酒石酸酯化物的合成与应用研究进展

综述了12种酒石酸酯化物的合成方法,重点介绍了酒石酸酯化物在手性助剂、手性配体、手性源合成配体、手性萃取选择剂等领域中的应用,提出了未来的研究方向和应用前景。参考文献69篇。     

Tandem One-Pot Conversion of Aldehydes into Ethyl Esters

A facile one-pot synthesis of ethyl esters from aldehydes has been developed. This tandem process involves the formation of a nitrile intermediate obtained from the reaction of an aldehyde with hydroxylamine hydrochloride in dimethylsulfoxide (DMSO) at 100 °C and the subsequent reaction of the nitrile with ethanol and sulfuric acid at 130 °C. The resulting ethyl ester products were produced in good yields (65–90%) and high purity (>95%).

Convenient Synthesis of Thiol Esters from Acyl Chlorides and Disulfides Using Zn/AlCl3

Summary.  Various thiol esters were prepared by condensation of acyl chlorides with disulfides in the presence of Zn/AlCl₃. The advantages of this method are high yields under relatively mild conditions, simple work-up, lack of toxicity, and low costs. Received July, 20, 2001. Accepted September 24, 2001     

Synthesis of Thiol Esters by the Reaction of Ricinoleic Acid with Thiols Under Solvent-Free Conditions

The synthesis of several ricinoleic acid thiol esters starting from cis-(R)-12-hydroxyoctadec-9-enoic acid and thiols in the presence of N,N′-dicyclohexylcarbodiimide (DCC) is described. The method is efficient for aromatic and aliphatic thiols, selectively affording the respective fat acid thiol esters in good yields under mild, neutral, and solvent-free conditions. The protocol is general and was extended to other carboxylic acids, furnishing the desired products in satisfactory yields. The (R,Z)-12-hydroxy-octadec-9-enylic acid benzylthiol ester 3a was successfully reduced to (R,Z)-12-hydroxyoctadec-9-enal 4.      

Chiral Borated Esters in Asymmetric Synthesis： 1. The First Asymmetric Reaction Catalyzed by Chiral Spiroborated Esters with an O3BN Framework

The first asymmetric reaction catalyzed by chiral spiroborated esters with an O3BN framework was reported. In the presence of 0.1 equivalent of (R,S)-1 or (S,S)-1, acetophenone was reduced by 0.6 equivalent of borane in THF at 0-5℃ for 2 h to give (R)-1-phenylethanol of up to 76% ee and 73% isolated yield. Influence of reaction conditions on the stereoselectivity of the reduction was investigated and a possible catalytic mechanism of the chiral spiroborated esters toward the reduction was also suggested.     

Synthesis of Selenol Esters from Acid Chlorides and Organic Diselenides in the Presence of the Zn/AlCl3 System

Summary.  Treatment of diphenyl and dibenzyl diselenides with aliphatic and aromatic acid chlorides in the presence of Zn/AlCl₃ affords selenol esters. Availability, low costs, and lack of toxicity of the catalysts, simple reaction work-up, and high yields under relatively mild condition are distinct advantages of this method. Corresponding author. E-mail: movassagh@hotmail.com Received August 26, 2002; accepted September 3, 2002 Published online April 3, 2003     

A Novel Conversion of N-Aryl-N-Methoxyamides into N-Arylhydroxamic Acids Using Alcl3/Thiol System

Treatment of N-aryl-N-methoxyamides with AlCl₃ in EtSH (or Me₂S) generates the corresponding N-aryl-N-hydroxyamides in high yields.     

CO2 Conversion into Esters by Fluoride‐Mediated Carboxylation of Organosilanes and Halide Derivatives

A one‐step conversion of CO₂ into heteroaromatic esters is presented under metal‐free conditions. Using fluoride anions as promoters for the C?Si bond activation, pyridyl, furanyl, and thienyl organosilanes are successfully carboxylated with CO₂ in the presence of an electrophile. The mechanism of this unprecedented reaction has been elucidated based on experimental and computational results, which show a unique catalytic influence of CO₂ in the C?Si bond activation of pyridylsilanes. The methodology is applied to 18 different esters, and it has enabled the incorporation of CO₂ into a polyester material for the first time.     

温和条件下 Cu-Zn/Al2O3 催化剂上酯加氢制醇

 制备了新型无铬非晶态 Al2O3 负载的 Cu-Zn 催化剂, 并采用 X 射线衍射、透射电镜、程序升温还原和红外光谱进行了表征, 考察了其液相酯加氢制高碳醇的催化性能, 并优化了反应条件. 结果表明, 在 240 °C 和 10 MPa 氢压相对温和的反应条件下, 髙碳醇收率达 86.3%, 远远高于相同条件下传统的 Cu-Cr 基催化剂. 对前体、焙烧后及还原后催化剂的物相进行了研究, 探讨了催化剂组分及表面羟基的作用.     

手性硼酸酯介入的不对称合成3† (R)-或(S)-1,1'-联-2-萘酚硼酸-(S)-脯氨酸酐促进的前手性亚胺的不对称硼烷还原

手性螺硼酸酯(R)-或(S)-1,1'-联-2-萘酚硼酸-(S)-脯氨酸酐[(R,S)-1或(S,S)-1]对前手性亚胺硼烷还原的不对称催化活性被观察到. 在(R,S)-1或 (S,S)-1存在下, 由前手性二烷基酮或烷基苯酮与苯胺缩合生成的前手性亚胺在THF中被硼烷还原, 高产率地给出手性仲胺, 其对映体纯度高达74% ee. 其中, 三种手性仲胺[N-(2-戊基)苯胺, N-(3-甲基-2-丁基)苯胺和N-(4-甲基-2-戊基)苯胺]系首次合成.     

(E)-2-乙氧基乙基-2-氰基-3-((4-(2,4-二氟苯氧基)苄基)氨基)-3-甲氧基丙烯酸酯对超螺旋质粒DNA的特异性切割(英文）

研究了一种新型丙烯酸酯 (E)-2-乙氧基乙基-2-氰基-3-((4-(2,4-二氟苯氧基)苄基)氨基)-3-甲氧基丙烯酸酯(MAZ)对超螺旋pUC19 DNA的定点切割作用。利用紫外吸收、荧光光谱、凝胶电泳和DNA测序技术研究其核酸切割特异性。紫外吸收光谱的红移和减色效应,以及静态荧光淬灭表明MAZ与DNA的作用属于典型的插入模式。不仅如此,凝胶电泳条带的变化以及DNA测序结果表明DNA的定点切割是通过DNA双链的分步水解完成。     

Highly Efficient One-Step Conversion of Selenol Esters into Symmetrical Diselenides in the Presence of Elemental Iodine in Methanolic Solution

A facile, efficient, and convenient procedure has been developed for the direct conversion of selenol esters into the corresponding diselenides in the presence of elemental iodine at room temperature.     

Conversion of 4- and 5-hydroxyaminothiazolidine-2-thiones under the action of alkalis

5-Hydroxyaminothiazolidine-2-thiones are oxidized in an alkaline medium to 5-hydroxyiminothiazolidine-2-thiones or undergo recyclization to derivatives of imidazolidine-2-thiones, depending on their structure. 4-Hydroxyaminothiazolidine-2-thiones break down under analogous conditions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1143–1145, August, 1989.     

Vapor-Phase Conversion of Esters into Ketones in the Presence of an Sn-, Ce-, and Rh-Containing Oxide Catalyst

The catalytic conversion of acyclic and cyclic esters into ketones was studied. Based on an analysis of data on the yields of the products of ester conversion, the conclusion was drawn that ketones result from a reaction between two ester molecules with the intermediate formation of a -ketoester. This reaction is accompanied by the partial thermal decomposition of esters to aldehydes (reverse Tishchenko reaction) with the subsequent condensation.     

Cl3CCONH2/PPh3: A Versatile Reagent for Synthesis of Esters

Cl₃CCONH₂/PPh₃ was a versatile reagent to convert carboxylic acids into their corresponding acid chlorides. This intermediate was clearly confirmed by spectroscopic methods (IR, ¹H, ¹³C NMR). This one-pot reaction of in situ acid chloride generated with various alcohols successfully furnished the corresponding esters in moderate to excellent yields.