Synthesis of Carbon-Phosphorus Bonds, Second Edition is a working guide for the laboratory, incorporating classical approaches with the recent developments of carbon-phosphorus (C-P) bond formation. These advances include the preparation of phosphoranes - specifically in the use of transient oxophosphoranes as intermediates in organophosphorus comp
Synthesis of Carbon-Phosphorus Bonds, Second Edition is a working guide for the laboratory, incorporating classical approaches with the recent developments of carbon-phosphorus (C-P) bond formation. These advances include the preparation of phosphoranes - specifically in the use of transient oxophosphoranes as intermediates in organophosphorus compound synthesis ñ along with the new approaches towards the preparation of compounds with aromatic and vinylic C-P bonds. Synthesis of Carbon-Phosphorus Bonds, Second Edition serves as a useful tool in the laboratory. It offers detailed surveys of IUPAC nomenclature recommendations, common notation systems, and various experimental examples. These features help to make this text an effective source of critical and annotated references, as well as a a working guide for organic and phosphorus chemists specifically, or for any chemists working with C-P bonds.
The work presented in this dissertation deals with the development of new methodologies for P-C bond formation as well as synthesizing biologically relevant organophosphorus compounds. A distinct emphasis is given to the important synthetic targets, the H-phosphinates. A review of relevant literature is provided in Chapter 1. Chapter 2 describes the synthesis and structural analyses, of triphenylmethyl-containing phosphorus compounds. For the first time, both phosphonothioic and boranophosphonic acids have been characterized by single X-ray diffractometry. The third chapter details the preparation and the reactivity of phosphine-borane complexes. Novel dialkoxyphosphine-borane complexes were introduced, both as general synthetic intermediates for the preparation of H-phosphinates or disubstituted phosphinic acids, and as boranophosphonate precursors. Related to this chemistry, silylation of an H-phosphinate intermediate can also be conducted and the resulting phosphonite protected with borane. This allows the temporary protection of the sensitive P-H group, so that manipulations of the alkyl chain might be conducted. In chapter 4, the palladium-catalyzed cross-coupling reaction of dialkylphosphites with aryl and heteroaryl halides is presented. An efficient, versatile and economically attractive alternative to the original Hirao cross-coupling by using only 1 mol% (or less) Pd(OAc)2/dppf is described. Moreover, first example of palladium-catalyzed P-C bond formation between activated aryl chlorides and a phosphite are herein reported. Chapter 5 focuses on the free-radical hydrophosphinylation of alkynes. The triethylborane-initiated radical addition of sodium hypophosphite to terminal alkyne affords the previously unknown 1,1-bis-H-phosphinates, precursors of the biologically relevant 1,1-bisphosphonates (e.g., treatment of bone diseases). Thus, the oxidative conversion of 1,1-bis-H-phosphinates to the corresponding bisphosphonates, as well as the synthesis of a series of bio-conjugates (steroids, carbohydrates, fluoroquinolones) was investigated. In the last chapter, the palladium-catalyzed hydrophosphinylation of hypophosphorous acid derivatives to terminal alkynes is reported. In an effort to improve the regioselectivity of the reaction, various terminal alkynes were tested, as well as the solvent and catalyst system.
The work in this dissertation deals with the continued development of new methodologies for P-C and P-O bond formation using alternative methods that avoid the use of PCl3. A review of the relevant literature that proceeds this work is presented in Chapter 1. Chapter 2 describes the study of the P(III) to P(V) tautomerization of phosphinylidene compounds and the structural influences that effect the thermodynamic and kinetic properties to favor the more reactive P(III) species. A collaboration using both computational and experimental methods, show that electron withdrawing groups such as phenyl stabilize the tautomerization of phosphinylidene compounds. The second part of this work highlights the influence of various catalysts on P(III) to P(V) tautomerization. Using computational chemistry as a screening tool, a variety of organic acids and bases were tested. The calculations and experimental results are in good agreement. Chapter 3 describes the work to develop the nickel-catalzyed hydrophosphinylation of unactivated alkenes, an extension of the work started with the nickel-catalyzed hydrophosphosphinylation of alkynes. The results show that nickel chloride is pre-activated to an active Ni(0) species and can be stabilized by the inexpensive bisphosphine ligand, ethylbis(diphenylphosphine), dppe. The reaction occurs at room temperature and works on a variety of different alkene substrates. Other manipulations used in tandem with the initial nickel hydrophosphinylation are highlighted, and show the reaction to be a versatile tool for making alkyl-H-phosphinate derivatives as precursors for further use. Chapter 4 details the development of manganese-promoted intermolecular and intramolecular additions of alkenes, alkynes and aryl compounds with H-phosphinates is described. The system utilizing catalytic Mn(OAc)2 either neat or in DMSO, is successful for a variety of different alkenes and two alkyne substrates. A more efficient and cost-effective system was recently developed for H-phosphinate arylations using catalytic Mn(OAc)2 and MnO2 as an oxidant, and further applied to alkene phosphonochlorination with LiCl. In Chapter 5, nickel-catalyzed oxidation of alkyl hypophosphites is utilized to prepare ubiquitous alkyl-H-phosphonates starting from hypophosphorous acid and avoiding the use of PCl3. The reaction can be considered a form of water splitting. The studies show that after the intitial esterification step, NiCl2 or Ni/SiO2 is enough to oxidize the first P-H bond to form the desired phosphonate. The reaction has been applied to the synthesis of the global herbicide glyphosate.
Chapter 1 takes the format of an "Outlook", and sets forth the case for developing sustainable methods in the synthesis of phosphorus-containing compounds. Methods used by nature for phosphorus-carbon bond-formation, or in the chemistry of other elements such as silicon, are discussed as model processes for the future of phosphorus in chemical synthesis. Chapter 2 describes the discovery of [TBA][P(SiCl3)2], prepared from [TBA]3[P3O9]-.2H2O and trichlorosilane. The bis(trichlorosilyl)phosphide anion is used to prepare compounds that contain P–C, P–O, P–F, and P–H bonds in a method that bypasses white phosphorus (P4), the traditional route to organophosphorus compounds. Chapter 3 extends the phosphate precursors to [TBA][P(SiCl3)2] from trimetaphosphate to crystalline phosphoric acid. Balanced equations are developed for the formation of [TBA][P(SiCl3)2] from phosphate sources and the byproducts are identified as hexachlorodisiloxane and hydrogen gas. Extension of trichlorosilane reduction to bisulfate provides improved access the known trichlorosilylsulfide anion, [TBA][SSiCl3]. This anion was used as a thionation reagent to prepare thiobenzophenone and benzyl mercaptan from benzophenone and benzyl bromide, respectively. Chapter 4 describes the synthesis of neutral phosphine, HP(SiCl3)2, obtained by protonation of [TBA]1 with triflic acid. HP(SiCl3)2 is a highly efficient reagent for photochemical hydrophosphination of terminal alkenes. The phosphorus-silicon bonds in the hydrophosphination products can be functionalized to provide compounds of the general formulae: RPCl2, RPH2, [RP(R')3]Cl, RP(O)(H)(OH), and RP(O)(OH)2. Chapter 5 describes a method to prepare phosphiranes (three-membered rings that contain a phosphorus atom) from anthracene-based phosphinidene precursors and styrenic olefins. The phosphinidene transfer reaction requires an organoiron and fluoride catalyst. The resulting phosphirane is prepared in good yield (73%) with high stereoselectivity (>99%). Experimental investigations into the mechanism point toward the intermediacy of an iron-coordinated fluorophosphide species.
This book explores the limitless ability to design new materials by layering clay materials within organic compounds. Assembly, properties, characterization, and current and potential applications are offered to inspire the development of novel materials. Coincides with the government's Materials Genome Initiative, to inspire the development of green, sustainable, robust materials that lead to efficient use of limited resources Contains a thorough introductory and chemical foundation before delving into techniques, characterization, and properties of these materials Applications in biocatalysis, drug delivery, and energy storage and recovery are discussed Presents a case for an often overlooked hybrid material: organic-clay materials
In this second edition of a best-selling handbook all the chapters have been completely revised and updated, while four completely new chapters have been added. In order to meet the needs of the practitioner, emphasis is placed on describing precisely the technology and know-how involved. Adopting a didactic and comprehensible approach, the book guides the reader through theory and applications, thus ensuring its warm welcome among the scientific community. An excellent, essential and exhaustive overview.
Organophosphorus Chemistry presents a groundbreaking resource in this branch of organic chemistry that demonstrates how phosphorus-containing compounds can be manipulated in a variety of organic reactions. The authors give an overview of the newest trends and synthesis strategies, introduce bioactive and environmentally friendly organophosphorus compounds and show their importance in mainstream organic chemistry.
A practical road map to the key families of biomaterials and their potential applications in clinical therapeutics, Introduction to Biomaterials, Second Edition follows the entire path of development from theory to lab to practical application. It highlights new biocompatibility issues, metrics, and statistics as well as new legislation for intellectual property. Divided into four sections (Biology, Biomechanics, Biomaterials Interactions; Biomaterials Testing, Statistics, Regulatory Considerations, Intellectual Property; Biomaterials Compositions; and Biomaterials Applications), this dramatically revised edition includes both new and revised chapters on cells, tissues, and signaling molecules in wound healing cascades, as well as two revised chapters on standardized materials testing with in vitro and in vivo paradigms consistent with regulatory guidelines. Emphasizing biocompatibility at the biomaterial-host interface, it investigates cell-cell interactions, cell-signaling and the inflammatory and complement cascades, specific interactions of protein-adsorbed materials, and other inherent biological constraints including solid-liquid interfaces, diffusion, and protein types. Unique in its inclusion of the practicalities of biomaterials as an industry, the book also covers the basic principles of statistics, new U.S. FDA information on the biomaterials-biology issues relevant to patent applications, and considerations of intellectual property and patent disclosure. With nine completely new chapters and 24 chapters extensively updated and revised with new accomplishments and contemporary data, this comprehensive introduction discusses 13 important classes of biomaterials, their fundamental and applied research, practical applications, performance properties, synthesis and testing, potential future applications, and commonly matched clinical applications. The authors include extensive references, to create a comprehensive, yet manageable didactic work that is an invaluable desk references and instructional text for undergraduates and working professionals alike.
