亲核性1,2-重排为何迁移基团的构型保持不变*

亲核性1,2-重排反应是有机化学的重要反应之一,重排中离去基团的离去和迁移基团的迁移步骤既可以是分步的,也可以是协同的,但是迁移基团的构型始终保持不变。本文用超共轭效应和反应过程中有机立体电子效应解释了此现象,掌握一般规律,希望能够从教学上便于教师讲授和学生学习理解。     

18O/16O-Encoding Strategy for Microscale Stereochemical Determination of Peptidic Natural Products

The demand for more efficient methods of establishing the undetermined stereochemistries of peptidic natural products continues unabated. A new method for microscale stereochemical determination was devised by integrating solid-phase synthesis, split-and-mix randomization, ¹⁸O/¹⁶O-encoding of d /l -configurations, tandem mass spectrometry, and biological evaluation. Here we applied gramicidin A as the molecule for a blind test. Gramicidin A and its 31 diastereomers were randomly prepared in microgram scale with ¹⁸O/¹⁶O-stereochemical encoding and subjected to MS/MS-structural determination and cytotoxicity assay. Only the parent gramicidin A was selected from among the 32 stereoisomers, validating the high reliability of the present strategy.     

大学基础化学教学中的知其所以然*

针对大学本科一年级基础化学如“化学概论”等课程教学中,学生对于不断出现的专业名词及物理化学含义的理解问题,以“焓”“熵”等外来词汇以及角动量l、能级分裂单位“Dq”等缩写为例,从专业名词来源开始讲解,使学生在学习过程中既知其然又知其所以然,更好地理解化学专业词汇,尤其是外来词汇的内涵与物理化学意义。     

“神龙一号”加速器束流输运系统研制

文章系统介绍了“神龙一号”直线感应加速器束流输运系统的研制过程和取得的成果, 重点阐述了螺线管线圈、二极校正线圈、多功能腔等关键单元部件的设计、传输元件的磁轴测量和准直安装、束线的总体布局、束流调试等研究内容. 束流调试结果表明, 该束流传输线的设计是成功的, 并且具有较宽的动态适应范围. 最后, 结合束流调试的经验, 提出了一些建议供以后工作参考.     

Regioselective Short Synthesis of Epiisoborneol Neopentyl Ether as Chiral Auxiliary: An Absolute Configuration Reset

The regio-selective four step synthesis of (1S,2R,3S,4R)-4,7,7-trimethyl-3-(neopentyloxy)bicyclo[2.2.1]heptan-2-ol, as recognized efficient chiral auxiliary, is presented. The strategy based on opening of the key acetal 15 (=(2S,3aR,4S,7R,7aS)-2-tert-butyl-4,8,8-trimethylhexahydro-2H-4,7-methano-1,3-benzodioxole) thus circumvents the poor reactivity of the neopentyl electrophile under alkylation conditions. Following the same strategy, but using the unreported acetal 22 (=(2R,3aS,4S,7R,7aR)-2-tert-butyl-4,8,8-trimethylhexahydro-2H-4,7-methano-1,3-benzodioxole), the corresponding unreported bis-endo alcohol 23 (=(1R,2R,3S,4S)-3-(2,2-dimethylpropoxy)-4,7,7-trimethylbicyclo[2.2.1]heptan-2-ol) could be isolated only in poor yield. An alternative regioselective synthesis, including an ultimate endo-reduction remains to be found. Several erroneous chiroptical properties from the literature are corrected.     

Using Terpene Synthase Plasticity in Catalysis: On the Enzymatic Conversion of Synthetic Farnesyl Diphosphate Analogues

Four synthetic farnesyl diphosphate analogues were enzymatically converted with three bacterial sesquiterpene synthases, including β-himachalene synthase (HcS) and (Z)-γ-bisabolene synthase (BbS) from Cryptosporangium arvum, and germacrene A synthase (SmTS6) from Streptomyces mobaraensis. These enzyme reactions not only yielded several previously unknown compounds, showing that this approach opened the door to a new chemical space, but substrates with blocked or altered reactivities also gave interesting insights into the cyclisation mechanisms and the potential to catalyse reactions with different initial cyclisation modes.     

空间光调制器曲面拼接实现全息三维显示视角拓展

本文对多空间光调制器不同拼接方式拓展全息三维再现像视角的方法进行了分析,基于多片空间光调制器拼接拓展视角的思想,利用平面反射镜、分光镜和两片透射式空间光调制器设计了曲面拼接系统,进行了全息三维再现像的视角拓展实验研究。用该系统对四棱锥物体的层析菲涅尔衍射全息图进行再现,结果表明,总视角由基于单片空间光调制器的1.7°增大到3.2°,即拓展到约1.9倍,分光镜能够消除两片空间光调制器间的间隙,实现无缝拼接。该方法同样适用于更多空间光调制器的曲面拼接中,可以有效地拓展全息再现像的视场角大小。     

Stereochemistry of the Three-Component Reaction Between the Ley′S Aldehyde,Benzyl Amines,and Trialkyl Phosphites. A New Approach to the Protected Enantiomerically Pure 1-Amino-2,3-Dihydroxypropylphosphonates

Abstract

Enantiomerically pure orthogonally protected dimethyl 1-aminophosphonates (2R,5R,6R,1′R)- and (2R,5R,6R,1′S)-10, phosphonate analogs of 4-hydroxythreonine, were prepared employing the three-component reaction between trimethyl phosphite, (2R,5R,6R)-5,6-dimethoxy-5,6-dimethyl-1,4-dioxane-2-carbaldehyde (Ley’s aldehyde), and benzhydrylamine. Since both aminophosphonates 10 exist in a chloroform solution as single rotamers, the absolute configurations at C1′ were unequivocally established based on ¹H and ¹³C NMR spectral data. Studies on stereochemistry of the addition of trialkyl phosphites showed that in chloroform in all cases the nucleophile preferentially attacks the si-face of the C?N bond, while in alcohols the 1,2-stereoinduction is negligible, and sense of chirality of phenylethylamines is solely responsible for a π-facial discrimination in the 1,3-asymmetric inductions.     

C,C‐ and N,C‐Coupled Dimers of 2‐Aminotetraphenylporphyrins: Regiocontrolled Synthesis,Spectroscopic Properties,and Quantum‐Chemical Calculations

β,β′‐Bisporphyrins are intrinsically chiral porphyrin dimers with fascinating properties. The configurational stability at their axes can be directed by variation of the central metal atoms. Herein, we present a regioselective functionalization of the monomeric 2‐amino‐tetraphenyl‐porphyrin as a versatile substrate for dimerization by oxidative coupling. By simple variation of the reaction conditions (solvent and oxidant), the oxidation selectively gave either the axially chiral C,C‐coupled diaminobisporphyrin in high yields or, under Ullmann conditions, the twofold N,C‐linked achiral dimer, also in good yields. A generalized mechanism for the coupling reaction is proposed based on DFT calculations. The axially chiral β,β′‐coupled porphyrin dimers were isolated as racemic mixtures, but can be resolved by HPLC on a chiral phase. TDDFT and coupled‐cluster calculations were used to explain the spectroscopic properties of the aminoporphyrins and their dimers and to elucidate the absolute configurations of the C,C‐coupled bisporphyrins.     

Determination of the Absolute Configuration of Perylene Quinone‐Derived Mycotoxins by Measurement and Calculation of Electronic Circular Dichroism Spectra and Specific Rotations

Altertoxins I–III, alterlosins I and II, alteichin (alterperylenol), stemphyltoxins I–IV, stemphyperylenol, stemphytriol, 7‐epi‐8‐hydroxyaltertoxin I, and 6‐epi‐stemphytriol are mycotoxins derived from perylene quinone, for which the absolute configuration was not known. Electronic circular dichroism (ECD) spectra were calculated for these compounds and compared with measured spectra of altertoxins I–III, alteichin, and stemphyltoxin III and with reported Cotton effects. Specific rotations were calculated and compared with reported specific rotations. The absolute configuration of all the toxins, except for stemphyltoxin IV, could thus be determined. The validity of the assignment was high whenever reported ECD data were available for comparison, and the validity was lower when the assignment was based only on the comparison of calculated and reported specific rotations. ECD spectra are intrinsically different for toxins with a biphenyl substructure and for toxins derived from dihydroanthracene.