氰醇碳酸脂的制备及作为酰基负离子等效剂的应用

亲核酰化反应是近年来人们在研究有机化合物极性翻转(Umpolung)时所注意到的一类新型反应,它能使许多用经典的方法难以实现的有机合成反应得以顺利进行,还可简化合成的途经,因此,对亲核酰化反应的理论及其在合成上的应用研究引起了人们极大的兴趣和重     

有机磷化合物的研究——氧化膦酰化反应—合成二烃基膦酸及其衍生物的新方法

本文报道了一个基于二烃基亚膦酸在碱及四氯化碳存在下与亲核试剂反应制备二烃基膦酸及其衍生物的新法,研究了反应条件与亲核剂的结构对氧化膦酰化反应得率的影响,讨论了反应机理。     

α′-乙酰基-α-噻吩基苯乙炔六羰基二钴和α′-乙酰基-α-噻吩基-P-乙酰基苯乙炔六羰基二钴的合成及结构

本文研究了α-噻吩基苯乙炔六羰基二钴同乙酰氯的傅氏酰化反应,证明噻吩核较苯核有更强的亲电酰化活性,而苯核又较乙酰化的噻吩核有更强的亲电酰化活性;通过酰化反应合成了两个新钴碳簇合物,即α′-乙酰基-α-噻吩基苯乙炔六羰基二钴Ⅰ和α′-乙酰基-α-噻吩基-P-乙酰基苯乙炔六羰基二钴Ⅱ。除用碳氢分析、IR和~1HNMR推得Ⅰ和Ⅱ的结构外,还测得Ⅱ的单晶结构。Ⅱ晶体属单斜晶系,空间群为PZ_1╱n,晶胞参数a=8.037(2),b=16.347(3),c=17.823(2),β=102.68(2)°,D_c=1.61g·cm~(-3),Z=4。最终偏离因子R=0.040。     

有机磺酰氯参与的磺酰化及脱磺酰化反应

作为一类活泼的亲电试剂,有机磺酰氯参与的脱磺酰化偶联反应已经发展成为一个新的研究热点.在适当的温度以及钯等过渡金属络合物的催化下,磺酰氯可以和多种亲核试剂发生脱磺酰化偶联反应,并在一些重要有机合成反应中显示出良好的应用前景.有鉴于此,特就过渡金属催化下磺酰氯的脱磺酰化交叉偶联的研究进展进行简要的评述,并与相应的磺酰化反应进行对照,以其找出脱磺酰化偶联的关键因素,为以后的相关研究提供参考.     

多核苷酸合成化学新进展

本文总结了近十年来多核苷酸合成化学的进展,重点论述了核苷和核苷酸的区域选择酰化反应,亲核性催化的保护基和新近发展的核苷酸间键合的形成方法。     

贝曲西班的改进合成

以5-甲氧基-2-硝基苯甲酸为起始原料,经氢化、酰化、与二甲胺进行亲核加成反应,制得贝曲西班,总收率达61%以上。该方法具有原料易得、反应条件温和、收率高等优点,降低了生产成本,有良好的工业化应用前景。     

达沙替尼的合成工艺改进

以3-乙氧基丙烯酰氯为起始原料,经酰化、环合及亲核取代反应合成靶向药物达沙替尼,总收率60.1％,纯度99.5%,其结构经^1H NMR确证。对合成工艺进行了优化,总收率由50.2％提高至60.1％。     

An-PIQ催化的β-碘代Morita-Baylis-Hillman加合物动力学拆分研究

β-碘代Morita-Baylis-Hillman(MBH)加合物作为一种多官能团的手性砌块,是多种天然产物和药物分子的重要中间体.以课题组最近开发的An-PIQ为亲核催化剂,首次利用非酶亲核酰化动力学拆分的方法获得了一系列高光学纯β-碘代MBH加合物,S值最高可达165.该方法不仅解决了脂肪醛衍生的MBH加合物二级醇在动力学拆分中的低选择性问题,而且具有条件温和,较好的底物普适性,并能放大到克级规模等特点.     

合成4-巯基-1-丁醇的新方法

报道了一种合成4-巯基-1-丁醇（1）的新方法。以1,4-丁二醇为原料,经磺酰化反应及亲核取代反应制得1,总收率达75%,纯度98%（GC）,其结构经¹H NMR和MS（ESI）确证。     

含1,3,4-噻二唑杂环的甲氧基丙烯酸酯类化合物的合成与杀菌活性研究

以多种取代苯甲酸为原料,通过酰化、醇解、肼解、亲核加成、脱水、亲核取代等多步反应,合成了16个未见文献报道的含1,3,4-噻二唑杂环的甲氧基丙烯酸酯类化合物,其结构均通过1H NMR,IR,MS,HRMS等予以表征确认,并对所有化合物进行了离体杀菌活性测试.结果表明:对水稻立枯和棉花枯萎病菌的防效好于番茄晚疫病菌,对西瓜炭疽病菌防效显著,其中化合物5a~5c,5g,6a~6c的抑制率均高于嘧菌酯,5g在100μg/mL下抑制率为77.5%.     

Recognition and Site‐Selective Transformation of Monosaccharides by Using Copper(II) Catalysis

We demonstrate copper(II)‐catalyzed acylation and tosylation of monosaccharides. Various carbohydrate derivatives, including glucopyranosides and ribofuranosides, are obtained in high yields and regioselectivities. Using this versatile strategy, the site of acylation can be switched by choice of ligand. Preliminary mechanistic studies support nucleophilic addition of a copper–sugar complex to the acyl chloride to be turnover limiting.     

乙酰胆碱酯酶催化硫代乙酰胆碱水解反应的量子化学研究

应用量子化学和分子力学方法研究乙酰胆碱酯酶催化疏代乙酰胆碱水解反应中的乙酰化反应,计算了反应物、过渡态、产物及中间体的几何结构-及电子结构.结果表明,乙酰化反应机理是质子化和亲核进攻同时进行的协同机理.     

Expanding the catalytic activity of nucleophilic N-heterocyclic carbenes for transesterification reactions

[reaction: see text] Currently, there is a renewed interest in reactions that are catalyzed by organic compounds. Typical organic catalysts for acylation or transesterification reactions are based on either nucleophilic tertiary amines or phosphines. This communication discusses the use of nucleophilic N-heterocyclic carbenes as efficient transesterification catalysts. These relatively unexplored and highly versatile organic catalysts were found to be mild, selective, and more active than traditional organic nucleophiles.     

Nucleophilic acylation of arylfluorides catalyzed by imidazolidenyl carbene

Imidazolidenyl carbene catalyzes nucleophilic acylation reaction of arylfluorides with electron withdrawing groups to give benzophenone derivatives.     

Nucleophilic metal complexes as acylation catalysts: solvent-dependent "switch" mechanisms leading to the first catalyzed Staudinger reaction

[formula: see text] Catalytic acylation using complex transition metal salts MCo(CO)4 is demonstrated. Surprisingly, a solvent-dependent mechanistic "switch" results in a Lewis acid-based acylation mechanism in nonpolar media and a nucleophilic mechanism in polar organic media. These observations lead to the first example of a catalyzed Staudinger reaction to form beta-lactams.     

Hydroacylation of activated ketones catalyzed by N-heterocyclic carbenes

N-heterocyclic carbenes derived from triazolium salts are effective catalysts between 10 and 15 mol % for the hydroacylation of activated ketones. The reducing equivalent is generated via the interaction of a nucleophilic carbene species and an aromatic aldehyde. The subsequent alcohol product can undergo an acylation event with the resulting acyl heteroazolium intermediate formed in situ between the NHC and the aldehyde. This unprecedented multiple bond-forming reaction can accommodate aromatic aldehydes as the hydride source and various electron-deficient ketones. Preliminary mechanistic evidence indicates that the reduction and acylation steps are sequential operations. The intramolecular variant of this organocatalytic reaction affords benzofuranones in good yield.     

Synthesis and structure of amino esters of menthol

The conditions for the acylation of (?)-menthol with monochloroacetyl chloride have been studied. Amino esters of (?)-menthol have been obtained by the nucleophilic replacement of the chlorine in (?)-menthol monochloroacetate by residues of secondary amines. Their properties and their mass, IR, and¹³C NMR spectra are described.     

<Emphasis Type="Italic">P</Emphasis>-Acylphosphonium salts and their vinyloges — application in synthesis

Review with 101 refs. of progress in synthetic applications and properties of P-acylphosphonium salts including acylation via P-acylphosphonium salts, enantioselective acylation using chiral phosphine ligands, nucleophilic (β)-oniovinylation, and reaction involving vinyloges of P-acylphosphonium salts formed by treatment conjugated alkenoates or alkynoates with phosphines.     

Reaction of 2-amino-5-aryl-1,3,4-oxadiazoles with compounds with activated double bonds

The reaction of 2-amino-5-aryl-1,3,4-oxadiazoles with unsaturated acids and their chlorides was studied. It was shown by IR spectroscopy and mass spectrometry that acylation with acrylic, methacrylic, and cinnamic acid chlorides takes place at the nitrogen atom of the exocyclic amino group. Depending on the solvent, two reaction pathways are realized with unsaturated acids: acylation of the starting 2-amino-5-aryl-1,3,4-oxadiazole occurs in bromobenzene, while nucleophilic addition to the unsaturated acid molecule is realized in DMF in the presence of potassium hydroxide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 825–829, June, 1990.