氢键活化的硝基烯参与的多组分不对称串联合成研究进展

有机催化多组分不对称串联反应是构建复杂手性化合物的最有效方法之一,双功能手性催化剂是一类重要的单分子双活化有机小分子催化剂,能同时对多个反应底物进行氢键活化,实现多个新键的形成和多个手性中心的立体选择性控制.基于双功能催化剂氢键活化的硝基烯是一类重要的有机反应合成子,能参与多种有机小分子催化的串联反应.对硝基烯参与的多组分不对称串联反应,根据双功能催化剂的结构特征,从双功能硫脲-胺催化、双功能方酰胺-胺催化、其它双功能催化剂催化三个方面进行文献综述.从反应类型、反应机理、反应特点及应用等方面进行了系统地阐述,并对该领域的研究应用和发展前景进行了展望.     

烯胺酮（酯）参与的串联反应构建吡咯衍生物的研究进展

作为多位点的有机合成子,烯胺酮（酯）参与的串联反应广泛应用于吡咯衍生物的合成。综述了烯胺酮（酯）与邻二羰基化合物,β 硝基烯烃和苯乙炔等参与的串联反应在吡咯单环和稠环衍生物合成中的应用进展,并对其未来发展进行了展望。参考文献49篇。     

镍催化的丁二烯、醛、炔和氢氯二茂锆的多组分偶联反应合成1,4-二烯

1,4-二烯结构广泛存在于一系列具有生物活性的化合物分子中,其构建是有机合成中的重要研究领域之一.使用简单易得的原料合成1,4-二烯具有重要的研究意义.发展了镍催化的1,3-丁二烯、醛、炔和氢氯二茂锆的多组分偶联反应,用于高效合成1,4-二烯产物.该反应的原料均简单易得,其中1,3-丁二烯更是大宗化工产品.通过简单的炔...     

Boc或Cbz保护的L-脯氨醇衍生物的稳定性

近年来,L-脯氨醇衍生物催化的不对称Michael加成反应已经成为手性催化研究领域的热点.而在L-脯氨醇衍生物的合成中,常常涉及到L-脯氨醇氨基的保护.为此,研究了Boc和Cbz保护的脯氨醇衍生物的稳定性,发现Boc保护的L-脯氨醇在羟基被取代为易离去基团时,就变得不稳定,在67℃就发生分子内环合生成化合物y-丁内酯;而Cbz保护的L-脯氨醇衍生物的稳定性要好得多,在140℃且有三乙胺存在时,才会发生类似的分子内环合反应.     

手性磷酸催化的C（3）-取代吲哚和甲基乙烯基酮不对称串联反应

3位含有季碳手性中心的吲哚啉并环化合物是一类非常重要的化合物, 广泛存在于各种天然产物和具有生物活性的分子中. 化学家们发展了多种有效的途径来合成这类化合物. 其中以方便易得的吲哚衍生物为起始原料, 利用不对称去芳构化\环化串联的方法最为简单高效, 但多数工作都是从色胺或色醇衍生物出发, 合成二氢吡咯并吲哚啉或二氢呋喃并吲哚啉化合物. 因此, 发展其他类型的吲哚衍生物的不对称去芳构化\环化反应显得非常有必要. 作者课题组发展了手性磷酸催化的吲哚衍生物与甲基乙烯基酮的不对称Michael加成\环化串联反应. 以5 mol% (R)-SPINOL为骨架的手性磷酸(R)-4c为催化剂, 以中等到良好的收率和优秀的对映选择性构建了一系列手性吲哚[2,3-b]并氢化喹啉化合物, 而且该催化体系对于克级规模反应同样能够获得很好的结果.     

β-烯胺酯为关键中间体的串联反应研究进展

串联反应具有原料简单易得、中间产物无需分离提纯、操作简单、节省溶剂和降低消耗等很多独特优点,已成为当前有机合成研究的热点课题.缺电子炔烃与芳香胺在温和条件下快速反应生成的β-烯胺酯,具有丰富的化学反应性质,可以作为多组分串联反应的关键中间体,和其它组分进行串联反应,构建结构复杂的碳链、碳环、杂环化合物和螺环化合物.综述了近年来此类直接生成的β-烯胺酯参与的多组分串联反应的最新研究进展.     

手性芳基邻二醇的不对称合成

具有特定功能基团的手性芳基邻二醇是许多具有特殊功能的药物、农药和信息素的重要中间体,近年来手性芳基邻二醇类化合物的合成与应用研究引起了人们的广泛关注。本文从生物催化不对称合成和化学催化不对称合成两方面综述了近年来手性芳基邻二醇的合成进展,概述了前手性底物上取代基的电子效应和空间效应、手性催化剂的种类和反应体系等因素对合成手性芳基邻二醇产率及光学活性的影响,并对手性芳基邻二醇不对称合成的发展趋势进行了展望。     

橙酮衍生氮杂二烯的化学反应进展

苯并呋喃衍生物具有重要的生理和药理活性,开发高效构建具有该核心骨架化合物的合成方法具有重要的研究价值和广泛的应用前景.受分子本身芳构化驱动力的影响,橙酮衍生氮杂二烯已经成为有机合成领域一类高反应活性的合成子,大量基于1,4-共轭加成和串联环化历程的反应被陆续地报道出来,在合成具有苯并呋喃结构基元的杂环化合物方面展现出极大的应用价值.综述了近年来橙酮衍生氮杂二烯参与的化学反应进展,重点阐述了反应所采用的催化体系,并对部分反应的机理进行了讨论.     

金鸡纳碱衍生物催化的异氰酸酯与硝基烯的不对称形式[3＋2]环化反应

手性2,3-二氢吡咯是合成天然生物碱的重要中间体, 而且可以很容易转化成多取代的吡咯烷, 因此发展高效合成手性二氢吡咯的方法对于有机合成化学具有重要意义. 不对称诱导和金属催化合成光学活性的吡咯烷的方法已有很多, 但还没有不对称催化合成手性2,3-二氢吡咯的报道. 金属化的异氰与不饱和烯烃可以环化生成消旋的二氢吡咯(Saegusa, T.; Ito, Y.; Kinoshita, H.; Tomita, S. J. Org. Chem. 1971, 36, 3316), 中国科学技术大学教授龚流柱小组首次报道了金鸡纳碱衍生物1催化的不对称异氰酸酯和硝基烯的环化反应, 以51%～99%的产率和90%～99% ee (dr值最高大于20∶1)得到相应的2,3-二氢吡咯衍生物.     

手性γ,γ-偕二芳基羰基化合物的催化不对称合成

正手性γ,γ-偕二芳基羰基化合物及其衍生物广泛存在于天然产物和药物分子中,如鬼臼毒素,Cladosporol和抗抑郁药舍曲林等.通常,手性γ,γ-偕二芳基羰基化合物的合成是以手性化合物为起始原料,通过催化不对称方式来构建这一关键骨架一直是一个挑战性的课题.铑催化芳基硼酸对芳基缺电子烯烃的不对称共轭加成是目前合成手性谐二芳基化合物有效途径之一.利用该策略,选用γ-芳基-β,γ-不饱和酮酸酯(或酮酰胺)类为底物,可能是实现手性γ,γ-偕二     

Catalytic asymmetric reactions in alkaloid and terpenoid syntheses

Catalytic asymmetric induction is one of the most important methods in current synthetic organic chemistry for designing efficient and attractive synthetic routes. The efficient total synthesis of a natural product can be achieved through the identification of appropriate method and strategy. This Letter introduces the catalytic asymmetric syntheses of alkaloids and terpenoids based on an overview of four recently reported types of asymmetric reaction: (1) asymmetric decarboxylative allylation, (2) organocatalytic cascade reaction, (3) polyene cyclization, and (4) asymmetric [2+2]-photocycloaddition catalyzed by a chiral Lewis acid.     

萘并呋喃类化合物的合成研究进展

萘并呋喃是一类重要的有机芳杂环,其分子骨架不仅是许多天然产物、药物分子的核心结构,而且还是重要的有机合成中间体,在材料化学中也具有广泛的应用价值。因此,萘并呋喃及其衍生物的合成一直是有机合成的研究热点之一。本文将对已有的萘并呋喃类化合物的主要合成策略、方法,结合笔者课题组的部分研究工作进行综述,包括如下几个方面:(1)碱或酸促进的环化反应;(2)过渡金属催化的串联环化反应;(3)自由基引发的环化反应;(4)其他非金属催化的环化反应。最后展望了萘并呋喃衍生物合成的研究和发展方向。     

Organocatalytic enantioselective multicomponent cascade reaction: facile access to tetrahydropyridines with C3 all-carbon quaternary stereocenters

A novel organocatalytic asymmetric multicomponent cascade reaction for the synthesis of valuable tetrahydropyridines has been developed. The merit of this cascade process is highlighted by its high efficiency of producing five new bonds and an all-carbon quaternary stereocenter in one operation, which otherwise is a big challenge to access by traditional strategies.     

Cascade Multicomponent Synthesis of Indoles,Pyrazoles, and Pyridazinones by Functionalization of Alkenes

The development of multicomponent reactions for indole synthesis is demanding and has hardly been explored. The present study describes the development of a novel multicomponent, cascade approach for indole synthesis. Various substituted indole derivatives were obtained from simple reagents, such as unfunctionalized alkenes, diazonium salts, and sodium triflinate, by using an established straightforward and regioselective method. The method is based on the radical trifluoromethylation of alkenes as an entry into Fischer indole synthesis. Besides indole synthesis, the application of the multicomponent cascade reaction to the synthesis of pyrazoles and pyridazinones is described.     

脯氨酸衍生物催化手性Michael加成的研究进展

Michael加成是有机合成中形成C-C键的重要反应.近年来,对于不对称催化Michael加成反应的研究成为手性催化研究领域的热点之一.不含贵金属的有机小分子催化剂由于其温和、廉价、对环境友好等优点,其应用已成为催化领域的重要发展趋势.本文综述了脯氨酸衍生物催化手性Michael加成反应的研究进展,并对其发展前景作了展望.     

Catalytic Asymmetric Dearomatization Reactions

This Review summarizes the development of catalytic asymmetric dearomatization (CADA) reactions. The CADA reactions discussed herein include oxidative dearomatization reactions, dearomatization by Diels–Alder and related reactions, the alkylative dearomatization of electron‐rich arenes, transition‐metal‐catalyzed dearomatization reactions, cascade sequences involving asymmetric dearomatization as the key step, and nucleophilic dearomatization reactions of pyridinium derivatives. Asymmetric dearomatization reactions with chiral auxiliaries and catalytic asymmetric reactions of dearomatized substrates are also briefly introduced. This Review intends to provide a concept for catalytic asymmetric dearomatization.     

Bioinspired Synthesis of (+)‐Cinchonidine Using Cascade Reactions

The development of efficient syntheses of complex natural products has long been a major challenge in synthetic chemistry. Designing cascade reactions and employing bioinspired transformations are an important and reliable means of achieving this goal. Presented here is a combination of these two strategies, which allow efficient asymmetric synthesis of the cinchona alkaloid (+)‐cinchonidine. The key steps of this synthesis are a controllable, visible‐light‐induced photoredox radical cascade reaction to efficiently access the tetracyclic monoterpenoid indole alkaloid core, as well as a practical biomimetic cascade rearrangement for the indole to quinoline transformation. The use of stereoselective chemical transformations in this work makes it an efficient synthesis of (+)‐cinchonidine.     

Development,Scope and Mechanisms of Multicomponent Reactions of Asymmetric Electron‐Deficient Alkynes with Amines and Formaldehyde

Based on the reactive behaviour of the substrates, two synthetic routes to polysubstituted pyrimidine derivatives are presented herein: 1) A catalyst‐free multicomponent reaction of electron‐deficient alkynes, aliphatic amines and formaldehyde and 2) Ag^I‐catalyzed synthesis of pyrimidines from electron‐deficient alkynes, anilines and formaldehyde by a domino reaction. Under optimized conditions, the multicomponent reactions were accomplished with high regioselectivity and excellent yields. A computational study was carried out by using the B3LYP density functional theory to elucidate the mechanisms of the catalyst‐free hydroamination reaction. Calculations showed the activation free energies of aliphatic amines were lower than those of anilines, which is consistent with the experimental results.     

Asymmetric organocatalytic Biginelli reactions: a new approach to quickly access optically active 3,4-dihydropyrimidin-2-(1H)-ones

The Biginelli reaction, known for over 100 years, is an important multicomponent reaction for accessing dihydropyrimidinones (DHPMs). The individual enantiomers of DHPMs exhibit different or even opposite pharmaceutical activities, which require synthetic methods to easily access the optically pure DHPMs. In recent decades, many efforts have focused on developing procedures for the preparation of optically active Biginelli products. In this article, we will summarize the developments in the synthetic methods to access optically active DHPMs with an emphasis on the recent advances in the asymmetric catalytic Biginelli reactions, along with concepts to design the organocatalytic asymmetric variants.