脂肪腈一步法制双脂肪烃基仲胺新工艺的研究

由氨合成气代替纯氢气使脂肪腈加压催化胺化，可一步制得双脂肪烃基仲胺。采用该工艺制得的仲胺产品质量技术指标，达到国内外同类产品水平。结果表明，该工艺具有工艺简单、投资少、成本低等优点。     

毛细管柱顶空气相色谱法测定水中酮、醇、腈和吡啶污染物研究

用大口径毛细管柱顶空气相色谱法同时测定水中丙酮、醇类、丙烯腈和吡啶等有机污染物，方法简便、快速、干扰少，0.25mL顶空气体进样，检出限分别为0.005mg/L、0.012mg/L、0.009mg/L、0.003mg/L和0.015mg/L，灵敏度高于直接进水样法，可用于水和不宜直接进样分析的样品测定。     

腈的生物转化不对称合成β-氨基酸和β-氨基酰胺

含有腈水合酶和酰胺水解酶的红球菌Rhodococcus erythropolis AJ270能在非常温和的条件下催化一系列β-氨基苯丙腈衍生物的水解反应, 生成相应的β-氨基酸和β-氨基酰胺. 底物结构对生物转化反应的效率及立体选择性影响很大. 3-氨基-3-苯丙腈的生物水解反应显示了较低的立体选择性, 而氮甲基取代衍生物的水解反应则显示了中等立体选择性, 生成相应S构型β-氨基酸和R构型β-氨基酰胺. 氮上大位阻取代基显著降低生物催化效率.     

Iron‐Catalyzed Dehydration of Aldoximes to Nitriles Requiring Neither Other Reagents Nor Nitrile Media

The dehydration of aldoximes is an environmentally benign reaction affording the desired nitrile and water as a by‐product. However, most of the reported catalytic dehydration reactions of aldoximes require a solvent containing nitrile to synthesize the corresponding nitrile compounds. Inspired by recent reports on the enzymatic synthesis under nitrile‐free conditions, we here describe that a simple iron salt catalyzes the dehydration of aldoximes requiring neither other reagents nor nitrile media. Our method can be applied to the one‐pot synthesis of nitiriles from aldehydes.     

Macromolecular Surface Design: Photopatterning of Functional Stable Nitrile Oxides

The efficient trapping of photogenerated thioaldehydes with functional shelf‐stable nitrile oxides in a 1,3‐dipolar cycloaddition is a novel and versatile photochemical strategy for polymer end‐group functionalization and surface modification under mild and equimolar conditions. The modular ligation in solution was followed in detail by electrospray ionization mass spectrometry (ESI‐MS). X‐ray photoelectron spectroscopy (XPS) was employed to analyze the functionalized surfaces, whereas time‐of‐flight secondary‐ion mass spectrometry (ToF‐SIMS) confirmed the spatial control of the surface functionalization using a micropatterned shadow mask. Polymer brushes were grown from the surface in a spatially confined regime by surface‐initiated atom transfer radical polymerization (SI‐ATRP) as confirmed by TOF‐SIMS, XPS as well as ellipsometry.     

Towards Structural‐Functional Mimics of Acetylene Hydratase: Reversible Activation of Acetylene using a Biomimetic Tungsten Complex

The synthesis and characterization of a biomimetic system that can reversibly bind acetylene (ethyne) is reported. The system has been designed to mimic catalytic intermediates of the tungstoenzyme acetylene hydratase. The thiophenyloxazoline ligand S‐Phoz (2‐(4′,4′‐dimethyloxazolin‐2′‐yl)thiophenolate) is used to generate a bioinspired donor environment around the W center, facilitating the stabilization of W–acetylene adducts. The featured complexes [W(C₂H₂)(CO)(S‐Phoz)₂] ( 2 ) and [WO(C₂H₂)(S‐Phoz)₂] ( 3 ) are extremely rare from a synthetic and structural point of view as very little is known about W–C₂H₂ adducts. Upon exposure to visible light, 3 can release C₂H₂ from its coordination sphere to yield the 14‐electron species [WO(S‐Phoz)₂] ( 4 ). Under light‐exclusion 4 re‐activates C₂H₂ making this the first fully characterized system for the reversible activation of acetylene.     

Copper-Catalyzed Borylative Couplings with C−N Electrophiles

Copper-catalyzed borylative multicomponent reactions (MCRs) involving olefins and C−N electrophiles are a powerful tool to rapidly build up molecular complexity. The products from these reactions contain multiple functionalities, such as amino, cyano and boronate groups, that are ubiquitous in medicinal and process chemistry programs. Copper-catalyzed MCRs are particularly attractive because they use a relatively abundant and non-toxic catalyst to selectively deliver high-value products from simple feedstocks such as olefins. In this Minireview, we explore this rapidly emerging field and survey the borylative union of allenes, dienes, styrenes and other olefins, with imines, nitriles and related C−N electrophiles.     

Neighboring-group participation by C-2 ether functions in glycosylations directed by nitrile solvents

Ether-protecting functions at C-2 hydroxy groups have been found to play participating roles in glycosylations when the reactions are conducted in nitrile solvent mixtures. The participation mechanism is based on intramolecular interaction between the lone electron pair of the oxygen atom of the C-2 ether function and the nitrile molecule when they are positioned in a cis configuration. A 1,2-cis glycosyl oxazolinium intermediate is formed. This participation, in conjunction with the anomeric effect of the glycosyl donor, confers high 1,2-trans selectivities on glycosylations. Further application of this concept has led to efficient preparations of α-(1→5)-arabinan oligomers.     

5-磷酰基-3-芳基异噁唑啉的合成及结构表征

通过乙烯基膦酸酯与氧化腈的环加成反应,合成了一系列区域专一的异噁唑啉.化合物3c的单晶X衍射证实产物为5-磷酰基异噁唑啉.目标化合物结构经核磁、电喷雾质谱和元素分析表证,生物活性测试表明这些化合物具有一定的神经氨酸酶抑制活性.