Diels-Alder reactions of N-acyl-2-alkyl(aryl)-5-vinyl-2,3-dihydro-4-pyridones

Readily available N-acyl-5-vinyl-2,3-dihydro-4-pyridones undergo Diels-Alder cyclization with various dienophiles to afford novel octahydroquinolines containing synthetically useful functionality. With dihydropyridone 5 and cis-disubstituted dienophiles, the resulting cycloadducts were obtained as single diastereomers in good to excellent yield. The corresponding reaction of 5 with methyl acrylate, acrylonitrile, and phenyl vinyl sulfone showed modest preference for the endo adducts. The effect of the dihydropyridone C-2 and C-4 substituents on the degree of diastereofacial control was examined. By using this methodology, the core decahydroquinoline skeleton of gephyrotoxin was prepared in a stereocontrolled fashion. Interesting reactivity was observed with certain dienophiles leading to ring-opening of the initially formed cycloadducts. This tandem reaction provides a route to uniquely substituted beta-aminoketones, alcohols, and unnatural amino acids.     

Synthesis of disubstituted imidazo[4,5-b]pyridin-2-ones

Regioselective palladium-catalyzed amination of 2-chloro-3-iodopyridine followed by a subsequent palladium-catalyzed amination leads to 2,3-diaminopyridines. Treatment with triphosgene affords highly functionalized unsymmetrical imidazo[4,5-b]pyridin-2-ones in just three synthetic steps. A two-step synthesis of pseudosymmetrically disubstituted imidazo[4,5-b]pyridin-2-ones, 1,4-disubstituted pyrido[2,3-b]pyrazinediones, and 1,3-disubstituted thiadiazolo[3,4-b]pyridin-2-ones is also described.     

ON BREAKING WAVES AND WAVE-CURRENT INTERACTION IN SHALLOW WATER: A 2DH FINITE ELEMENT MODEL

A two-dimensional (horizontal plane) coastal and estuarine region model, capable of predicting the combined effects of gravity surface shallow- water waves (shoaling, refraction, diffraction, reflection and breaking), and steady currents, is described and numerical results are compared with those obtained experimentally. Two series of observations within a wave flume and a combined wave-current facility were developed. In the first case, the wave was generated via a hinged paddle located within a deepened section at one end of the channel, as, in the second case, the wave propagating with or against the current was generated by a plunger-type wavemaker; the re-circulating current was introduced via one passing tank connected to a centrifugal pump. Several comparisons for a number of 1D situations and one 2D horizontal plane case are presented.     

Studies of porous media by thermally polarized gas NMR: current status

Three examples of thermally polarized gas NMR performed at New Mexico Resonance are presented to demonstrate its unique advantages in porous media studies. 1) In-vivo animal lung imaging by Kuethe et al., in which useful quality 3D images of rat lungs were obtained in 30 min. It is conjectured that comparable human lung images would take much less time to make, possibly by the ratio of body weights, a factor of several hundred. 2) The success of the lung imaging suggested other porous media as candidates for thermally polarized gas NMR. Caprihan and coworkers obtained excellent images from partially sintered ceramics and Vycor glass. Since then, Beyea has developed the technique of spatially resolved BET curves for ceramics and other nanoporous solids. In this way, surface area, pore size, and porosity, averaged over an image voxel, can be spatially resolved. This greatly aids in the characterization of such materials, especially with regards to spatial heterogeneities. 3) Finally, we describe Codd's propagator experiments on propane gas flowing through a packed bed of 300 microm beads. In order to increase signal-to-noise ratio, the flowing gas was pressurized to 170 kPa. Excellent quality propagators showing the discrete nature of the bead pack were obtained. This type of information is not available in comparable liquid studies because most spins will not diffuse far enough to sample the walls in the time available.     

Bicriteria Scheduling on a Series-Batching Machine to Minimize Makespan and Total Weighted Completion Time with Equal Length Job

It is known that the problem of minimizing total weighted completion time on a series-batching machine is NP-hard. We consider a series-batching bicriteria scheduling problem of minimizing makespan and total weighted completion time with equal length job simultaneously. A batching machine can handle up to b jobs in a batch, where b is called the batch capacity of the machine. We study the unbounded model with b≥n, where n denotes the number of jobs. A dynamic programming algorithm is proposed to solve the unbounded model, which can find all Pareto optimal schedules in O（n3） time.     

THE ROLE OF ISSUE LINKAGE IN MANAGING NONCOOPERATING BASINS: THE CASE OF THE MEKONG

The Mekong River (MR) is the major water source in Southeast Asia, sharedby six countries. There is a rush, by riparian states, to acquire sources of alternative energy and other benefits to meet growing demands for water and energy. China and Myanmar have refused to cooperate fully in the MR Forum, leading to increase risks within the region. Development of the water resources of the MR Basin is the subject of intense debate both within the Mekong region and internationally. This paper investigates the concept of issue linkage to resolve unidirectional externalities in the MR. Using linked games, the paper shows that the downstream nations can consider the use of linkage as a form of side payment in achieving a basin‐wide agreement. While this approach supports the Integrated Water Resource Management‐based Basin Development Strategy adopted by the Mekong River Commission in April 2011 for managing the region's sustainability development, facts on the ground suggest that traditional issues to be linked may not be sufficient. The paper addresses this observation and suggests a cadre of issues, including nontraditional ones, to be analyzed in a future work.     

A biocatalytic/reductive etherification approach to substituted piperidinyl ethers

A synthetically useful protocol has been developed for the preparation of highly functionalized piperidinyl ethers. Biocatalytic reduction of cyclhexanones 7, 10, and 14 allows for the preparation of both cis- and trans diastereomers with an extremely high degree of stereochemical control. Reductive etherification of the corresponding trimethylsilylethers with 1-(benzyloxycarbonyl)-4-piperidinone 17 in the presence of triethylsilane and catalytic TMSO-Tf provides the desired piperidinyl ethers in good to excellent yields. Finally hygrogenolysis of the nitrogen protecting group leads to piperidinyl ethers in near quantitative yields. Application of the methodology to a range of piperidinyl ethers, including the core scaffolds of diphenylpyraline and ebastine, is also described.     

A concise synthesis of (S)-N-ethoxycarbonyl-alpha-methylvaline

A practical and efficient protocol for the three-step synthesis of (S)-N-ethoxycarbonyl-alpha-methylvaline 3 is described which utilizes readily available commercial starting materials. The key transformations involve resolution-crystallization of tartrate salt 6 followed by a one-pot procedure for the preparation of 3 which is isolated as the dicyclohexylamine salt in 45% overall yield and in 91-95% ee.     

A practical, one-pot synthesis of sulfonylated pyridines

A concise and efficient one-pot synthesis of functionalized sulfonylated pyridines via an S(N)Ar reaction of readily available pyridines and sodium sulfinate salts in the presence of tetrabutylammonium chloride is presented.     

一种HBV多聚酶基因检测系统的光学系统设计

基于荧光偏振理论,设计了一套HBV多聚酶基因检测光学系统。该光学系统包括荧光激发系统和荧光检测系统。使用荧光激发系统对激发样品产生荧光,由荧光检测系统对荧光进行水平和垂直两个方向的荧光强度检测,从而获得荧光的偏振度。通过更换该套系统中的滤光片可实现对400～550nm范围内的样品荧光偏振度的检测。运用该光学系统进行了临床实验,结果表明,系统测试方法具有简单易行、灵敏度高、精确可靠、抗干扰能力强的特点。