手性双二茂铁基配体的合成、表征及固体CD光谱

以甲酰基二茂铁(1)和手性1,2-二苯基乙二胺[(1R, 2R)-1,2-二苯基乙二胺(2R), (1S,2S)-1,2-二苯基乙二胺(2S)]为原料, 经缩合、还原和N-烷基化反应, 制备了一对新型手性四齿双二茂铁基配体[N,N’-二(二茂铁基甲基)-N,N’-二(2-羟基丙基)-(1R,2R)-1,2-二苯基乙二胺(5R)和N,N’-二(二茂铁基甲基)-N,N’-二(2-羟基丙基)-(1S,2S)-1,2-二苯基乙二胺(5S)]. 用元素分析、红外(IR)、质子核磁共振(1H NMR)、紫外-可见(UV-Vis)、固体圆二色(CD)光谱等对手性产物(3R-5S)进行了表征. 固体CD光谱研究表明, 配体5R(或5S)的手性特征和4R(或4S)相似而与3R(或3S)却有一定差别.     

新型手性Schiff碱的合成

从手性联萘酚出发,经四步反应合成了一种水杨醛类衍生物(4); 4与(1S,2R)-(+)-2-氨基-1,2-二苯基乙醇反应合成了一种新型手性Schiff碱(6); 6经NaBH4还原制得其类似物.其结构经1H NMR和IR表征.     

新型2，6-双（3，5-二取代吡唑基-1-羰基）吡啶的合成

报道了四种吡唑衍生物和它们四种新型的杂环酰胺衍生物的合成，它们是3，5-二甲基吡唑(1)，5-甲基-3-苯基吡唑(2)，3，5-二苯基吡唑(3)，5-甲基-3-二茂铁基吡唑(4)，2，6-双(3，5-二甲基吡唑基-1-羰基)吡啶(5)，2，6-双(5-甲基-3-苯基吡唑基-1-羰基)吡啶(6)，2，6-双(3，5-二苯基吡唑基-1-羰基)吡啶(7)和2，6-双(5-甲基-3-二茂铁基吡唑基-1-羰基)吡啶(8)．并对它们进行了元素分析，FT-IR，^1H NMR和^13C NMR等波谱分析．     

新型2,6-双(3,5-二取代吡唑基-1-羰基)吡啶的合成

报道了四种吡唑衍生物和它们四种新型的杂环酰胺衍生物的合成 ,它们是 3 ,5 二甲基吡唑 (1) ,5 甲基 3 苯基吡唑(2 ) ,3 ,5 二苯基吡唑 (3 ) ,5 甲基 3 二茂铁基吡唑 (4 ) ,2 ,6 双 (3 ,5 二甲基吡唑基 1 羰基 )吡啶 (5 ) ,2 ,6 双 (5 甲基 3 苯基吡唑基 1 羰基 )吡啶 (6) ,2 ,6 双 (3 ,5 二苯基吡唑基 1 羰基 )吡啶 (7)和 2 ,6 双 (5 甲基 3 二茂铁基吡唑基 1 羰基 )吡啶 (8) .并对它们进行了元素分析 ,FT IR ,1HNMR和13 CNMR等波谱分析 .     

一种新的具有C_2对称轴的含N,O的手性多齿配体的合成

以(1R,2R)-1,2-二苯基乙二醇和2-甲氧基-4,6-二氯-1,3,5-三嗪为原料,经保护、取代和去保护反应合成了一种新的手性多齿配体——2-甲氧基-4,6-二[(1R,2R)-1,2-二苯基-2-羟基乙氧基]-1,3,5-三嗪,其结构经1HNMR,13CNMR,IR及LC-MS表征。     

手性多齿配体的合成及其在二乙基锌对苯甲醛不对称加成反应中的应用

以(1R,2R)-1,2-二苯基乙二醇和2,4,6-三氯-1,3,5-三嗪为原料,经保护、取代、去保护等反应合成了3个新的手性多齿配体,并将其应用于二乙基锌对苯甲醛不对称加成反应中。结果表明,2,4-二(4-吗啉基)-6-((1R,2R)-1,2-二苯基-2-羟基乙氧基)-1,3,5-三嗪在此反应中的效果最好,所得产物ee值为32%。     

一种含三嗪单元多齿手性配体的合成

以（R,R）-1,2-二苯基乙二醇和氰尿酰氯为原料,经保护、醚化、去保护、取代等反应合成了一种新的手性多齿配体2-乙氧基-4-（2-甲氧基-乙氧基）-6-(（1R,2R）-1,2-二苯基-2-甲氧基-乙氧基)-1,3,5-三嗪,并通过1HNMR 、LCMS和元素分析对目标化合物的结构进行了表征。     

碘-二甲基亚砜促进新型四环噻唑并[3',2':2,3]吡啶并[4,5-d]吡啶并[1,2-a]嘧啶酮类衍生物的合成（英文）

介绍了在碘-二甲基亚砜(I_2-DMSO)促进作用下,通过Pictet-Spengler反应合成噻唑并[3',2':2,3]吡啶并[4,5-d]吡啶并[1,2-a]嘧啶酮(5)衍生物的合成方法.该反应的关键中间体2-(3-氨基-5-苯氨基噻唑-2-基)-4H-吡啶[1,2-a]嘧啶-4-酮(3),由2-氯甲基-4H-吡啶[1,2-a]嘧啶-4-酮(1)与N-苯基-N'-氰基-咪唑硫代碳酸钾(2)通过Thorpe-Ziegler异构化反应制得.该合成方法反应条件温和,操作简单,收率高.     

温和条件下高效合成咪唑并杂环-肼类衍生物的三组分串联反应（英文）

为了合成咪唑[1,2-a]并吡啶-肼类衍生物,发展了一种以简单易得的甲酰甲基溴化物、2-氨基吡啶衍生物和偶氮二甲酸酯为原料的三分子串联反应的方法.该串联反应先生成咪唑[1,2-a]并吡啶,然后紧接着连续发生C(3)—H键肼基化反应,而不像传统的一步接一步反应的方法.该方法具有操作简单、反应条件温和(无需过渡金属且反应温度低等)以及底物适用性广的特点.实验结果表明,带有给电子取代基的甲酰甲基溴化物和2-氨基吡啶衍生物有利于反应的进行,并以优秀的产率获得目标产物.     

2-吡啶基咪唑并[1,2-a]吡啶的水中合成

2-乙酰基吡啶1经溴化反应后得到2-(2-溴乙酰基)吡啶氢溴酸盐2,2在水中与NaHCO3发生中和反应生成2-(2-溴乙酰基)吡啶,不经分离直接于水中和2-氨基吡啶衍生物3a-3h反应生成2-吡啶基咪唑并[1,2-a]吡啶4a-4h.采用核磁共振谱仪、红外光谱仪及质谱仪表征了产物的结构.结果表明,利用该方法可以在温和的反应条件下高产率得到目标产物,且方法操作简便、对环境友好.     

Convergent synthesis of (2R,3R,8R,9R)-N-Boc-ADDA

The convergent synthesis of N-Boc-(2R,3R,8R,9R,4E,6E)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldecadenoic acid (enantio-N-Boc-ADDA) is reported. Our flexible approach takes advantage of highly efficient non-aldol aldol and cross-metathesis methodologies.     

Total Synthesis of (6R,10R,13R,14R,16R,17R,19S,20R,21R,24S, 25S,28S,30S,32R,33R,34R,36S,37S,39R)‐Azaspiracid‐3 Reveals Non‐Identity with the Natural Product

A convergent and stereoselective total synthesis of the previously assigned structure of azaspiracid‐3 has been achieved by a late‐stage Nozaki–Hiyama–Kishi coupling to form the C21?C22 bond with the C20 configuration unambiguously established from l ‐(+)‐tartaric acid. Postcoupling steps involved oxidation to an ynone, modified Stryker reduction of the alkyne, global deprotection, and oxidation of the resulting C1 primary alcohol to the carboxylic acid. The synthetic product matched naturally occurring azaspiracid‐3 by mass spectrometry, but differed both chromatographically and spectroscopically.     

Röntgenweit- und Röntgenkleinwinkeluntersuchungen an Zellulose

Zusammenfassung Für verschiedene Zelluloseproben wurden mittels Röntgenweitwinkelstreuung die mittleren lateralen Kristallitgrößen und ihre Gestaltellipse in der Ebene senkrecht zur Kettenrichtung bestimmt. Die Gaußanalyse der Weitwinkelreflexe zeigt teilweise eine Aufspaltung in Vielfache einer kleinsten Kristallitgröße. Dies wird auf teilweise Rekristallisation zurückgeführt. Die Gaußanalyse der kontinuierlichen Kleinwinkelstreuung liefert in allen Fällen gleichfalls Vielfache einer kleinsten Einheit. Zeigt der Weitwinkelreflex keine Aufspaltung, kann das Kleinwinkelergebnis nicht durch Rekristallisation, sondern durch einfache Clusterbildung erklärt werden.Weitwinkel- und Kleinwinkelergebnisse stimmen sehr gut miteinander überein.

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Summary The mean lateral crystallite sizes and the shape ellipse in the plane perpendicular to the chain direction have been estimated for different cellulose samples by wide angle X-ray diffraction. Gaussian analysis of the wide angle reflexions partly shows a splitting into multiples of a smallest crystallite size. This is explained by partly recrystallization. Gaussian analysis of the continuous small angle diffraction in all cases yields multiples of a smallest unit, too. If the wide angle reflexion does not show any splitting, the small angle result cannot be explained by recrystallization, but simply by clustering of the fibrils.There is an excellent agreement between the wide angle and the small angle results.

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Mit 4 Abbildungen und 4 Tabellen     

Vapour-liquid equilibrium measurements for binary mixtures of R32, R143a, R134a and R125 with a perfluoropolyether lubricant

In the present work, vapour-liquid equilibria of four binary systems refrigerant-lubricant oil have been investigated, CF₃CHF₂ (R125), CF₃CH₂F (R134a), CF₃CH₃ (R143a) and CH₂F₂ (R32) as refrigerants and a commercial perfluoropolyether (PFPE), Fluorolink D10H, as lubricant. Vapour-liquid equilibrium data, consisting of isothermal measurement of equilibrium pressure at a fixed composition, have been correlated with an extended Flory-Huggins equation and the corresponding parameters have been determined. Good agreement has been found between experimental data and the model predictions.     

Asymmetric synthesis of (S,R)- and (R,R)-methiin stereoisomers

Abstract

An asymmetric synthesis of (+)- and (–)-methiine (S-methyl-(R)-cysteine sulfoxide) diastereomers has been developed. These natural sulfur compounds were isolated from a variety of Brassica vegetables. As the starting compound, (R)-cysteine was used, which was methylated to form (R)-S-methylcysteine. Then the oxidation of S-methylcysteine with tert-butyl hydroperoxide catalyzed by the chiral tetra(isopropylate)titanium/(S)- or (R)-Binol complex led to the formation of (1?R,2S)-(+)- or (1?R,2R)-(–)-methiin stereomers.     

Studies on the transformation of nitrosugars into iminosugars III: synthesis of (2R,3R,4R,5R,6R)-2-(hydroxymethyl)azepane-3,4,5,6-tetraol and (2R,3R,4R,5R,6S)-2-(hydroxymethyl)azepane-3,4,5,6-tetraol

A divergent synthesis of the two novel polyhydroxylated azepanes (2R,3R,4R,5R,6R)-2-(hydroxymethyl)azepane-3,4,5,6-tetraol and (2R,3R,4R,5R,6S)-2-(hydroxymethyl)azepane-3,4,5,6-tetraol from d-mannose is described. The method involves a Henry reaction between dimethyl-tert-butylsilyl 2,3-O-isopropylidene-α-d-lyxo-pentodialdo-1,4-furanoside and 2-nitroethanol followed by a reductive ring closure of the resulting epimeric nitro aldols. Glycosidase inhibition tests showed that (2R,3R,4R,5R,6S)-2-(hydroxymethyl)azepane-3,4,5,6-tetraol exhibits a weak but selective inhibition against α-l-fucosides.     

R?ntgenspektralanalyse

Ohne Zusammenfassung