Spelling suggestions: "subject:"neck reaction"" "subject:"beck reaction""
1 |
Studies towards the total synthesis of galanthamine and the total synthesis of 2-Benzoyl-9-azabicyclo[4.2.1]non-2-ene : phenyl analogue of (#+-#)Anatoxin-aSumoreeah, Ravi Leckman January 2002 (has links)
This thesisd escribess yntheticw ork carriedo ut on two separatep rojects. (i) Synthetics tudiest owardst he total synthesiso f galanthamine (ii) The total synthesis of 2-Benzoyl-9-azabicyclo[4.2.1 ]non-2-ene Galanthamine is an amaryllidaceae alkaloid processing a rigid tetracyclic structure with a fused dihydrobenzofuran onto a cyclohexenol and a bridging tertiary amine. 2-Benzoyl-9-azabicyclo[4.2.1]non-2-ene is an analogue of anatoxin-a, whereby the acetyl side chain has been substituted with a benzoyl group. Anatoxin-a itself possesses a 9-azabicyclo[4.2.1]nonane framework. Although structurally very different they both share a common feature in that they interact with acetylcholine receptors. Hence chapter 1 is an introduction to Alzheimer's disease which is primarily caused by a lack of acetylcholine. A literature review of the total syntheses of galanthamine and a background of galanthamine is described in chapter 2, whilst chapter 3 details the forward synthesis to the galanthamine framework but with a cyclopentenyl instead of a cyclohexenyl moiety and subsequent attempts for the elaboration of the cyclopentenyl into its corresponding cyclohexenyl moiety. Chapter 4 and 5 describes the published total syntheses of anatoxin-a and analogues of anatoxin-a, whilst chapter 6 concludes the total synthesis of the phenyl analogue of anatoxin-a via a key selenium mediated transannular cyclisation of a Boc-(3-Lactam to furnish the 9-azabicyclo[4.2. l]nonane ring system.
|
2 |
Ruthenium and palladium catalysed cyclisation reactionsGleasure, A. J. January 2002 (has links)
No description available.
|
3 |
Synthesis of Mesoporous Palladium Nanoparticles and Its Application in Heck ReactionLi, Jheng-Guang 20 January 2009 (has links)
In our study, 3D interconnection channels of mesoporous silica MCM-48 was used as template. We try to fill the channels with the metal precussor by ¡§incipient wetness¡¨ technique. After the reduction with H2, the composites containning metal Pd and MCM-48 could be obtained. Then, Pd nanowire network was obtained through HF etching.
The mesoporous palladium nanoparticles are obtained and we try to use it as the catalyst in the Heck coupling reaction of £\-methylstyrene and p-bromoacetophenone. We find that our catalyst have different effect in this Heck reaction. The terminal and internal (E/Z form) isomer ratio variated in the reaction. In the future, we will attempt to apply our mesoporous Palladium nanoparticles as organic molecule storage.
The MCM-48 and mesoporous Palladium nanoparticles were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution nitrogen adsorption.We used NMR and GC to trace the reaction. Heck reaction was performed as a test reaction to compare catalytic performances of the meosoporous Palladium nanoparticles and the catalyst of refrence.
|
4 |
Cobalt-mediated radical and cationic cyclisation reactionsRoan, Graeme A. January 1996 (has links)
No description available.
|
5 |
Synthesis of unnatural [alpha] - amino acidsMiddleton, Richard John January 1996 (has links)
No description available.
|
6 |
Screening of substituted pyrazolone and pyrazole as ligands with palladium precursors in the Heck reactionBout, Wanda 03 1900 (has links)
M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology): Vaal University of Technology / The arylation and alkenylation of alkenes under the influence of a palladium catalyst, commonly referred to as the Heck reaction, has been extensively exploited by synthetic chemists since its debut in the late 1960’s. A traditional Heck coupling is based on an aryl iodide or bromide as the electrophilic partner and a terminal alkene as the nucleophilic partner. Academic and industrial interest in this reaction has increased in recent years, fueled by the development of more active catalyst systems, the discovery of waste-free versions, and the desire to put the vast empirical data on a sound mechanistic basis. In this study, we wish to report the use of commercially available substituted pyrazolones (1-(4-Sulfophenyl)-3-methyl-5-pyrazolone (L1), 1-(2,5-Dicloro-4-sulfophenyl)-3-methyl-5-pyrazolone (L2) and 5-oxo-1-phenyl-2-pyrazolin-3-carboxylic acid (L3)) and pyrazoles (α-[(2-Ethoxy-2-oxoethoxy)imino]-3-pyrazole acetic acid (L4) and 3.5 dimethyl pyrazole (L5)) as auxiliary ligands in the Heck coupling reaction. These ligands were used either with PdCl2 or Pd(OAc)2 to catalyze the Heck reaction of iodobenzene with ethyl acrylate or butyl acrylate. GC-MS was used to monitor the reaction, percentage (%) conversions were determined based on the consumption of iodobenzene.
Different reaction parameters such as ligands, temperature, base, solvent and influence of time were investigated. It was observed that the lower conversion was obtained for ethyl acrylate and conversions above 80% were obtained for butyl acrylate. Ligand effect proved to be very crucial during the Heck coupling reactions of iodobenzene with butyl acrylate and ethyl acrylate. For instance in the absence of ligands with PdCl2, the conversions were 29 % and 44 % for butyl acrylate and ethyl acrylate, respectively. When Pd(OAc)2 was used in the absence of ligands the conversions were 25 % and 36 % for butyl acrylate and ethyl acrylate, respectively. In the study for the effect of temperature, 80 ◦C was observed as the best temperature since promising conversions were obtained with little or no sign of deactivation of the catalysts. On the other hand, increasing the temperature to 120 ◦C and above high percent conversions are observed; however deactivation of the catalysts occurs as observed from the precipitation of palladium black at the bottom of the vial. From the results obtained it is clear that pyrazolone and pyrazole ligands/palladium systems are important at very low catalyst loadings and mild temperatures. Based on the employed reaction conditions the influence of base suggested that the organic base triethylamine was the reagent of choice since better conversions were obtained compared to inorganic bases. The inhomogeneity of the inorganic base proved to be a disadvantage in the reaction of iodobenzene with butyl acrylate at employed reaction conditions. It was also found that parameters such as solvents and time effects were important in the Heck reaction. Polar aprotic solvents proved to be solvents of choice rather than non-polar solvents, from the investigated solvents DMF gave better conversions under the used reaction conditions giving average conversions of 78 % and 75 % for all the ligands in the presence of PdCl2 and Pd(OAc)2, respectively. During the investigation of time effect, it was noteworthy to observe that L4 had a slow initiation rate, for instance after 0.5 h conversions of 2 % and 10 % were obtained for catalytic systems, PdCl2 and Pd(OAc)2 respectively. Also it was observed that under the investigated parameters there was no need to run the reaction for 24 h because after 4 h not much of a difference in conversions was observed. In comparing the influence of these two different auxiliary ligands, pyrazolone based ligands were more efficient than pyrazole based ligands under the investigated parameters. The fully detailed information supporting this has been discussed in Chapter 4.
|
7 |
Benzyne in synthesis : a search for palladium catalysed three-component couplingsHenderson, Jaclyn January 2008 (has links)
It is over 100 years since scientists first postulated the existence of arynes as reactive intermediates. Their use in organic synthesis is now well-established and investigations into novel methods for their generation and utility in carbon-carbon bond forming reactions continue to this day. In 1983 Kobayashi and co-workers introduced a novel method of generating benzyne under mild conditions, using a fluoride induced decomposition of 2-(trimethylsilyl)phenyl triflate 1. This development has opened the door to employing arynes in a variety of transitionmetal mediated carbon-carbon bond forming processes. Intermolecular carbopalladation, in particular, stands out as a powerful methodology for the construction of diverse 1,2-functionalised arenes through multi-component coupling processes. Initial benzyne carbopalladation with an organopalladium species produces the arylpalladium intermediate 3, which can then undergo a second coupling to any one of the vast numbers of nucleophiles that have been demonstrated to work in palladium cross coupling. Presented herein are investigations towards the realisation of such methodology. Initial efforts focussed on its application to the Heck reaction, using acryates as the nucleophilic component. The chemistry has been developed to incorporate a variety of organo-halides in order to generate a variety of molecular architectures; the resultant 1,2-substituted diaryls being useful in the synthesis of both natural products and medicinal chemistry targets. Following successful development of the Heck reaction, investigations of other palladium catalysed couplings were also undertaken, in particular the Buchwald reaction. Initial mechanistic studies are also discussed.
|
8 |
Elaboration of azine and azole anhydrobases via intra- and intermolecular cyclizations for heterocycle constructionJoshi, Madhur Satish 01 August 2017 (has links)
Aza-heterocycles such as pyridines, imidazoles, piperidines, etc. are ubiquitous structural motifs found in various natural products and pharmacologically active compounds. Thus, they are of unparalleled importance to synthetic, medicinal, and materials chemists. Despite their structural significance, organic transformations available for the functionalization of these heterocycles remain underdeveloped. The development of several synthetic methods to construct aza-heterocyclic building blocks is described in this thesis, which, in turn, should facilitate the assembly of more elaborate frameworks present in bioactive molecules.
An intramolecular palladium catalyzed Mizoroki-Heck cyclization of 4-alkylidene dihydropyridines with tethered aryl iodide electrophiles is demonstrated. This provides access to substituted isoindolinones and oxindoles in high yields. An asymmetric variant of this reaction using chiral phosphine ligands delivers enantioenriched oxindoles and isoindolinones. Additionally, an intramolecular Mizoroki-Heck reaction for the synthesis of 2-substituted pyridine derivatives is also developed. An array of fused isoindolinones is constructed as a mixture of diastereomers and further manipulated using chemical transformations to yield the corresponding pyridine and piperdine derivatives.
Moreover, a formal [3+2] cyclocondensation of alkylidene dihydropyridines and aryl diazonium salts has been discovered for the synthesis of triazole derivatives. Tertiary amides deliver substituted 1,2,4-triazolium salts, whereas, secondary amides provide substituted, neutral 1,2,4-triazoles in excellent yields, under mild reaction conditions.
Furthermore, an intramolecular direct arylation of 2- and 4-substituted alkylpyridines is developed for the synthesis of 2,3- and 3,4-cyclized pyridines. It is shown that 4-alkylpyridines tethered to aryl halides participate in a palladium catalyzed direct arylation to give fused 7-membered lactams in excellent yields.
Lastly, an intramolecular cyclization of 1,2-alkylimidazoles is reported. Alkylidene imidazolines tethered to electrophilic keto-amide sidechains participate in an aldol-like reaction to yield γ-lactam products in good yields as mixtures of diastereomers.
|
9 |
Fast Microwave-Enhanced Intra-, Pseudo-intra- and Intermolecular Heck ReactionsSvennebring, Andreas January 2006 (has links)
<p>The Heck reaction is one of the most appreciated methods for carbon-carbon bond formation. Due to its mildness and ability to be tuned by additives, it often leaves few alternative competitive reactions. It has also proven easy to develop the reaction conditions in an environmentally benign direction. Through the introduction of palladium chelating groups in olefinic precursors for the Heck reaction, it has been possible to direct the substitution in the following Heck arylation in favor of the terminal position with good regioselectivity. In this thesis, the concept has been utilized to produce a small array of drug-like compounds at useful yields under fast microwave-enhanced conditions utilizing the thermostable Herrmanns palladacycle. During the last decade, this, together with other palladacycles has become commonly employed as precatalyst for the Heck reaction. However, there have been conflicting opinions regarding the mechanisms governing its catalytic effect. A Pd<sup>II</sup>-Pd<sup>IV</sup> catalytic cycle has been suggested to be operative, in contrast to the classical Pd<sup>0</sup>-Pd<sup>II</sup> cycle. In order to clarify the presence of such a mechanism, a set of Heck reactions was performed with the advent of different palladium precatalysts (classical and palladacycles), which revealed that the regiochemicαal substitution pattern is highly conserved, regardless of which precatalyst was employed, and thus, the same mechanism seems to be operative. This is also supported by data from ESI-MS investigations where all the reactions investigated gave rise to the same set of oxidative addition complexes. A crafted route to 3-aryl-1,2-cyclohexandiones has been developed in which 1,2-cyclohexandione is produced <i>is situ</i> from 2,3-epoxycyclohexanone, followed by Heck arylation. A diverse array of aryl bromides encompassing electron-rich, electron-poor, neutral and sterically hindered repressentatives has been successfully utilized to produce the corresponding products at useful yields.The intramolecular Heck reaction offers a route to quaternary carbonic centersand is being increasingly exploited in synthetic endeavors. However, the use of electron-rich olefinic precursors is only reported in a few cases. The implementation of one capto-dative and five electron-rich olefins has therefore been successfully subjected to Heck reaction conditions rendering the corresponding spiro compounds.</p>
|
10 |
Mechanism of the Heck reaction: nature of oxidative addition and migratory insertionEvans, Anthony Steven 15 November 2004 (has links)
The mechanism of carbon coupling reactions is traditionally represented in a very broad schematic. This thesis seeks to explore the mechanism of these reactions by focusing on Heck olefination. The Heck reaction has become a powerful tool in synthetic labs but the mechanism of this reaction has remained a topic of debate since the reaction's discovery. The catalytic cycle that has come to be accepted, while accurate in its own right, is not nearly as detailed as the complexity of the various stages of the Heck reaction suggest it should be. This study seeks to elucidate the nature of the oxidative addition of aryl halide to a palladium catalyst using a ligand that has been shown to have high activity in facilitating oxidative addition of aryl chlorides and bromides in other coupling reactions. This information is then compared to other studies in the field so that conclusions can be drawn about the oxidative addition. Also, selectivity studies seek to determine the nature of the migratory insertion of an olefin into the Pd-Ar bond. Again, comparison of results obtained in this study are compared to previous results so that a more definitive conclusion can be drawn about the oxidative addition.
|
Page generated in 0.071 seconds