双水相体系中Proline/CuI催化Heck反应的研究

以双水相为反应溶剂,丙烯酸酯、苯乙烯与多种芳卤化合物在催化剂碘化亚铜、配体L-脯氨酸的存在下,在较低的温度(75～85 ℃)下得到了产物,该方法具有反应时间短、产率较高、选择性较好等特点,为该反应及该类化合物的合成提供了一种新方法。产物通过熔点、红外、核磁共振氢谱、碳谱等方法的表征。     

Application of Cyclopentadiene and its Derivatives in Natural Product Synthesis

Approaches toward the synthesis of iridoids and 9-isocyanopupukeanane starting from cy-clopentadiene are discussed.     

A study of Heck cyclization reactions to form phenanthridine ring systems

A survey of conditions for the palladium catalyzed intramolecular Heck cyclization of protected amines has shown that the Herrmann-Beller palladacycle can be exploited under ‘cationic’ conditions to provide a robust and rapid route (<2 h) to the synthesis of single double bond isomer phenanthridines in excellent yield (76-99%). In addition, the same cyclization can be performed under ‘neutral’ conditions to provide phenanthridines with a double bond isomer profile suitable for exploitation in diversity-based applications. We have also shown that the highly reactive (^tBu₃P)₂Pd catalyst can induce cyclization at low temperatures (≤50 °C), giving similar results to the ‘neutral’ conditions, and offering an alternative pathway for sensitive substrates.     

Heck反应合成1,2-二芳基乙烯类衍生物的新方法

以1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷（DVS）为烯源与溴代芳烃通过Heck反应一步法合成了1,2-二苯乙烯（V-bisPh）及1,2-二苯并环丁烯基乙烯（V-bisBCB）。 优化了反应条件：DMF/H2O为溶剂,温度120 ℃,溴化物（R-Br）与烯源DVS的投料摩尔比为5∶1,反应48 h,1,2-二苯并环丁烯基乙烯产率为45.1%,1,2-二苯乙烯产率为48.6%。     

三级烯酰胺的串联Heck反应——一种反式2,5-二芳基-3-吡咯啉化合物新颖的合成方法

3-吡咯啉化合物不仅是重要的有机合成中间体, 而且其骨架结构广泛存在于具有生物活性的化合物中. 利用五元环三级烯酰胺的串联Heck反应, 实现了反式2,5-双取代-3-吡咯啉化合物简便、快捷的合成. 该方法首次将环状烯酰胺的α-芳基化反应和双键异构化进行了有效的结合, 为2,5-双取代-3-吡咯啉化合物的合成提供了一种全新的合成方法. 得到的3-吡咯啉产物可分别经氧化反应和还原反应方便地转化成吡咯或吡咯烷化合物.     

Reactions of vinyltributylgermanes and aryl halides under Heck conditions

We describe the palladium-mediated reaction of vinyltributylgermanes with aryl halides under Heck conditions. Depending on their degree of substitution, (E)-vinyltributylgermanes preferentially afford either the cine or Z-alkenyl coupled products in moderate yields. Substituents at the allylic position, especially oxygen, impact regio- and stereoselectivity.     

Schmidt反应及其在全合成中的应用

主要介绍了Schmidt反应的机理,影响Schmidt重排的因素,以及Schmidt反应在天然产物和具有生物活性的复杂含氮化合物合成中的应用。     

Palladium-Catalyzed 8-Exo Trig Intramolecular Heck Reaction Under Microwave Irradiation in the Presence of Basic Alumina

The Heck cross-coupling reaction has been employed for efficient conversion of quinolines to benzoxocinoquinoline through a microwave-assisted palladium-catalyzed intramolecular cyclization in the presence of basic alumina.     

Convenient Synthesis of 2-Aminothiophene Derivatives by Acceleration of Gewald Reaction Under Ultrasonic Aqueous Conditions

Under ultrasound irradiation and in the presence of H₂O/Et₂NH, ethyl cyanoacetate or malononitrile can combine with α-methylene carbonyl compounds and elemental sulfur to efficiently yield 2-aminothiophene derivatives within a few minutes. Products are easily obtained by simple filtration because of their spontaneous precipitation in the reaction mixtures.     

Heck reactions of aryl halides in phosphonium salt ionic liquids: library screening and applications

The Heck cross-coupling of aryl iodides and bromides with olefins proceeds in the phosphonium salt ionic liquid trihexyl(tetradecyl)phosphonium chloride (THP-Cl) in excellent yields. Furthermore, it is shown that the counter anion matched to the phosphonium cation exerts a measurable effect on the overall yield.     

Intramolecular Heck reaction of methylenephthalimidine derivatives: a simple route to lennoxamine and chilenine

A new concise route to the key intermediate for isoindolobenazepine alkaloids, lennoxamine and chilenine, was developed using amine and keto-ester condensation followed by Heck reaction.     

有机膦催化环化及环加成反应在天然产物全合成中的应用研究进展*

有机膦小分子催化是一种反应条件温和、环境友好的有机合成方法,已广泛应用于有机合成领域。其中亲核有机膦催化的环化及环加成反应已经逐渐发展成为构建碳环和杂环化合物以及天然产物的重要工具之一。通过介绍近年来发展的有机膦催化环化及环加成反应的方法学,综述了近年来有机膦催化的环化及环加成反应在天然产物全合成中的应用研究进展。     

Palladium-catalyzed domino Heck/cyanation: synthesis of 3-cyanomethyloxindoles and their conversion to spirooxoindoles

3′-Alkyl-3-cyanomethyloxindoles, prepared by a palladium-catalyzed domino Heck/cyanation, were efficiently converted to spiropyrrolidinyl-, spiropiperidinyl- and spirocyclopropyl-oxindoles. The so-obtained spirooxindoles bearing three diversity points were further functionalized via selective N-acylation, N-alkylation, N-sulfonylation, S_NAr reaction and Buchwald-Hartwig N-arylation reaction to reach diverse set of heterocycles.     

Palladium catalyzed Heck reaction of 2-iodoanilines under ligand-free conditions in air

Palladium catalyzed Heck reaction of 2-iodoanilines and acrylate has been developed. The palladium catalyzed Heck reaction of 2-iodoanilines can readily occur in CH₃CN using Pd(OAc)₂ (5.0?mol%) as catalyst, NEt₃ as base under ligand-free conditions. And 2-alkenylanilines were obtained as the cross-coupling products with medium to high yield.     

Synthesis of Bio-Inspired 1,3-Diarylpropene Derivatives via Heck Cross-Coupling and Cytotoxic Evaluation on Breast Cancer Cells

The Heck cross-coupling reaction is a well-established chemical tool for the synthesis of unsaturated compounds by formation of a new C-C bond. In this study, 1,3-diarylpropene derivatives, designed as structural analogues of stilbenoids and dihydrostilbenoids, were synthesised by the palladium-catalysed reactions of 2-amidoiodobenzene derivatives with either estragole or eugenol. The products were obtained with high (E) stereoselectivity but as two regioisomers. The ratios of isomers were found to be dependent on the nature of the allylbenzene partner and were rationalised by electronic effects exercising a determining influence in the β-hydride elimination step. In addition, the cytotoxic effects of all the Heck reaction products were evaluated against MCF-7 and MDA-MB-231 human breast cancer cells, with unpromising results. Among all, compound 7d exhibited weak cytotoxic activity towards MCF-7 cell lines with IC₅₀ values of 47.92 µM in comparison with tamoxifen and was considered to have general toxicity (SI value < 2).     

A General Synthesis of Alkenyl‐Substituted Benzofurans,Indoles, and Isoquinolones by Cascade Palladium‐Catalyzed Heterocyclization/Oxidative Heck Coupling

Structurally diverse C3‐alkenylbenzofurans, C3‐alkenylindoles, and C4‐alkenylisoquinolones are efficiently prepared by using consecutive Sonogashira and cascade Pd‐catalyzed heterocyclization/oxidative Heck couplings from readily available ortho‐iodosubstituted phenol, aniline, and benzamide substrates, alkynes, and functionalized olefins. The cyclization of O‐ and N‐heteronucleophiles follows regioselective 5‐endo‐dig‐ or 6‐endo‐dig‐cyclization modes, whereas the subsequent Heck‐type coupling with both mono‐ and disubstituted olefins takes place stereoselectively with exclusive formation of the E isomers in most cases.     

Desymmetrisation of bicyclo[4.4.0]decadienes: A planar-chiral complex proved to be most effective in an asymmetric Heck reaction

The synthesis and desymmetrisation of bicyclo[4.4.0]decadienes is described; the enantioselective Heck reaction using JOSIPHOS as a planar-chiral complex produces a tetracyclic system with three stereogenic centers in up to 84% enantiomeric purity.     

复分解反应发生条件中生成物的有关问题

指出教材中复分解反应发生条件叙述中存在的问题,论述了不同问题范围内相应的生成物概念。引入了可能生成物概念并对教材中相关内容的修改提出了建议。     

Intramolecular Heck cyclization to the galanthamine-type alkaloids: total synthesis of (±)-lycoramine

A novel approach towards the construction of the galanthamine skeleton was demonstrated by the total synthesis of (±)-lycoramine. The key steps include a Pd-catalyzed intramolecular cyclization to form the seven-membered azepane ring and a spontaneous intramolecular Michael addition to afford the five-membered furan ring. This synthetic route has also been demonstrated to be useful for the preparation of novel derivatives with simplified galanthamine skeletons.     

Synthesis and characterization of silica-supported Pd nanoparticles and its application in the Heck reaction

Well-dispersed palladium nanoparticles immobilized onto modified silica(SiO 2-pr-NH-cyanuric-SH) have been prepared in some facile steps.The catalyst exhibits high catalytic activity in the Heck reaction,and can be easily recovered and reused without significant loss of its activity in several runs.