Phosphines as Reagents and Catalysts in Organic Synthesis provides comprehensive coverage of metal-free organic reactions with phosphines as reagents or catalysts as well as their synthetic uses. The work begins with a short historical overview of the use of phosphines in metal-free organic reactions, followed by details of their physical properties, as well as the source and preparation methods for representative phosphines and chiral variants. The applications of phosphines as reagents and catalysts in organic synthesis are discussed, along with case studies organized according to reaction type. These reactions include halogenation under Appel conditions, Wittig reaction, Staudinger reaction, Mitsunobu reaction, alcohol acylation and kinetic resolution, Rauhut-Currier reaction, Morita-Baylis-Hillman reaction, conjugate addition, umpolung additions, annulation reactions, allylic substitution, allylic amination, and isomerization reactions. For each reaction an overview of the state of art is presented along with the reaction data, enantioselective version using chiral phosphine, and its application in the synthesis of biologically active compounds and total synthesis of natural products. The work concludes with a summary that highlights the most promising reactions for future development in this field of research. Researchers, graduate students and undergraduates working in organic synthesis will find this work to be an invaluable resource. Covers the application of organic reactions involving phosphine as reagents and catalysts in organic synthesis and biological chemistry Features synthetic methods for creating heterocyclic compounds Includes comprehensive coverage of organic reactions and reaction mechanisms involving phosphine as reagents and catalysts

This dissertation, "Development of phosphorus-mediated reactions in organic synthesis / y Xia Xuanshu, B. Sc., Sun Yat-sen U" by Xuanshu, Xia, 夏轩庶, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Polymer-supported catalysts and reagents have been widely used in organic chemistry because they could facilitate the purification procedures and usually be recycled. Much research has been directed to polymer-supported catalysts and reagents, mainly focusing on these aspects, such as new polymer support, new application in organic chemistry, different modifications and so on. Many polymer-supported phosphine reagents have been developed for Wittig reaction. However, most of them suffer from swelling issue or low loading. A new polyethlyeneimine-supported triphenylphosphine has been synthesized and used as a highly loaded bifunctional homogeneous reagent in a range of one-pot Wittig reactions. All the substrates afforded desired products in high yields after only simple purification procedures. Furthermore, it also served efficiently in reaction cascades involving a one-pot Wittig reaction followed by conjugate reduction of alkene products. In these transformations the phosphine oxide generated in Wittig reaction served as the catalyst for activating trichlorosilane in the subsequent reduction reaction. Triphenylphosphine oxide is always considered as a byproduct of Wittig and Mitsunobu reactions which complicates the purification procedures. One option to utilize it is its application in halogenation reaction with oxalyl halide. Heterogeneous polymer-supported triphenylphosphine oxides based on the rasta resin architecture have been synthesized, and applied as reagent precursors in a wide range of halogenation reactions. The rasta resin-triphenylphosphine oxides reacted with either oxalyl chloride or oxalyl bromide to form the corresponding halophosphonium salts, and these in turn reacted with alcohols, aldehydes, aziridines and epoxides to form halogenated products in high yields after simple purification. The polymer-supported triphenylphosphine oxides formed as a byproduct during these reactions could be recovered and reused numerous times with no appreciable decrease in reactivity. Another option is to use triphenylphosphine oxide as catalyst in organic synthesis. A highly regioselective 1,4-reduction of conjugated polyunsaturated ketones catalyzed by triphenylphosphine oxide is described. In the presence of triphenylphosphine oxide, conjugated di-, tri-, and tetraenones were selectively α,β-reduced using trichlorosilane without over reduction or isomerization, and all the substrates rendered desired products in high yields. Furthermore, 1,4-reduction products were successfully obtained in sequential one-pot Wittig/conjugate reduction reaction, triphenylphosphine oxide generated in Wittig reaction served as the catalyst for reduction reaction. In addition, natural moth pheromones and their analogues were synthesized in high yields using this method. Finally, the synthesis of γ-sanshool and hydroxy-γ-sanshool is depicted. The synthetic route started from simple and commercially available building blocks using an alkyne for E, E-2,4-diene group of the key synthetic intermediate 2E,4E,8Z,10E,12E-tetradecapentaenoic acid, which in turn was converted into both γ-sanshool and hydroxy-γ-sanshool by reaction with the appropriate amines. DOI: 10.5353/th_b5435655 Subjects: Supported reagents Polymers

Basic chemistry of organopalladium compounds; Classification of the reactions involving Pd(II) compounds and Pd(O) complexes.

Based on the papers and posters presented at the 15th Conference on Catalysis of Organic Reactions, this work covers developments in the study of catalysis as it relates to organic synthesis, emphasizing applications in industrial processes. Over 1000 bibliographic citations and over 250 tables, drawings, and photographs are provided. Theoretical and practical aspects of the field are highlighted.

The long awaited Handbook for all synthetic chemists working on coupling reactions, compiling all major catalyst components in use in the area. Consists of a compilation of articles taken from the EROS database, with the inclusion of about 20 newly commissioned catalysts/pre-catalysts/ligands that have made an impact in this area of synthetic organic chemistry. Includes catalyst systems used in Heck, Kumada-Tamao-Corriu, Suzuki-Miyaura, Hiyama-Hatanaka, Negishi, Migita-Kosugi-Stille, Buchwald-Hartwig, and Tsuji-Trost coupling reactions.

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.