Alkyl-heteroatom Bond Forming Reactions from the Late Transition Metals PDF Download
Are you looking for read ebook online? Search for your book and save it on your Kindle device, PC, phones or tablets. Download Alkyl-heteroatom Bond Forming Reactions from the Late Transition Metals PDF full book. Access full book title Alkyl-heteroatom Bond Forming Reactions from the Late Transition Metals by Tyler Eugene Stevens. Download full books in PDF and EPUB format.
Author: Tyler Eugene Stevens Publisher: ISBN: Category : Alkenes Languages : en Pages : 183
Book Description
C(sp3)-N bond formation is a potential high value reaction in transition metal catalysis, however, only a handful of examples of this fundamental coupling reaction step have been reported. Presented in this thesis are new efforts to promote this challenging reaction. Group 9 and 10 metals bound by the pincer ligands Pybox and PCP, respectively, were initially investigated. Evidence suggests the Ir-Et complex ([(dmPybox)Ir(Et)(OAc)][PF6] (12)) undergoes a [Beta]-H deprotonation, similar to an E2 type elimination in organic chemistry, rather than the desired SN2 nucleophilic attack. Use of strong nucleophiles, i.e. sulfur nucleophiles, resulted in the ring opening of the pybox ligand. Ir-Et complexes bound by the MeBPA ligand ([(MeBPA)Ir(OOCR)Et][PF6] (20 and 21)), however, did undergo the desired reaction to form C-N bonds upon reaction with neutral nitrogen nucleophiles. A computational investigation of the mechanism revealed that rather than the direct attack at the Ir-Et (generally observed for high valent Pd and Pt) the complex first undergoes [Beta]-hydrogen elimination to form an Ir ethylene complex. Nucleophilic attack by amine at the olefin then forms the C-N bond. In the final chapter the synthesis and characterization of new a new Rh-Me complex ((DPEphos)RhMe(I)2 (25)), which undergoes C(sp3)-I reductive elimination, is described. A kinetic investigation of the mechanism indicated two competing mechanisms involving SN2 attack by iodide at both cationic and neutral Rh-Me species. The demonstration of bond formation via nucleophilic attack at the Rh-Me allowed for the room temperature functionalization of the methyl ligand with both nitrogen and sulfur nucleophiles.
Author: Tyler Eugene Stevens Publisher: ISBN: Category : Alkenes Languages : en Pages : 183
Book Description
C(sp3)-N bond formation is a potential high value reaction in transition metal catalysis, however, only a handful of examples of this fundamental coupling reaction step have been reported. Presented in this thesis are new efforts to promote this challenging reaction. Group 9 and 10 metals bound by the pincer ligands Pybox and PCP, respectively, were initially investigated. Evidence suggests the Ir-Et complex ([(dmPybox)Ir(Et)(OAc)][PF6] (12)) undergoes a [Beta]-H deprotonation, similar to an E2 type elimination in organic chemistry, rather than the desired SN2 nucleophilic attack. Use of strong nucleophiles, i.e. sulfur nucleophiles, resulted in the ring opening of the pybox ligand. Ir-Et complexes bound by the MeBPA ligand ([(MeBPA)Ir(OOCR)Et][PF6] (20 and 21)), however, did undergo the desired reaction to form C-N bonds upon reaction with neutral nitrogen nucleophiles. A computational investigation of the mechanism revealed that rather than the direct attack at the Ir-Et (generally observed for high valent Pd and Pt) the complex first undergoes [Beta]-hydrogen elimination to form an Ir ethylene complex. Nucleophilic attack by amine at the olefin then forms the C-N bond. In the final chapter the synthesis and characterization of new a new Rh-Me complex ((DPEphos)RhMe(I)2 (25)), which undergoes C(sp3)-I reductive elimination, is described. A kinetic investigation of the mechanism indicated two competing mechanisms involving SN2 attack by iodide at both cationic and neutral Rh-Me species. The demonstration of bond formation via nucleophilic attack at the Rh-Me allowed for the room temperature functionalization of the methyl ligand with both nitrogen and sulfur nucleophiles.
Author: Aiwen Lei Publisher: John Wiley & Sons ISBN: 3527336885 Category : Technology & Engineering Languages : en Pages : 243
Book Description
The first handbook on this emerging field provides a comprehensive overview of transition metal-catalyzed coupling reactions in the presence of an oxidant. Following an introduction to the general concept and mechanism of this reaction class, the team of authors presents chapters on C-C cross-coupling reactions using organometallic partners, C-Heteroatom bond forming reactions via oxidative couplings, and C-H couplings via C-H activation. The text also covers such groundbreaking topics as recent achievements in the fields of C-C and C-X bond formation reactions as well as C-H activation involving oxidative couplings. With its novel and concise approach towards important building blocks in organic chemistry and its focus on synthetic applications, this handbook is of great interest to all synthetic chemists in academia and industry alike.
Author: Nai-Wen Tseng Publisher: ISBN: 9780494611197 Category : Languages : en Pages : 0
Book Description
This thesis focuses on the development of carbon-carbon/carbon-heteroatom bond forming reactions using strained ring systems under transition metal catalysis. The first chapter describes the use of bifunctional organoboron reagents with a rhodium catalyst to synthesize carbocycles through a cascade sequence. The reaction of norbornene derivatives gives vinylcyclopropane and cyclopentene products in moderate to good yield. The mechanistic proposal and insights into the reaction mechanism are presented. Preliminary results from studies toward an enantioselective sequential addition/cyclization process are described. The methodology is subsequently applied in the synthesis of a variety of polycyclic heteroaromatics using bifunctional heteroaryl boronate esters. The second chapter describes studies toward the formation of carbon-heteroatom bonds using cyclopropane derivatives. Under a recently developed Pd(OAc) 2/PhI(OAc)2 catalytic system, methylenecyclopropanes are isomerized to substituted pyridines via a sequential fragmentation/cyclization process. Under same reaction conditions, allylic acetate products are obtained from the isomerization of cyclopropanes through a similar process.
Author: Arkadi Vigalok Publisher: Springer ISBN: 3642120733 Category : Science Languages : en Pages : 198
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: Robert H. Crabtree Publisher: John Wiley & Sons ISBN: 0471718750 Category : Science Languages : en Pages : 600
Book Description
Fully updated and expanded to reflect recent advances, this Fourth Edition of the classic text provides students and professional chemists with an excellent introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction mechanisms and detailed descriptions of contemporary applications.
Author: Philip L. Fuchs Publisher: John Wiley & Sons ISBN: 1119279836 Category : Science Languages : en Pages : 640
Book Description
From Boron Trifluoride to Zinc, the 52 most widely used reagents in organic synthesis are described in this unique desktop reference for every organic chemist. The list of reagents contains classics such as N-Bromosuccinimide (NBS) and Trifluoromethanesulfonic Acid side by side with recently developed ones like Pinacolborane and Tetra-n-propylammonium Perruthenate (TPAP). For each reagent, a concise article provides a brief description of all important reactions for which the reagent is being used, including yields and reaction conditions, an overview of the physical properties of the reagent, its storage conditions, safe handling, laboratory synthesis and purification methods. Advantages and disadvantages of the reagent compared to alternative synthesis methods are also discussed. Reagents have been hand-picked from among the 5000 reagents contained in EROS, the Encyclopedia of Reagents for Organic Synthesis. Every organic chemist should be familiar with these key reagents that can make almost every reaction work.
Author: David Morales-Morales Publisher: Elsevier ISBN: 0128129328 Category : Science Languages : en Pages : 756
Book Description
Pincer Compounds: Chemistry and Applications offers valuable state-of-the-art coverage highlighting highly active areas of research—from mechanistic work to synthesis and characterization. The book focuses on small molecule activation chemistry (particularly H2 and hydrogenation), earth abundant metals (such as Fe), actinides, carbene-pincers, chiral catalysis, and alternative solvent usage. The book covers the current state of the field, featuring chapters from renowned contributors, covering four continents and ranging from still-active pioneers to new names emerging as creative strong contributors to this fascinating and promising area. Over a decade since the publication of Morales-Morales and Jensen's The Chemistry of Pincer Compounds (Elsevier 2007), research in this unique area has flourished, finding a plethora of applications in almost every single branch of chemistry—from their traditional application as very robust and active catalysts all the way to potential biological and pharmaceutical applications. - Describes the chemistry and applications of this important class of organometallic and coordination compounds - Includes contributions from global leaders in the field, featuring pioneers in the area as well as emerging experts conducting exciting research on pincer complexes - Highlights areas of promising and active research, including small molecule activation, earth abundant metals, and actinide chemistry
Author: Andrei K. Yudin Publisher: John Wiley & Sons ISBN: 3527633405 Category : Science Languages : en Pages : 541
Book Description
Written by an experienced editor widely acclaimed within the scientific community, this book covers everything fromo9xygen to nitrogen functionalities. From the contents: Palladium-Catalyzed Syntheses of Five-Member Saturated Heterocyclic and of Aromatic Heterodynes Palladium-Catalysis for Oxidative 1, 2-Difunctionalization of Alkenes Rhodium-Catalyzed Amination of C-H-Bonds Carbon-Heteroatom Bond Formation by RH(I)-Catalyzed Ring-Opening Reactions Transition Metal-Catalyzed Synthesis of Lactones and of Monocyclic and Fused Five-Membered Aromatic heterocycles the Formation of Carbon-Sulfur and Carbon-Selenium bonds by Substitution and Addition reactions catalyzed by Transition Metal Complexes New Reactions of Copper Acetylides Gold Catalyzed Addition of Nitrogen, Sulfur and Oxygen Nucleophiles to C-C Multiple Bonds. The result is an indispensable source of information for the Strategic Planning of the Synthetic routes for organic, catalytic and medicinal chemists, as well as chemists in industry.
Author: Robert H. Crabtree Publisher: John Wiley & Sons ISBN: 1118210859 Category : Science Languages : en Pages : 418
Book Description
"One impressive and compressive book. . . . This review would have to be book size to do full justice to all the insights in this volume." —Journal of Metals Online Fully updated and expanded to reflect recent advances, this Fifth Edition of the classic text provides students and professional chemists with a comprehensive introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction mechanisms and detailed descriptions of contemporary applications. With increased focus on organic synthesis applications, nanoparticle science, and green chemistry, the Fifth Edition brings this vital resource up to date. New to the Fifth Edition: Chapters have been updated with relevant examples in the field, modern trends, and new applications; the organic applications chapter has been completely rewritten New end-of-chapter problems, along with their solutions Coverage enhanced with developments in nanoparticle science Increased focus on green chemistry An unparalleled pedagogic resource as well as a valuable working reference for professional chemists, with comprehensive coverage and up-to-date information, students and researchers in organic and organometallic chemistry will turn to The Organometallic Chemistry of the Transition Metals, Fifth Edition for the critical information they need on organometallic compounds, their preparation, and their use in synthesis.
Author: Yury Kissin Publisher: Elsevier ISBN: 0080557996 Category : Technology & Engineering Languages : en Pages : 607
Book Description
During the past 30 years, the field of alkene polymerization over transition metal catalysts underwent several major changes:1. The list of commercial heterogeneous Ziegler-Natta catalysts for the synthesis of polyethylene and stereoregular polyolefins was completely renewed affording an unprecedented degree of control over the polymer structure.2. Research devoted to metallocene and other soluble transition-metal catalysis has vastly expanded and has shifted toward complexes of transition metals with multidentate ligands.3. Recent developments in gel permeation chromatography, temperature-rising fractionation, and crystallization fractionation provided the first reliable information about differences between various active centers in transition-metal catalysts.4. A rapid development of high-resolution 13C NMR spectroscopy resulted in greatly expanded understanding of the chemical and steric features of polyolefins and alkene copolymers. These developments require a new review of all aspects of alkene polymerization reactions with transition-metal catalysts. The first chapter in the book is an introductory text for researchers who are entering the field. It describes the basic principles of polymerization reactions with transition-metal catalysts, the types of catalysts, and commercially manufactured polyolefins. The next chapter addresses the principal issue of alkene polymerization catalysis: the existence of catalyst systems with single and multiple types of active centers. The subsequent chapters are devoted to chemistry and stereochemistry of elemental reaction steps, structures of catalyst precursors and reactions leading to the formation of active centers, kinetics of polymerization reactions, and their mechanisms.The book describes the latest commercial polymerization catalysts for the synthesis of polyethylenes and polypropylene The book provides a detailed description of the multi-center nature of commercial Ziegler-Natta catalysts. The book devotes specialized chapters to the most important aspects of transition metal polymerization catalysts: the reactions leading to the formation of active centers, the chemistry and stereochemistry of elemental polymerization steps, reaction kinetics, and the polymerization mechanism. The book contains an introductory chapter for researchers who are entering the field of polymerization catalysis. It describes the basic principles of polymerization reactions with transition-metal catalysts and the types of commercially manufactured polyolefins and copolymersThe book contains over 2000 references, the most recent up to end of 2006.
Author: Tyler Eugene Stevens
Author: Tyler Eugene Stevens
Author: Aiwen Lei
Author: Nai-Wen Tseng
Author: Arkadi Vigalok
Author: Robert H. Crabtree
Author: Philip L. Fuchs
Author: David Morales-Morales
Author: Andrei K. Yudin
Author: Robert H. Crabtree
Author: Yury Kissin