Filling the gap for a comprehensive handbook and ready reference with a focuson synthetic methods, this book covers all modern developments within the field, including biochemical aspects. The chemistry chapters are organized according to the different reactivities of various selenium compounds and reagents, with each chapter dealing with a special reaction type. Also includes a table with 77Se NMR shifts to aid in practical problems. INDICE: Preface XI List of Contributor XIII 1 Electrophilic Selenium 1 Claudio Santi and Stefano Santoro 1.1 General Introduction 1 1.1.1 Synthesis of Electrophilic Selenium Reagents 3 1.1.2 Reactivity and Properties 7 1.2 Addition Reactions to Double Bonds 11 1.2.1 Addition Reaction Involving Oxygen-Centered Nucleophiles 11 1.2.2 Addition Reaction Involving Nitrogen-Centered Nucleophiles 22 1.2.3 Addition Reactions Involving Carbon-Centered Nucleophiles 26 1.2.4 Addition Reaction Involving Chiral Nucleophiles or Chiral Substrates 28 1.3 Selenocyclizations 30 1.3.1 Oxygen Nucleophiles 31 1.3.2 Nitrogen Nucleophiles 35 1.3.3 Competition between Oxygen and Nitrogen Nucleophiles 40 1.3.4 Carbon Nucleophiles 42 1.3.5 Double Cyclization Reactions 44 References 45 2 Nucleophilic Selenium 53 Michio Iwaoka 2.1 Introduction 53 2.1.1 Development of Nucleophilic Selenium Reagents 53 2.1.2 Examples of Recent Applications 54 2.2 Properties of Selenols and Selenolates 56 2.2.1 Electronegativity of Selenium 562.2.2 Tautomerism of Selenols 57 2.2.3 Nucleophilicity of Selenolates 58 2.3 Inorganic Nucleophilic Selenium Reagents 59 2.3.1 Conventional Reagents 59 2.3.2 New Reagents 61 2.4 Organic Nucleophilic Selenium Reagents 65 2.4.1 Preparation 65 2.4.2 Structure 66 2.4.3 Ammonium Selenolates (NH4+) 67 2.4.4 Selenolates of Group 1 Elements (Li, Na, K, and Cs) 67 2.4.5 Selenolates of Group 2 Elements (Mg, Ca, and Ba) 70 2.4.6 Selenolates of Group 3 Elements (Sm, Ce, Pr, Nb, and U) 71 2.4.7 Selenolates of Group 4 Elements (Ti, Zr, and Hf) 73 2.4.8 Selenolates of Group 5 Elements (V, Nb, and Ta) 74 2.4.9 Selenolates of Group 6 Elements (Mo and W) 75 2.4.10 Selenolates of Group 7 Elements (Mn and Re) 762.4.11 Selenolates of Group 8 Elements (Fe, Ru, and Os) 78 2.4.12 Selenolatesof Group 9 Elements (Co, Rh, and Ir) 81 2.4.13 Selenolates of Group 10 Elements (Ni, Pd, and Pt) 84 2.4.14 Selenolates of Group 11 Elements (Cu, Ag, and Au) 90 2.4.15 Selenolates of Group 12 Elements (Zn, Cd, and Hg) 92 2.4.16 Selenolates of Group 13 Elements (B, Al, Ga, and In) 95 2.4.17 Selenolates of Group 14 Elements (Si, Ge, Sn, and Pb) 97 2.4.18 Selenolates of Group 15 Elements (P, As, Sb, and Bi) 100 References 102 3 Selenium Compounds in Radical Reactions111 W. Russell Bowman 3.1 Homolytic Substitution at Selenium to Generate Radical Precursors 111 3.1.1 Bimolecular SH2 Reactions: Synthetic Considerations 112 3.1.1.1 Radical Reagents 115 3.1.2 Alkyl Radicals from Selenide Precursors 115 3.1.3 Acyl Radicals from Acyl Selenide Precursors 119 3.1.4 Imidoyl Radicals from Imidoyl Selenides 123 3.1.5 Other Radicals from Selenide Precursors 125 3.2 Selenide Building Blocks 126 3.3 Solid-Phase Synthesis 128 3.4 Selenide Precursors in Radical Domino Reactions 130 3.5 Homolytic Substitution at Selenium for the Synthesis of Se-Containing Products 132 3.5.1 Intermolecular SH2 onto Se 132 3.5.2 Intramolecular SH2: Cyclization onto Se 132 3.6 Seleno Group Transfer onto Alkenes and Alkynes 134 3.6.1 S
- ISBN: 978-3-527-32944-1
- Editorial: Wiley-VCH
- Encuadernacion: Cartoné
- Páginas: 462
- Fecha Publicación: 02/11/2011
- Nº Volúmenes: 1
- Idioma: Inglés