Bischler-Napieralski反应研究进展

Bischler-Napieralski反应是合成3,4-二氢异喹啉的经典方法。通过文献调研,对其机理、影响因素、拓展研究及应用进行综述,发现Bischler-Napieralski反应已被广泛运用于医药、化工等重要中间体的合成,但三氯氧磷、五氧化二磷等脱水剂的使用仍较频繁。     

异喹啉酮类衍生物的合成研究

以间甲氧基苯乙胺和氯甲酸乙酯为原料,通过亲核取代、关环、四氢铝锂还原得到1,2,3,4-四氢异喹啉衍生物.其中关键步骤环化反应实现了使用多聚磷酸(PPA)简便有效地进行了关环,合成了一系列异喹啉酮类衍生物.     

碘催化的亚胺Diels-Alder反应：有效地合成四氢喹啉衍生物

Iodine was found to be an efficient catalyst for the imino Diels-Alder reaction of N-arylimine with enol ethers toprovide tetrahydroquinolines in good yields.The influence of the loading of iodine,reaction solvent,the structure ofimine and enol ethers was studied.One pot synthesis of tetrahydroquinolines from aldehyde,aniline and enol etherscatalyzed by iodine was also applicable and provided tetrahydroquinolines in comparable yields.Mild reaction con-ditions,facile experimental procedure,low price of iodine and good yield of products render this new method at-tractive for practical synthesis of many tetrahydroquinoline derivatives.     

分子内Diels-Alder反应的立体化学

Diels-Alder反应是研究得最多的环化加成反应,它的反应历程、立体化学等问题是近年来有机化学工作者广泛探讨的一个领域。本文在不对称分子间Diels-Alder反应的立体化学基础上,初步介绍分子内Diels-Alder反应(以下简称IMDA反应)的立体选择性。第一个IMDA反应于1953年由Alder和Schumaker提出,它是一个苯乙烯的衍生物,     

非对称烯烃反应的立体化学

通过实例就非对称烯烃反应(加卤素、加次卤酸、溶剂汞化-脱汞反应、硼氢化-氧化反应、稀冷高锰酸钾氧化反应、过酸氧化反应等)的区域选择性和立体专一性进行详细分析,并根据反应机理讨论了产物的立体构型。     

四氢异喹啉衍生物的合成研究

以间甲氧基苯乙胺和氯甲酸乙酯为原料,通过亲核取代、关环、铝锂氢还原、脱甲基以及在N位上Boc保护及脱保护等9步反应得到一系列重要的1,2,3,4-四氢异喹啉及其衍生物.产物的结构经核磁共振氢谱、红外光谱及元素分析确证.与传统四氢异喹啉衍生物的合成工艺相比,该工艺反应条件温和、简便、经济、产率高且对环境友好.     

四氢异喹啉阿司匹林衍生物的设计、合成及抗肿瘤活性研究

运用药物分子片段原理及拼合原理,设计了四氢异喹啉阿司匹林衍生物。以取代苯甲酸、3,4-二甲氧基苯乙胺或胡椒乙胺为原料,通过酰胺化反应、Bischler-Napieralski反应和亲核取代反应等步骤,合成了12个全新的四氢异喹啉阿司匹林衍生物。以5-氟尿嘧啶为阳性对照药,采用SRB法对所合成化合物进行抗肿瘤活性初步筛选。结果显示：所合成化合物对A549、MCF-7、HepG2肿瘤细胞具有一定的抑制作用,且除化合物8k外,其余化合物对A549肿瘤细胞的抑制活性均比阳性对照5-氟尿嘧啶强。     

手性四氢咪唑衍生物的合成及与醛的反应

用含有C2对称轴的手性1，2－二胺同n-Bu3Sn取代的醛类化合物反应，制得了 具有手性辅助基的烯醇化物等价体。再利用金属交换反应将生成的烯醇负离子同醛 类化合物进行缩合反应，制得具有立体选择性的羟基化合物。     

苯并异喹啉酮衍生物的合成及其荧光性质

苯并异喹啉酮衍生物的合成及其荧光性质;苯并咪唑苯并异喹啉酮;萘酰亚胺;荧光量子产率;亲核取代反应;合成     

四氢喹啉-4-醇类衍生物的合成

以1,2,3,4-四氢喹啉为初始原料,经N-酰基保护、氧化、脱保护、还原等反应合成了一系列1,2,3,4-四氢喹啉-4-醇类的衍生物,总产率17%~41%,其结构经1H NMR和13C NMR确证。     

Flexible Synthesis of Enantiomeric and Racemic 3-Hydroxymethyl-1,2,3,4-tetrahydroisoquinolines via Bischler-Napieralski Reaction

With methyl ester of N-acylated L-3-(3,4-dihydroxyphenyl)alanine(L-DOPA) as starting material, racemic derivatives of 3-hydroxymethyl-1,2,3,4-tetrahydroisoquinoline were obtained with cyclization by Bischler-Napie- ralski(BN) reaction followed by reduction of methyl ester group to hydroxymethyl, while the optical pure enantiomers were prepared by the reduction of the methyl ester group to hydroxymethyl prior to cyclization with BN reaction. Racemerization took place in the BN stage in the presence of methyl ester, an electron-withdrawing group adjacent to chiral center. Therefore, the sequence of synthetic stages of cyclization and reduction, and subsequently whether there is electron-withdrawing group or not determines the chiral optical activity of the products.     

Spectrophotometric Determination of Narcotine

Abstract

Narcotine reacts with potassium iodate and antimony potassium tartarate to give a yellowish orange colour having maximum absorbance at 430–440 nm. The reaction is specific for narcotine, having 1 ug/10 ml as visual limit of identification and provides a basis for a new spectropho-tometric determination of pure narcotine and in the presence of other drugs. The maximum tolerable limits of these are reported.     

Solid-phase synthesis of isoquinolinones using Bischler-Napieralski cyclization

Isoquinolinone is a structural unit found in many natural products having various important biological activities. A traceless solid-phase synthetic approach has been developed to prepare isoquinolinone derivatives. This approach enables one to synthesize isoquinolinones having various moieties on benzene nuclei and also can produce derivatives with a proton on the amide nitrogen.     

Synthesis of 8-substituted-6-phenyl-6,7,8,9-tetrahydro-3H-pyrazolo[4,3-f]isoquinolines using Pictet-Spengler and Bischler-Napieralski cyclisation methods

In the following communication we report routes for the synthesis of a set of 8-substituted-6-phenyl-6,7,8,9-tetrahydro-3H-pyrazolo[4,3-f]isoquinolines. Pictet-Spengler and Bischler-Napieralski methodologies were employed on the relevant indazole precursors and the merits of the two cyclisation reactions for preparing these structures were assessed.     

置换反应制备双金属纳米催化剂

双金属纳米颗粒具有比单金属纳米颗粒更加优异的催化、光学及电学等性能,常见的双金属纳米颗粒制备方法有共还原法、连续还原法、电沉积法、微乳液法及置换反应法等.其中,置换反应是一种重要的双金属纳米颗粒制备方法,具有反应条件温和、无需其他还原剂、所制备的纳米颗粒粒径分布均匀、结构可调可控等特点.采用该方法制备的合金结构、核壳结构以及空心结构的双金属纳米颗粒均表现出优异的催化性能,本文综述了近年来置换反应制备不同结构双金属纳米颗粒的研究现状,并且提出了置换反应制备双金属纳米颗粒研究中存在的问题和今后可能的发展方向.     

Bischler-Napieralski Reaction of 2-(3,4-Dimethoxy-2-nitrophenyl)-N-[2-(3,4-dimethoxyphenyl)ethyl]-N-[(S)-1-phenylethyl] acetamide Accompanied by Elimination of Chiral Auxiliary

Chiral 1-benzyltetrahydroisoquinoline alkaloids can be asymmetrically synthesized via Bischler-Napieralski (B-N) cyclization followed by stereoselective NaBH4 reduction (Polniaszek抯 method) of the N- (2-phenylethyl)-2-phenylacetamides bearing chiral auxiliary such as (S)-1-phenylethyl group on the nitrogen atom1-4. Recently Y. Ohishi and co-workers found an unusual B-N reaction on the carbon at 2-position of the A ring, which bears a bromine atom5, 6. They indicated that the steric ef…     

The Influence of Exocyclic Stereochemistry on the Tethered Aminohydroxylation Reaction

A new strategy that employs an exocyclic stereocenter to effect diastereocontrol in the tethered aminohydroxylation (TA) reaction is applied to the stereoselective synthesis of a range of amino alcohols in good to excellent yields, and with anti selectivities of up to 20:1. The influence of the reaction conditions and substrate parameters on the level of diastereocontrol is described. Furthermore, an “inside alkoxy” model is employed to rationalize the sense and degree of stereoselectivity observed in these systems.     

Synthesis and characterization of <Emphasis Type=Italic>S,N</Emphasis>-heteroacenes by Bischler-Napieralski reaction

Bischler-Napieralski cyclization has been successfully employed to prepare planar S,N-heteroacenes (SNHs) with the analogue structures to 1,10-phenanthroline. The opto-/electrical properties and the packing modes of these S,Nheteroacenes were examined, which were dependent on the structure of the fused groups. SNH-based copolymers with high molecular weight and good solubility in common organic solvents or water have been synthesized by Suzuki-Miyaura- Schlüter polycondensation. The photophysical property studies revealed that the copolymers may be a promising chemosensor material.     

Bischler-Napieralski cyclocondensation in the synthesis of new 11H-pyrimido[4,5-b][1,4]benzodiazepines

A synthetic strategy based on nitrosation-aminolysis-nitroso reduction and Bischler-Napieralski cyclocondensation has been developed for the synthesis of a family of 2-amino-4-methoxy-11H-pyrimido[4,5-b][1,4]benzodiazepines.