Mass Spectrometric Screening of Chiral Catalysts by Monitoring the Back Reaction PDF Download
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Author: Constanze Annelie Müller
Publisher: Cuvillier Verlag
ISBN: 3867276145
Category :
Languages : en
Pages : 287
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Book Description
Author: Constanze Annelie Müller
Publisher: Cuvillier Verlag
ISBN: 3867276145
Category :
Languages : en
Pages : 287
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Book Description
Author: Antje Maria Teichert
Publisher: Cuvillier Verlag
ISBN: 3867274452
Category :
Languages : en
Pages : 225
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Book Description
Author: Anne Zehnacker
Publisher: CRC Press
ISBN: 1420082280
Category : Science
Languages : en
Pages : 250
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Book Description
Understanding the molecular interactions responsible for chiral recognition is of primary importance in life chemistry. Gas-phase experiments on either neutral or ionic adducts of chiral molecules allow for the study of intrinsic properties of chiral recognition in solvent-free conditions. With contributions from a panel of international experts ex
Author: Patrick G. Isenegger
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Author: Christian Ebner
Publisher: Cuvillier Verlag
ISBN: 3736940416
Category : Science
Languages : en
Pages : 262
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This work was dedicated to the development and evaluation of new chiral catalysts for asymmetric C-C and C-H bond forming reactions. In the first part of the thesis an ESI-MS screening method is described, which allows the determination of a chiral catalyst´s selectivity in the palladium catalyzed asymmetric allylic alkylation by testing its racemic form. The value of this new method was demonstrated when different new aryl-PHOX-type ligands, which are not easily accessible in their enantiopure form, were evaluated. In the second part new PHOX-type ligands were tested in the iridium-catalyzed asymmetric hydrogenation of different unsaturated compounds. Although low activities and selectivities were found in most cases, one ligand showed promising results in the hydrogenation of allylic alcohols and imines. Furthermore air- and moisture-stable secondary phosphine oxide (SPO) containing bidentate ligands were tested in the palladium-catalyzed asymmetric allylic alkylation reaction. SPO,N-ligands bearing a PHOX type backbone were inactive in this transformation as they tend to form inactive palladium-bis-ligand complexes. SPO,P ligands however, were able to promote the desired reaction in a highly selective fashion although only low activities were found. During this work as well a new organo-catalyst, based on the structure of 2,3-dihydrobenzo[1,4]oxazine, was developed which allows for the asymmetric organo-catalyzed transfer-hydrogenation of α,β-unsaturated aldehydes. This catalyst was able to reduce for the first time β, β-diaryl acrylaldehydes with very good activities and high enantioselectivities. Moreover an ESI-MS based mechanistic study on the tripeptide catalyzed conjugate addition reaction of aldehydes to nitroolefins was carried out. By this all reaction intermediates postulated for an enamine mechanism have been detected. Furthermore the attack of the enamine onto the nitroolefin was found to be the selectivity determining step in this process. The last part of this work aimed for the asymmetric α -allylation of carbonyl compounds by a tandem-catalysis approach. An intensive screening of both the organo-catalyst and the palladium-ligand led to reaction conditions which allowed for the selective mono-allylation of ketones in high yields. The formation of a quaternary center by α -allylation of α -branched aldehydes was also achieved. However, only low enantiomeric excesses were obtained in this transformation for the different catalyst systems tested.
Author: Montserrat Diéguez
Publisher: John Wiley & Sons
ISBN: 3527804072
Category : Technology & Engineering
Languages : en
Pages : 431
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Book Description
An important reference for researchers in the field of metal-enzyme hybrid catalysis Artificial Metalloenzymes and MetalloDNAzymes in Catalysis offers a comprehensive review of the most current strategies, developed over recent decades, for the design, synthesis, and optimization of these hybrid catalysts as well as material about their application. The contributors—noted experts in the field—present information on the preparation, characterization, and optimization of artificial metalloenzymes in a timely and authoritative manner. The authors present a thorough examination of this interesting new platform for catalysis that combines the excellent selective recognition/binding properties of enzymes with transition metal catalysts. The text includes information on the various applications of metal-enzyme hybrid catalysts for novel reactions, offers insights into the latest advances in the field, and contains an informative perspective on the future: Explores the development of artificial metalloenzymes, the modern and strongly evolving research field on the verge of industrial application Contains a comprehensive reference to the research area of metal-enzyme hybrid catalysis that has experienced tremendous growth in recent years Includes contributions from leading researchers in the field Shows how this new catalysis combines the selective recognition/binding properties of enzymes with transition metal catalysts Written for catalytic chemists, bioinorganic chemists, biochemists, and organic chemists, Artificial Metalloenzymes and MetalloDNAzymes in Catalysis offers a unique reference to the fundamentals, concepts, applications, and the most recent developments for more efficient and sustainable synthesis.
Author: Shengming Ma
Publisher: Springer Science & Business Media
ISBN: 3642194729
Category : Science
Languages : en
Pages : 368
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Book Description
Qi-Lin Zhou and Jian-Hua Xie: Chiral Spiro Catalysts.- Fuk Loi Lam, Fuk Yee Kwong and Albert S. C. Chan: Chiral Phosphorus Ligands with Interesting Properties and Practical Applications.- Jiang Pan, Hui-Lei Yu, Jian-He Xu, Guo-Qiang Lin: Advances in Biocatalysis: Enzymatic Reactions and Their Applications.- Mei-Xiang Wang: Enantioselective Biotransformations of Nitriles.- Man Kin Wong, Yiu Chung Yip and Dan Yang: Asymmetric Epoxidation Catalyzed by Chiral Ketones.- W. J. Liu, N. Li and L. Z. Gong: Asymmetric Organocatalysis.- Qing-Hua Fan and Kuiling Ding: Enantioselective Catalysis with Structurally Tunable Immobilized Catalysts.- Chang-Hua Ding, Xue-Long Hou: Transition Metal-Catalyzed Asymmetric Allylation.- Jian Zhou and Yong Tang: Enantioselective Reactions with Trisoxazolines.- Xiang-Ping Hu, Duo-Sheng Wang, Chang-Bin Yu, Yong-Gui Zhou, and Zhuo Zheng: Adventure in Asymmetric Hydrogenation: Synthesis of Chiral Phosphorus Ligands and Asymmetric Hydrogenation of Heteroaromtics.
Author: Herman Borg
Publisher:
ISBN: 9789038601069
Category : Catalysis
Languages : en
Pages : 156
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Book Description
Author: Michelle Yan Chi Ting
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Book Description
Suzuki-Miyaura cross-coupling is a well-known method for making biaryls. With bifunctional monomers, Suzuki polycondensation (SPC) can be used to make polyaryls. Given the complexity of the reacting solution, studying the mechanism of SPC is extremely tough. To solve this problem, we used tandem mass spectrometric (MS/MS) methods to observe the dynamic behaviour of catalytically relevant species in real time. Catalysis involves a complex soup of reactants, intermediates and products. We used an ESI-MS with a triple quadrupole mass analyzer to monitor the SPC in positive ion mode using pressurized sample infusion (PSI) in real time. Full scan, selected ion recording (SIR), product ion scan, neutral loss scan (NLS) and multiple reaction monitoring (MRM) MS/MS methods were applied. Tetrakistriphenylphosphine palladium(0) was the catalyst of this reaction and a positively charged phosphonium aryl iodide tag (m/z 478) was implemented into the first catalytic cycle, enabling us to track all the intermediate oligomers up to the 4th addition. Product ion scan revealed all the intermediate oligomers lose a triphenylphosphine fragment (m/z 262) which would either come from the complex or the charged tag. Three significant intermediate types were observed in each stage of the catalysis, oxidative addition, transmetallation and reductive elimination and their behavior was studied in a chronogram, normalized to the total ion current. As expected, the use of selected ion recording, and neutral loss scan dramatically improved the signal-to-noise ratio. Ultimately, multiple reaction monitoring showed the best chronogram data due to the fact that this scan acts as a "double filter" in a soup of reactive species and contaminants. Real time reaction monitoring has proven to provide detailed insights regarding a reaction. MS/MS methods are promising for improving data quality, selectivity and sensitivity in reaction monitoring. The principle is broadly applicable to other systems, from an intricate catalytic reaction with short-lived ionic intermediates to a reaction with only a single product generated. Reaction dynamics for an exceptionally complex reaction can be made simple and easy by utilizing tandem mass spectrometry methods in time resolved reaction monitoring.
Author: Isaac Obeng Omari
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Book Description
Reactions can be monitored in real-time or off-line for qualitative and quantitative information on reaction systems under study. The work presented in this dissertation was focused on the application of reaction monitoring techniques by means of electrospray ionization mass spectrometry (ESI-MS), and ultraviolet-visible (UV-Vis) spectroscopy to solve various problems. For example, in a complex petroleum matrix, naphthenic acids were selectively derivatized using a charge-tagging technique and all the acid derivatives were identified by tandem electrospray ionization mass spectrometry (ESI-MS/MS). To understand the increased visibility of analytes profiled with charge-tagged reagents in ESI-MS, ESI response of permanently charged analytes of different sizes and structures were examined. It turned out that factors, such as the analyte structure, molecular weight and solvent could influence the signal strength of analytes. In a separate study on the effect of magnesium (Mg2+) on Maillard reaction, ESI-MS was used to characterize reaction species, and it was found through UV-Vis spectroscopy that, magnesium can accelerate Maillard chemistry in a dose-dependent manner. ESI-MS was also employed to investigate hydrolysis of aryltrifluoroborates in real-time complemented by pH analysis, whereby a dynamic series of equilibria for numerous ions was determined. As well, by using ESI-MS for on-line reaction monitoring, reaction intermediates of a palladium-catalyzed cyclization reaction of carbamates, and an acid-catalyzed cyclization reaction of benzoxazine were identified. Furthermore, to ensure uniform stirring in reactions conducted simultaneously, a 3D printed circular vial holder enabled standardized stirring conditions in ten vials; and ESI-MS revealed data reproducibility could be achieved through the standardized stirring conditions offered by the vial holder. In a nutshell, the findings given provide practical considerations, and some insights into fundamental ESI-MS science.
