Reagents for new heteroannelation reactions III. 2-(Methylthio)-2-thiazoline

Summary A variety of partly novel tri- and tetracyclic hetero systems were obtained by reaction of heteroaromatic 2-aminoesters with 2-(methylthio)-2-thiazoline, yielding double-annelation of a thiazolo[2,3-b]pyrimido moiety in a one-pot process.On leave from University of Chittagong, Bangladesh     

Reversal of Regioselectivity of Nitrone Cycloadditions by Lewis Acids

The regio‐ and stereoselectivity of cycloadditions of the nitrone 1a and the chiral, sugar‐derived nitrones 13a and 13b with 3‐(prop‐2‐enoyl)‐1,3‐oxazolidin‐2‐one ( 2 ) depends on the nature of the Lewis acid catalyst used. Addition of Lewis acid reverses the regioselectivity of the cycloaddition, and improves the anti‐diastereoselectivity in the case of chiral nitrones. The sterically favored isoxazolidin‐5‐yl‐substituted adducts 3, 4 , and 14 – 17 are produced as the major products in the absence of Lewis acid, while the electronically favored regioisomers with isoxazolidin‐4‐yl substituents ( 5, 6 , and 18 – 21 , respectively) are obtained as major products in the [Ti(OⁱPr)₂Cl₂] catalyzed reactions. The reactions of nitrone 13b with 2 in the presence of other Lewis acids such as ZnCl₂, ZnBr₂, ZnI₂ and MgI₂/I₂ gave both regioisomeric pairs of the diastereoisomers, favoring the 4‐substituted congeners. The diastereoisomeric isoxazolidines 3a – 6a were reduced with NaBH₄ in THF/H₂O with subsequent desilylation to yield the separable diols 9 – 12 . Reduction of the diastereoisomeric isoxazolidines 19a and 18a afforded the chiral alcohols 23 and 22 , the latter of which was analyzed by X‐ray crystallography.     

Carbocyclic galanthamin analogs: 4a,5,9,10,11,12‐hexahydro‐6H‐benzo[b]cyclohepta[cd]benzofurans

The synthesis of a novel unnatural carbocyclic analog of the acetylcholine esterase inhibitor galanthamine with a K₃[Fe(CN)₆] promoted oxidative tandem cyclization as the key step is reported.     

Live Monitoring of Strain-Promoted Azide Alkyne Cycloadditions in Complex Reaction Environments by Inline ATR-IR Spectroscopy

The strain-promoted azide alkyne cycloaddition (SPAAC) is a powerful tool for forming covalent bonds between molecules even under physiological conditions, and therefore found broad application in fields ranging from biological chemistry and biomedical research to materials sciences. For many applications, knowledge about reaction kinetics of these ligations is of utmost importance. Kinetics are commonly assessed and studied by NMR measurements. However, these experiments are limited in terms of temperature and restricted to deuterated solvents. By using an inline ATR-IR probe we show that the cycloaddition of azides and alkynes can be monitored in aqueous and even complex biological fluids enabling the investigation of reaction kinetics in various solvents and even human blood plasma under controlled conditions in low reaction volumes.     

Stability analysis of data-driven local model networks

This article discusses stability analysis of data-driven dynamic local model networks. In contrast to traditional fuzzy modelling, the structure and complexity of such model architectures is not unique when only observed input- and output data are available for their parametrization. The present article complements the well-known trade-off between accuracy and complexity by the notion of stability. For this purpose, existing Lyapunov stability criteria for local model networks are extended by a decay rate which represents a scalar and quantitative stability measure. It allows to compare models with different degrees of complexity also in view of their stability. For some of the commonly available Lyapunov stability criteria, the individual local model transitions are crucial. Therefore, in this article, an approach is introduced to determine the actually occurring model transitions by means of the identification data. The methods presented in the article are illustrated and discussed by means of a simulation example. It is shown how model complexity and the related approximation quality can have an adverse impact on the stability and how the outcome of different Lyapunov criteria is affected by the proper determination of local model transitions.     

AlxGa1−xN bulk crystal growth: Crystallographic properties and p–T phase diagram

The recent results on the growth of the Al_xGa_1−xN bulk single crystals (0.22≤x≤0.91) from solution in liquid Ga under high nitrogen pressure are discussed. We focus on the influence of temperature and the choice of the Al source on the crystal growth. The experiments involving different sources of aluminum such as Al metal, pre-reacted polycrystalline Al_yGa_1−yN and AlN powder are compared. The best results were achieved using pre-reacted polycrystalline Al_yGa_1−yN or/and AlN. Single-crystal structure refinement data of these Al_xGa_1−xN crystals are presented. We also update the p–T phase diagram of (Al,Ga)N compound at high N₂ pressure for various Al content, which is the basis for (Al,Ga)N synthesis.