Total Synthesis of (±) and (+)-Lyconadin A and Mechanistic Studies of Oxidative C-N Bond Formation PDF Download
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Author: Scott P. West
Publisher:
ISBN:
Category :
Languages : en
Pages : 490
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Book Description
An overview of the Lycopodium alkaloids is presented covering their isolation, structural classification and biosynthesis. The isolation, biological activity and biosynthesis of the miscellaneous group of the Lycopodium alkaloids are discussed in detail. Synthetic studies on the miscellaneous Lycopodium alkaloids are summarized and an overview of a previous total synthesis of (+)-lyconadin A and an approach to lyconadin A is presented. The development of a unified strategy to access several miscellaneous Lycopodium alkaloids has been achieved. Utilizing this approach, the racemic and enantioselective syntheses of lyconadin A were achieved in 17 steps. Key strategic bond formations in the synthesis include olefin cross-metathesis, intramolecular Heck reaction, Curtius rearrangement, and intramolecular reductive amination. The lyconadin pentacycle was assembled by an unprecedented oxidative C-N bond-forming reaction from a dianion intermediate. The enantioselective route utilizes a Corey-Bakshi-Shibata reduction and a diastereoselective hydrogenation to set three key stereocenters. An overview of oxidative bond-forming reactions from dianion intermediates is presented. The mechanism of the oxidative C-N bond formation was examined. NMR studies and DFT calculations were conducted to investigate the structure of the dianion intermediate. Several oxidants were found to promote C-N bond formation by oxidation of the dianion intermediate. The reactivity studies revealed that the C-N bond formation may proceed by polar or SET mechanisms and that the mechanistic pathway is dependent on the type of oxidant utilized.
Author: Scott P. West
Publisher:
ISBN:
Category :
Languages : en
Pages : 490
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Book Description
An overview of the Lycopodium alkaloids is presented covering their isolation, structural classification and biosynthesis. The isolation, biological activity and biosynthesis of the miscellaneous group of the Lycopodium alkaloids are discussed in detail. Synthetic studies on the miscellaneous Lycopodium alkaloids are summarized and an overview of a previous total synthesis of (+)-lyconadin A and an approach to lyconadin A is presented. The development of a unified strategy to access several miscellaneous Lycopodium alkaloids has been achieved. Utilizing this approach, the racemic and enantioselective syntheses of lyconadin A were achieved in 17 steps. Key strategic bond formations in the synthesis include olefin cross-metathesis, intramolecular Heck reaction, Curtius rearrangement, and intramolecular reductive amination. The lyconadin pentacycle was assembled by an unprecedented oxidative C-N bond-forming reaction from a dianion intermediate. The enantioselective route utilizes a Corey-Bakshi-Shibata reduction and a diastereoselective hydrogenation to set three key stereocenters. An overview of oxidative bond-forming reactions from dianion intermediates is presented. The mechanism of the oxidative C-N bond formation was examined. NMR studies and DFT calculations were conducted to investigate the structure of the dianion intermediate. Several oxidants were found to promote C-N bond formation by oxidation of the dianion intermediate. The reactivity studies revealed that the C-N bond formation may proceed by polar or SET mechanisms and that the mechanistic pathway is dependent on the type of oxidant utilized.
Author: Pher G. Andersson
Publisher: John Wiley & Sons
ISBN: 3527646604
Category : Science
Languages : en
Pages : 375
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Book Description
C-H, C-O, C-C, and C-Heteroatom bond forming processes by using metal-ligand approaches for the synthesis of organic compounds of biological, pharmacological and organic nanotechnological utility are the key areas addressed in this book. Authored by a European team of leaders in the field, it brings together innovative approaches for a variety of catalysis reactions and processes frequently applied in organic synthesis into a handy reference work. It covers all major types of catalysis, including homogeneous, heterogeneous, and organocatalysis, as well as mechanistic and computational studies. Special attention is paid to the improvements in efficiency and sustainability of important catalytic processes, such as selective oxidations, hydrogenation, and cross-coupling reactions, and to their utilization in industry. The result is a valuable resource for advanced researchers in both academia and industry, as well as graduate students in organic chemistry aiming for chemo-, regio- or stereoselective synthesis of organic compounds by using novel catalytic systems.
Author: Arkadi Vigalok
Publisher: Springer
ISBN: 3642120733
Category : Science
Languages : en
Pages : 198
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Book Description
Contents: Kilian Muñiz: Transition Metal Catalyzed Electrophilic Halogenation of C-H bonds in alpha-Position to Carbonyl Groups; Arkadi Vigalok * and Ariela W Kaspi: Late Transition Metal-Mediated Formation of Carbon-Halogen Bonds; Paul Bichler and Jennifer A. Love*: Organometallic Approaches to Carbon-Sulfur Bond Formation; David S. Glueck: Recent Advances in Metal-Catalyzed C-P Bond Formation; Andrei N. Vedernikov: C-O Reductive Elimination from High Valent Pt and Pd Centers; Lukas Hintermann: Recent Developments in Metal-Catalyzed Additions of Oxygen Nucleophiles to Alkenes and Alkynes; Moris S. Eisen: Catalytic C-N, C-O and C-S bond formation promoted by organoactinide complexes.
Author: Jihui Li
Publisher:
ISBN:
Category :
Languages : en
Pages : 0
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Book Description
This thesis consists in three parts: bibliographic background, copper-catalyzed reactions for synthesis of N-containing compounds, approach to the synthesis of raputindoles.The first part introduces the domino reactions and their applications, then, copper-mediated reactions for construction of C-N bond formation are reviewed including Ullmann, Goldberg and Chan-Lam coupling, oxidative C-H activation/C-N formation, insertion of nitrenes and carbenoids, and hydroamination of multi-C-C bonds. This can be used as guides to design domino reaction. Following these copper-mediated single C-N bond formation reactions, recent developments of copper-catalyzed domino reactions for synthesis of heterocycles are described.The second part can be divided into three sections: 1) synthesis of benzimidazoles, 2) synthesis of imidazoles and 3) synthesis of guanidines. Each section summarizes the existing methods used for their synthesis. Following it, our synthetic work involving copper-catalyzed C-N bond formation domino reactions is discussed in detail. Our objectives include the synthesis of benzimidazoles through copper-catalyzed sequential reaction of benzamidines and boronic acids, synthesis of imidazoles via copper-catalyzed domino reaction of benzamidines and acetylenes, and synthesis of guanidines and 2-aminobenzimidazoles by Cu-catalyzed three-component reaction of cyanamides, boronic acids and amines. These copper-catalyzed domino reactions show high efficiencies from readily available and simple starting materials.The last part is about the total synthesis of raputindoles. The structure and bioactivities of raputindoles and key reactions for the total synthesis of raputindoles are introduced first, the synthetic strategies are then proposed on basis of relative synthetic methods. The key reactions we use for the synthesis of raputindoles are iridium catalyzed [3+2] annulation of o-formylarylboronic acids and 1,3-dienes, Leimgruber-Batcho indole synthesis, transition-metal catalyzed SN2 substitution and alkylborylation-protondeborylation. According to the three strategies we proposed, lots of relative reactions were investigated. The results show that it is possible to synthesize the raputindole molecules based on the iridium catalyzed [3+2] annulation of 2-formylarylboronic acids and 1,3-dienes.
Author: Alexandra Eve Strom
Publisher:
ISBN:
Category :
Languages : en
Pages : 323
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Book Description
The following dissertation discusses reactions for the formation of carbon-nitrogen bonds mediated by organotransition metal reagents and catalysts. Chapter 1 presents a synthetic method for the formal hydroamination of unactivated alkenes to form anti-Markovnikov primary and secondary amine products. This transformation is accomplished through the hydrozirconation and subsequent amination of alkenes. The method is then applied to the reaction of complex molecules to emphasize the functional group tolerance of these reactions. Chapter 2 of this thesis comprises the synthesis and evaluation of a series of rhodium-phosphine hydroamination catalysts. These complexes are evaluated in a series of catalytic intramolecular Markovnikov hydroamination reactions. The mechanism of hydroamination catalyzed by the rhodium(I) complexes in this study was examined computationally, and the turnover-limiting step was elucidated. The difference in reactivity of electron-rich and electron-poor catalysts was compared to the computational results of a computational ligand screen, and it was found that the computational analysis of reaction intermediates overestimated the reactivity of electron-poor catalysts. The analysis of the catalysts in this study was expanded to include the binding preference of each ligand, compared to the unsubstituted ligand, which corrects for the disparity between observed reactivity and the calculated overall reaction barrier for electron-poor ligands. The ligand-binding preferences for new ligand structures were calculated, and it was found that ligands that were predicted to bind strongly to rhodium had improved reactivity in catalytic reactions. Chapter 3 discusses the mechanistic study of the palladium-catalyzed aminocarbonylation of aryl halides with ammonia and CO to form primary benzamides. Conditions for reactions of aryl bromides, chlorides, and iodides are described, and the mechanism of reactions of aryl bromides was studied. The kinetic order in the concentration of aryl bromide was found to be first order, and the order in the pressure of CO was found to be inverse first order. These studies were complemented by DFT calculations on the mechanism of oxidative addition of aryl bromides. The products of oxidative addition, aroyl bromide palladium intermediates, were reacted with ammonia in the presence of additives to gain insight into the mechanism of release of product. The overall dependence on the rate of the catalytic reaction was found to be insensitive to excess ammonia, indicating that the overall turnover-limiting step of the reaction is during the oxidative addition step.
Author: Michael Harmata
Publisher: Academic Press
ISBN: 0123865395
Category : Science
Languages : en
Pages : 423
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Book Description
A classic in the area of organic synthesis, Strategies and Tactics in Organic Synthesis provides a forum for investigators to discuss their approach to the science and art of organic synthesis. Rather than a simple presentation of data or a second-hand analysis, this book vividly demonstrates through first hand accounts how synthesis is really done and how by discovering new reactions, creating new designs and building molecules with atom and step economies, the advancement of the science of organic synthesis is providing solutions through function to create a better world. - Presents state-of-the-art developments in organic synthesis - Provides insight and offers new perspective to problem-solving - Written by leading experts in the field
Author: Salima Filali
Publisher:
ISBN:
Category :
Languages : en
Pages : 113
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Book Description
Author: Jie Jack Li
Publisher: Springer Science & Business Media
ISBN: 3642340652
Category : Science
Languages : en
Pages : 292
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Book Description
'Total Synthesis of Natural Products' is written and edited by some of today's leaders in organic chemistry. Eleven chapters cover a range of natural products, from steroids to alkaloids. Each chapter contains an introduction to the natural product in question, descriptions of its biological and pharmacological properties and outlines of total synthesis procedures already carried out. Particular emphasis is placed on novel methodologies developed by the respective authors and their research groups. This text is ideal for graduate and advanced undergraduate students, as well as organic chemists in academia and industry.
Author: Alfred Hassner
Publisher: Elsevier
ISBN: 1483287343
Category : Science
Languages : en
Pages : 462
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Book Description
Synthetically useful organic reactions or reagents are often referred to by the name of the discoverer(s) or developer(s). Older name reactions are described in text books, but more recently developed synthetically useful reactions that may have been associated occasionally with a name are not always well known. For neither of the above are experimental procedures or references easy to find. In this monograph approximately 500 name reactions are included, of which over 200 represent newer name reactions and modern reagents. Each of these reactions are extremely useful for the contemporary organic chemistry researcher in industry or academic institutions. This book provides the information in an easily accessible form. In addition to seminal references and reviews, one or more examples for each name reaction are provided and a complete typical experimental procedure is included, to enable the student or researcher to immediately evaluate reaction conditions. Besides an alphabetical listing of reactions and reagents, cross references permit the organic practitioner to find those name reactions or reagents that enable specific transformations, such as, conversion of amines to nitriles, stereoselective reduction, fluoroalkylation, phenol alkynylation, asymmetric syntheses, allylic alkylation, nucleoside synthesis, cyclopentanation, hydrozirconation, to name a few. Emphasis has been placed on stereoselective and regioselective transformations as well as on enantioselective processes. The listing of reactions and reagents is supported by four indexes.
Author: Hans-Joachim Knoelker
Publisher: Springer Science & Business Media
ISBN: 3642255280
Category : Science
Languages : en
Pages : 268
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Book Description
Lycopodium Alkaloids: Isolation and Asymmetric Synthesis, by Mariko Kitajima and Hiromitsu Takayama.- Synthesis of Morphine Alkaloids and Derivatives, by Uwe Rinner and Tomas Hudlicky.- Indole Prenylation in Alkaloid Synthesis, by Thomas Lindel, Nils Marsch and Santosh Kumar Adla.- Marine Pyrroloiminoquinone Alkaloids, by Yasuyuki Kita and Hiromichi Fujioka.- Synthetic Studies on Amaryllidaceae and Other Terrestrially Derived Alkaloids, by Martin G. Banwell, Nadia Yuqian Gao, Brett D. Schwartz and Lorenzo V. White.- Synthesis of Pyrrole and Carbazole Alkaloids, by Ingmar Bauer and Hans-Joachim Knölker.-
