Stereodirected Synthesis with Organoboranes [Paperback]

1 Introduction to Borane Chemistry.- 1.1 Beginnings.- 1.2 Structure and Bonding in Organoboranes.- 1.2.1 General Characteristics of Boranes.- 1.2.2 Size.- 1.2.3 Bond Strengths.- 1.3 General Chemical Properties of Organoboranes.- 1.3.1 Oxidation States of Boron.- 1.3.2 Ligand Exchange on Boron.- 1.3.3 Acidities.- 1.4 Safety Considerations.- 1.4.1 General Hazards.- 1.4.2 Laboratory Handling.- 1.5 References.- 2 Sources of Compounds Containing BoronCarbon Bonds.- 2.1 Industrial Sources of Boron Compounds.- 2.2 The Organometallic Route.- 2.2.1 Boronic Esters.- 2.2.1.1 Grignard and Lithium Reagents.- 2.2.1.2 Other Organometallics.- 2.2.2 Di-, Tri-, and Tetraborylmethanes.- 2.2.3 Borinic Esters (Dialkylalkoxyboranes).- 2.2.4 Trialkylboranes.- 2.3 Hydroboration.- 2.3.1 General Considerations.- 2.3.2 Mechanism of Hydroboration.- 2.3.3 Hydroborating Agents.- 2.3.3.1 Borane Sources.- 2.3.3.2 Alkylborane reagents.- 2.3.3.3 Oxygen substituted hydroborating agents.- 2.3.3.4 Haloboranes.- 2.3.4 Catalyzed Hydroborations.- 2.4 Haloborations.- 2.5 Other Routes to CarbonBoron Bonds.- 2.6 References.- 3 General Reactions of Organoboranes.- 3.1 Introduction.- 3.2 Oxidative Replacement of Boron.- 3.2.1 Introduction.- 3.2.2 Oxygen Electrophiles.- 3.2.2.1 Hydrogen peroxide.- 3.2.2.2 Migratory aptitudes.- 3.2.2.3 Sodium perborate and other peroxides.- 3.2.2.4 Trimethylamine N-oxide.- 3.2.2.5 Molecular oxygen.- 3.2.2.6 Other reagents.- 3.2.3 Nitrogen Electrophiles.- 3.2.3.1 Chloramine and hydroxylaminesulfonic acid.- 3.2.3.2 Alkyl azides.- 3.2.3.3 Rearrangement of a-aminoboranes.- 3.2.4 Halogenation.- 3.2.4.1 Stereoselective replacements.- 3.2.4.2 Halogenation at carbon adjacent to boron.- 3.2.5 Sulfur.- 3.2.6 Protonolysis.- 3.2.7 Metalation.- 3.3 Boron Substituted Carbanions.- 3.3.1 By Deboronation.- 3.3.2 By Destannylation.- 3.3.3 By Deprotonation.- 3.3.4 By Michael Addition.- 3.4 Replacement of Boron by Carbon.- 3.4.1 Introduction.- 3.4.2 ?-Eliminations as Nuisance Reactions.- 3.4.3 Mil³’