of the Ce³⁺ ion, but enhances the amount of Ce³⁺ ions built in. Under optical excitation, besides the typical Ce³⁺ doublet emission in the ultraviolet spectral region, band emission around 445 nm was observed. This band emission was not assigned to emission from a Ce³⁺ centre, but to emission from an impurity-trapped exciton. Under X-ray excitation, both Ce³⁺ emission and an emission band around 380 nm was observed. This band was assigned to emission from a self-trapped exciton.     

用于白光LED的高亮度蓝白色荧光粉Ca2SiO3Cl2：Eu2+的发光性质

采用固相法在较低温度下合成了Eu²⁺激活的Ca₂SiO₃Cl₂高亮度蓝白色发光材料,并对其发光性质进行了研究。其发射光谱由两个谱带组成,峰值分别位于420,498nm处,归结为Ca₂SiO₃Cl₂晶体中占据两种不同Ca²⁺格位的Eu²⁺离子的5d→4f跃迁发射。改变Eu²⁺浓度,可以使样品的发光在蓝白色和绿白色之间变化。当Eu²⁺浓度为0.005mol^-1时,样品呈现很亮的蓝白色发光。两个发射峰的激发光谱均分布在250~410nm的波长范围内,峰值分别位于333,369nm处。Ca₂SiO₃Cl₂:Eu²⁺可被InGaN管芯产生的近紫外辐射有效激发,是一种性能良好的白光LED用单一基质蓝白色荧光粉。     

Fundamental processes in long air gap discharges

The development of atmospheric lightning is initiated and sustained by the formation in virgin air of ‘streamer corona’ and ‘leader’ discharges, very similar to those observed in laboratory long sparks. Therefore, the experimental and theoretical investigations of these laboratory discharges have become of large interest to improve the physical knowledge of the lightning process and to develop self-consistent models that could be applied to new protection concepts.In the present paper the fundamental processes of the subsequent phases of long air gap discharges are analyzed, from the first corona inception and development to the leader channel formation and propagation. For all these processes simulations models are discussed that have been essentially derived and simplified by the authors, in order to develop sequential time-dependent simulation of the laboratory breakdown, with both positive and negative voltages. The possibility of extending these models to the case of natural lightning is discussed in the companion paper, presented in this same volume. To cite this article: I. Gallimberti et al., C. R. Physique 3 (2002) 1335–1359.     

2-fold and 3-fold mixing: why 3-dot-type counterexamples are impossible in one dimension

V.A. Rohlin asked in 1949 whether 2-fold mixing implies 3-fold mixing for a stationary process (ξ_i )_i2ℤ, and the question remains open today. In 1978, F. Ledrappier exhibited a counterexample to the 2-fold mixing implies 3-fold mixing problem, the socalled 3-dot system, but in the context of stationary random fields indexed by ℤ². In this work, we first present an attempt to adapt Ledrappier's construction to the onedimensional case, which finally leads to a stationary process which is 2-fold but not 3-fold mixing conditionally to the σ-algebra generated by some factor process. Then, using arguments coming from the theory of joinings, we will give some strong obstacles proving that Ledrappier's counterexample can not be fully adapted to one-dimensional stationary processes.