Structural Studies on Biaryl Phosphines and Palladium Complexes Composed of Biaryl Phosphines

Structural Studies on Biaryl Phosphines and Palladium Complexes Composed of Biaryl Phosphines PDF Author: Timothy E. Barder
Publisher:
ISBN:
Category :
Languages : en
Pages : 898

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Book Description
(cont.) Chapter 4. Structural Insights into Amine Binding to Biaryl Phosphine-Palladium Complexes via Density Functional Theory and Experimental Studies. Chapter 5. Experimental and Theoretical Analysis of an Arene/Phosphine Ligated Pd(I) Dimer. Chapter 6. A Rationale for the Resistance of Dialkylbiaryl Phosphines Toward Oxidation by Molecular Oxygen. Chapter 7. Benchtop Monitoring of Reaction Progress via Visual Recognition with a Handheld UV Lamp: In Situ Sensing of Boronic Acids in the Suzuki-Miyaura Reaction.

Structural Studies on Biaryl Phosphines and Palladium Complexes Composed of Biaryl Phosphines

Structural Studies on Biaryl Phosphines and Palladium Complexes Composed of Biaryl Phosphines PDF Author: Timothy E. Barder
Publisher:
ISBN:
Category :
Languages : en
Pages : 898

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Book Description
(cont.) Chapter 4. Structural Insights into Amine Binding to Biaryl Phosphine-Palladium Complexes via Density Functional Theory and Experimental Studies. Chapter 5. Experimental and Theoretical Analysis of an Arene/Phosphine Ligated Pd(I) Dimer. Chapter 6. A Rationale for the Resistance of Dialkylbiaryl Phosphines Toward Oxidation by Molecular Oxygen. Chapter 7. Benchtop Monitoring of Reaction Progress via Visual Recognition with a Handheld UV Lamp: In Situ Sensing of Boronic Acids in the Suzuki-Miyaura Reaction.

Design of Precatalysts and Phosphine Ligands for Pd-catalyzed Transformations

Design of Precatalysts and Phosphine Ligands for Pd-catalyzed Transformations PDF Author: Bryan Taylor Ingoglia
Publisher:
ISBN:
Category :
Languages : en
Pages : 373

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Book Description
The work described in this thesis pertains to the formation of carbon-heteroatom bonds facilitated by palladium catalysts supported by bulky phosphine ligands. The first chapter is a summary of how biaryl monophosphine ligands have been used for carbon-heteroatom bond formations, including a ligand selection guide. The second chapter demonstrates how phosphinesupported Pd(II) oxidative addition complexes can be used as precatalysts in a variety of cross-coupling reactions. The third chapter presents a systematic study of the ligand architecture in an effort to rationally design new ligands capable of facilitating the challenging C-F reductive elimination from Pd(II). The fourth chapter highlights a structurally interesting side-product that resulted during ligand synthesis. Chapter 1: Biaryl Monophosphine Ligands in Palladium-Catalyzed C-N Coupling: An Updated User's Guide Over the past three decades, Pd-catalyzed cross-coupling reactions have become a mainstay of organic synthesis. In particular, catalysts derived from biaryl monophosphines have shown wide utility in forming C-N bonds under mild reaction conditions. This work summarizes a variety of C-N cross-coupling reactions using biaryl monophosphines as supporting ligands, with the goal of directing synthetic chemists toward the ligands and conditions best suited for a particular coupling. Chapter 2. Oxidative Addition Complexes as Precatalysts for Cross-Coupling Reactions Requiring Extremely Bulky Biarylphosphine Ligands. Palladium-based oxidative addition complexes were found to be effective precatalysts for C-N, C-O, and C-F cross-coupling reactions with a variety of aromatic electrophiles. These Pd(II) complexes are easily prepared and offer a convenient alternative to previously developed classes of precatalysts as they can be formed even with extremely large phosphine ligands, for which palladacycle-based precatalysts do not readily form. The complexes were found to be stable to long-term storage under ambient conditions. Chapter 3. Structure-Activity Relationship of Phosphine Ligands for the Fluorination of Five-membered Heteroaromatic Compounds Palladium catalysts supported by bulky dialkyl triaryl monophosphine ligands have been shown to promote the coupling of metal fluorides with (hetero)aryl bromides and triflates in good yield. A limitation of this methodology is the use of five-membered heteroaryl bromides, as the reductive elimination is more challenging due to the smaller size and electron-rich nature of the aryl electrophiles. In order to understand which structural features of the ancillary ligand are critical to facilitating the desired transformation, the ligand backbone was systematically varied and the initial rate of fluorination was monitored. These studies revealed that substitution at the 2" and 6" positions of the ligand scaffold has a dramatic impact on the reaction rate. As a result of these studies, new ligands were proposed which may be better able to accelerate the fluorination reaction. Chapter 4: Discovery of a Sterically Encumbered Hexasubstituted Arene through the Pdmediated Dearomative Rearrangement of Biaryl Monophosphine Ligands A key feature of the Pd-catalyzed aromatic fluorination reaction is the presence of the aryl group at the 3' position of the ligand backbone. It has been shown that supporting ligands lacking substitution at this position can be modified through a dearomative rearrangement, which incorporates one catalytic equivalent of the aryl electrophile into the ligand backbone when very bulky biarylphosphines are used. In Chapter 3, it was demonstrated that this rearrangement reaction is useful for rapidly accessing a variety of dialkyl triaryl monophosphine derivatives. During these studies, it was noted that for electron-rich aryl groups, this arylation occurred twice to form an unusual sterically congested hexasubstituted arene. X-ray crystallographic data indicates that the fully substituted aromatic ring is not planar.

Dissertation Abstracts International

Dissertation Abstracts International PDF Author:
Publisher:
ISBN:
Category : Dissertations, Academic
Languages : en
Pages : 980

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Synthesis and Characterization of Long-chain Alkyldiphenyl-phosphines and X-ray Structural Studies of Platinum(II) Phosphine Complexes

Synthesis and Characterization of Long-chain Alkyldiphenyl-phosphines and X-ray Structural Studies of Platinum(II) Phosphine Complexes PDF Author: Rashid Syed
Publisher:
ISBN:
Category : Phosphine
Languages : en
Pages : 1046

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Development of Novel P-bridged Biaryl Phosphines for Palladium-catalysed Cross Coupling Reactions

Development of Novel P-bridged Biaryl Phosphines for Palladium-catalysed Cross Coupling Reactions PDF Author: Lesibana Jairus Lamola
Publisher:
ISBN:
Category : Ligands
Languages : en
Pages : 0

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Palladium Reagents and Catalysts

Palladium Reagents and Catalysts PDF Author: Jiro Tsuji
Publisher: Wiley
ISBN: 9780470850336
Category : Science
Languages : en
Pages : 670

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Book Description
Jiro Tsuji, one of the pioneers in this field of organic synthesis, provides synthetic organic chemists with a remarkable overview of the many applications of organopalladium chemistry. Tsuji discusses the recent developments in the field as well as the explosive growth over the last five years. Highlighting the most recent discoveries in this rapidly expanding field, the book; Focuses on new aspects of organopalladium chemistry, putting emphasis on synthetic applications Investigates the new perspectives on the synthetic uses of contemporary organopalladium chemistry This volume, together with Innovations in Organic Synthesis, Tsuji's previous title, provides complete coverage of over 40 years of organopalladium chemistry. Palladium Reagents and Catalysts: New Perspectives for the 21st Century is an essential reference source and companion for students, and both industrial and academic research chemists working in organic synthesis, particularly on synthesis of natural products and medicinal compounds. Those studying development of new synthetic methodology and organometallic chemistry will also find this book valuable.

New Horizons in Modern Catalysis: Five Different Perspectives

New Horizons in Modern Catalysis: Five Different Perspectives PDF Author:
Publisher: Elsevier
ISBN: 0443186723
Category : Science
Languages : en
Pages : 196

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Book Description
New Horizons in Modern Catalysis: Six Different Perspectives, Volume 72 in the Advances in Catalysis series, highlights new advances in the field, with this new volume presenting interesting chapters on Carbanion-functionalized phosphines: New design elements for catalyst development, Molecular Electrocatalysts for Organic Electrosynthesis, Mechanistic aspects of secondary sphere modification in organocatalysis, Earth-Abundant Transition Metal-Catalyzed reactions with Iodine(III) reagents: from catalysis to mechanistic studies, Design of metal nanoparticles for better performance in catalysis, and Computational design of industrially relevant enzymes. Provides the authority and expertise of leading contributors from an international board of authors Presents the latest release in the Advances in Catalysis series Acts as a comprehensive platform for experimental and theoretical researchers

Inorganic Syntheses, Volume 23

Inorganic Syntheses, Volume 23 PDF Author:
Publisher: John Wiley & Sons
ISBN: 0470132892
Category : Science
Languages : en
Pages : 284

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Book Description
The volumes in this continuing series provide a compilation of current techniques and ideas in inorganic synthetic chemistry. Includes inorganic polymer syntheses and preparation of important inorganic solids, syntheses used in the development of pharmacologically active inorganic compounds, small-molecule coordination complexes, and related compounds. Also contains valuable information on transition organometallic compounds including species with metal-metal cluster molecules. All syntheses presented here have been tested.

Applied Cross-Coupling Reactions

Applied Cross-Coupling Reactions PDF Author: Yasushi Nishihara
Publisher: Springer Science & Business Media
ISBN: 3642323685
Category : Science
Languages : en
Pages : 247

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Book Description
“Applied Cross-Coupling Reactions” provides students and teachers of advanced organic chemistry with an overview of the history, mechanisms and applications of cross-coupling reactions. Since the discovery of the transition-metal-catalyzed cross-coupling reactions in 1972, numerous synthetic uses and industrial applications have been developed. The mechanistic studies of the cross-coupling reactions have disclosed that three fundamental reactions: oxidative addition, transmetalation, and reductive elimination, are involved in a catalytic cycle. Cross-coupling reactions have allowed us to produce a variety of compounds for industrial purposes, such as natural products, pharmaceuticals, liquid crystals and conjugate polymers for use in electronic devices. Indeed, the Nobel Prize for Chemistry in 2010 was awarded for work on cross-coupling reactions. In this book, the recent trends in cross-coupling reactions are also introduced from the point of view of synthesis design and catalytic activities of transition-metal catalysts.

Boronic Acids

Boronic Acids PDF Author: Dennis G. Hall
Publisher: John Wiley & Sons
ISBN: 3527606823
Category : Science
Languages : en
Pages : 571

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Book Description
For the first time, the whole field of organoboronic acids is presented in one comprehensive handbook. Professor Dennis Hall, a rising star within the community, covers all aspects of this important substance class, including applications in chemistry, biology and medicine. Starting with an introduction to the structure, properties, and preparation of boronic acid derivatives, together with an overview of their reactions and applications, the book goes on to look at metal-catalyzed borylation of alkanes and arenas, coupling reactions and rhodium-catalyzed additions of boronic acids to alkenes and carbonyl compounds. There follows chapters on copper-promoted C-O and C-N cross-coupling of boronic acids, recent applications in organic synthesis, as well as alpha-haloalkylboronic esters in asymmetric synthesis. Later sections deal with cycloadditions, organoboronic acids, oxazaborolidines as asymmetric inducers, and boronic acid based receptors and sensors. The whole is rounded off with experimental procedures, making this invaluable reading for organic, catalytic and medicinal chemists, as well as those working in organometallics.