Total synthesis of (±) maculalactone A, maculalactone B and maculalactone C and the determination of the absolute configuration of natural (+) maculalactone A by asymmetric synthesis

Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (−) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature.     

Large deviation for the empirical eigenvalue density of truncated Haar unitary matrices

Let U_m be an m×m Haar unitary matrix and U_[m,n] be its n×n truncation. In this paper the large deviation is proven for the empirical eigenvalue density of U_[m,n] as m/n→λ and n→∞. The rate function and the limit distribution are given explicitly. U_[m,n] is the random matrix model of quq, where u is a Haar unitary in a finite von Neumann algebra, q is a certain projection and they are free. The limit distribution coincides with the Brown measure of the operator quq.     

C2（a 3Πu）+NO 的反应机理研究

在G2 (CC ,MP2 )理论水平上研究了C2 (a3 Πu)自由基与NO分子的反应 .计算了反应体系最低二重态势能面上各驻点的构型参数、振动频率和能量 ,揭示了此反应存在两种反应机理 :由NO中的O原子进攻C2 自由基形成CCON中间体的CCON机理和NO中的N进攻C2 自由基形成CCNO中间体的CCNO机理 ,分析了对应与这两种反应机理的五个可能的反应通道 ,得出了由NO中的N原子进攻3 C2 自由基 ,生成中间体CCNO自由基 ,最终得到产物CN +CO的通道是最有利的通道 .     

时间分辨红外发射光谱法对自由基反应的研究

在过去的 15年中 ,傅立叶变换红外发射光谱法广泛应用于研究气相自由基反应 .Sloan首先研究了O(1D)的反应 ,随后Leone和Hancock研究了O(3 P)的反应 .此后 ,孔繁敖和朱起鹤等研究了小自由基 ,包括CH、CH2 、CH3 、C2 H3 、C2 H5、C2 H、C3 H3 和C3 H5与O2 、NO、N2 O、NO2 等分子的反应。在红外光谱中观察到各个反应的初生产物和初步反应通道 ,和从头算的理论研究结合起来 ,这些反应的机理已基本弄清 .     

Diels-Alder-Reaktionen von Vinylindolen mit Arin und 1,4-Benzochinonen: Neue potentielle DNA-Interkalatoren

Summary Diels-Alder reactions of 2- and 3-vinylindoles with aryne, 1,4-benzo- and 1,4-naphtho-quinone lead to new six-ring annellated carbazoles. Molecular modeling studies predict that the compounds with coplanar framework are able to intercalate with the B-DNA.

     

Nitroxide‐mediated radical polymerization in miniemulsion: Bimolecular termination in monomer‐free model systems

Bimolecular termination in nitroxide‐mediated radical polymerization in miniemulsion has been investigated through the heating of a polystyrene–2,2,6,6‐tetramethylpiperidinyl‐1‐oxy macroinitiator and its 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy analogue in an aqueous toluene dispersion with sodium dodecyl benzenesulfonate as a surfactant at 125 °C. The level of bimolecular termination by combination, evaluated from the high‐molecular‐weight shoulder, was higher in miniemulsion than in solution and increased with decreasing particle size. Quantitative analysis revealed that these results cannot be rationalized solely by nitroxide partitioning to the aqueous phase. The results are explained by an interface effect, by which nitroxide is adsorbed or located at the aqueous–organic interface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4995–5004, 2007     

A note on strongly π-regular rings

Let R be an associative ring with unit and let N(R) denote the set of nilpotent elements of R. R is said to be stronglyπ-regular if for each x∈R, there exist a positive integer n and an element y∈R such that x ⁿ=x ^{n +1} y and xy=yx. R is said to be periodic if for each x∈R there are integers m,n≥ 1 such that m≠n and x ^m=x ⁿ. Assume that the idempotents in R are central. It is shown in this paper that R is a strongly π-regular ring if and only if N(R) coincides with the Jacobson radical of R and R/N(R) is regular. Some similar conditions for periodic rings are also obtained. This revised version was published online in June 2006 with corrections to the Cover Date.     

α，ω-二羧基-甲基丙烯酸丁酯低聚物的合成及MS分析

利用传统自由基聚合法，在四氢呋喃溶液中自由基引发聚合甲基丙烯酸丁酯单体而得到ω-羧基-甲基丙烯酸丁酯低聚物(CTBMA)(分子量在1500左右)；利用CTBMA末端酯基的反应特性，在二氧六环／水／KOH混合溶液中皂化CTBMA，使之转化为α，ω-羧基甲基丙烯酸丁酯低聚物(di-CTBMA)；研究了溶剂的类别、反应时间等反应条件对皂化产物结构的影响；利用MALDI-TOF-MS及LSIMS对皂化各阶段产物进行了分析监测．实验表明，在适当的皂化条件下，CTBMA皂化时主要为末端酯基转化为羧基，相应得到的产物di-CTMBA具有很好的结构特性，其官能团度(functionality)接近2．     

Kaon absorption from kaonic atoms and formation spectra of kaonic nuclei

We considered the kaon absorption from atomic states into the nucleus. We found that the nuclear density probed by the atomic kaon significantly depends on the kaon orbit. Then, we re-examined the meanings of the observed strengths of one-body and two-body kaon absorption, and investigated the effects to the formation spectra of kaon bound states by in-flight (K ^-, p) reactions. As a natural consequence, if the atomic kaon probes a smaller nuclear density, the ratio of the two-body absorption at nuclear center is larger than the observed value in kaonic atoms, and the depth of the imaginary potential is deeper even at smaller kaon energies as in kaonic nuclear states because of the large phase space for the two-body processes. This deeper imaginary potential makes the signals of kaonic nucleus formation more unclear in the (K ^-, p) spectra.     

Molecular flow and wall collision age distributions

The use of storage cells has become a standard technique for internal gas targets in conjunction with high energy storage rings. In case of spin-polarized hydrogen and deuterium gas targets the interaction of the injected atoms with the walls of the storage cell can lead to depolarization and recombination. Thus the number of wall collisions of the atoms in the target gas is important for modeling the processes of spin relaxation and recombination. It is shown in this article that the diffusion process of rarefied gases in long tubes or storage cells can be described with the help of the one-dimensional diffusion equation. Mathematical methods are presented that allow one to calculate collision age distributions (CAD) and their moments analytically. These methods provide a better understanding of the different aspects of diffusion than Monte Carlo calculations. Additionally it is shown that measurements of the atomic density or polarization of a gas sample taken from the center of the tube allow one to determine the possible range of the corresponding density weighted average values along the tube. The calculations are applied to the storage cell geometry of the HERMES internal polarized hydrogen and deuterium gas target. Received 9 July 2001 and Received in final form 18 September 2001