Matteson, D: Stereodirected Synthesis with Organoboranes

Migrations to Electron-Deficient ?-Carbon.- 3.4.3.1 Introduction.- 3.4.3.2 Discovery of process and mechanism.- 3.4.3.3 Favored reaction pathways.- 3.4.3.4 Routes to ?-haloalkylboron compounds.- 3.4.3.5 The stereocontrollable route to halo boronic esters.- 3.4.3.6 Alkylation of (halomethyl)boronic esters.- 3.4.3.7 Simple homologation of boronic and borinic esters.- 3.4.3.8 Rearrangement of a,b-unsaturated borates.- 3.4.3.9 Carbonylation and cyanidation.- 3.4.3.10 Other chain extensions.- 3.4.4 Displacement of Boron by Electrophilic Carbon.- 3.4.4.1 Polar displacements.- 3.4.4.2 Small ring formation.- 3.4.4.3 Radical displacement mechanisms.- 3.4.5 Allylborane Chemistry.- 3.4.5.1 Introduction.- 3.4.5.2 Triallylborane.- 3.4.5.3 Intramolecular allylic rearrangements.- 3.4.5.4 Allylic bisboranes.- 3.4.5.5 Three-carbon chain extension of boronic esters.- 3.4.5.6 3-Borolenes.- 3.4.5.7 Allenyl and propargyl boranes.- 3.4.6 Photochemical Rearrangements.- 3.5 Reactions at Sites Other than the B-C Bond.- 3.5.1 Introduction.- 3.5.2 Nucleophilic Reactions of a-Halo Boronic Esters.- 3.5.2.1 Displacements.- 3.5.2.2 Eliminations.- 3.5.3 ?-Bromination.- 3.5.4 Oxidations of Other Functions in the Presence of C-B Bonds.- 3.5.5 Additions to Double Bonds.- 3.5.5.1 Radical additions.- 3.5.5.2 Polar and catalytic additions.- 3.5.5.3 Cycloadditions.- 3.5.5.4 Cyclopropanation.- 3.6 References.- 4 Alkenylboranes and Control of Olefinic Geometry.- 4.1 Introduction.- 4.2 ?-Elimination Routes to Unsaturated Compounds.- 4.2.1 Simple Alkenes.- 4.2.1.1 Introduction.- 4.2.1.2 Stereochemistry.- 4.2.1.3 Fragmentation.- 4.2.1.4 Alkenes from enamines.- 4.2.2 Routes to Alkenylboranes.- 4.2.2.1 (E)-1 - Alkenylboranes from 1 -alkynes.- 4.2.2.2 Alkenylboranes from disubstituted alkynes.- 4.2.3 Inversion of (E)- to (Z)-Alkenylboranes.- 4.2.4 Other Routes to Alkenylboranes.- 4.2.5 The Zweifel Olefin Synthesis.- 4.3 The Suzuki Coupling Reaction.- 4.3.1 Scope of the Reaction.- 4.3.2 Synthetic Applications.- 4.4 Other Stereoselective Routes to Alkenes.- 4.4.1 Alkenylpropargylic and Alkenylallenic Boranes.- 4.4.2 Insertion into Carbon-Boron Bonds.- 4.4.3 ?,?-Unsaturated Ketones from Boron Enolates.- 4.5 References.- 5 Asymmetric Synthesis via (a-Haloalkyl)boronic Esters.- 5.1 Introduction.- 5.1.1 Overview.- 5.1.2 Nomenclature Notes.- 5.1.2.1 Chirality descriptors.- 5.1.2.2 Bond illustration conventions.- 5.1.2.3 Drawings of bicyclic structures.- 5.2 Synthetic Methodology: Pinanediol Esters.- 5.2.1 Original Process.- 5.2.1.1 Preparation of pinanediol.- 5.2.1.2 Discovery of pinanediol boronic ester chemistry.- 5.2.1.3 Epimerization of (a-chloroalkyl)boronic esters.- 5.2.2 Zinc Chloride Promotion of a-Halo Boronic Ester Formation.- 5.2.3 Functional Group Compatibility.- 5.2.3.1 Alkoxy substituents.- 5.2.3.2 An azido substituent.- 5.2.3.3 Thioether substituents.- 5.2.3.4 Halogen substituents.- 5.2.3.5 Carboxylic ester substituents.- 5.2.3.6 Unsaturated boronic esters.- 5.2.4 Quaternary Chiral Centers.- 5.2.5 Pinanediol Recovery.- 5.2.6 Nonequivalent Faces of Boron in Pinanediol Esters.- 5.3 Synthetic Methodology: Chiral Directors Having C2 Symmetry.- 5.3.1 Butanediol Esters.- 5.3.1.1 Synthetic routes made possible by C2 symmetry.- 5.3.1.2 Nomenclature of cyclic boronic esters.- 5.3.2 Diisopropylethanediol (DIPED) Esters.- 5.3.2.1 Introduction.- 5.3.2.2 Synthesis of DIPED.- 5.3.3 Dicyclohexylethanediol (DICHED) Esters.- 5.3.3.1 Introduction.- 5.3.3.2 Synthesis of DICHED.- 5.3.4 Ultrahigh Stereoselectivity with C2 Symmetry.- 5.3.4.1 Introduction.- 5.3.4.2 Background.- 5.3.4.3 Discovery of enhanced selectivity.- 5.3.4.4 Kinetic resolution.- 5.3.4.5 Mechanistic interpretation.- 5.3.5 Convergent Connection of Two Asymmetric Centers.- 5.3.6 Reaction of Enolates.- 5.3.7 Allylic Boronic Esters.- 5.3.7.1 (?-Haloallyl)boronic esters.- 5.3.7.2 Asymmetric synthesis of an allylic boronic ester.- 5.3.7.3 Chain extension of allylboronic esters.- 5.4 Synthetic Applications.- 5.4.1 A Useful Mnemonic for Chiral Direction.- 5.4.2 Amido Boronic Esters.- 5.4.3 Insect Pheromones.- 5.4.3.1 Introduction.- 5.4.3.2 exo-Brevicomin.- 5.4.3.3 Eldanolide.- 5.4.3.4 (3S,4S)- and (3R,4S)-4-Methyl-3-heptanol.- 5.4.3.5 Stegobiol and stegobinone.- 5.4.4 Polyols.- 5.4.4.1 L-Ribose.- 5.4.4.2 Asymmetrically deuterated glycerol.- 5.4.5 Amino Acids.- 5.5 References.- 6 Asymmetric Hydroboration Chemistry.- 6.1 Introduction.- 6.2 Asymmetric Hydroboration.- 6.2.1 Reagents.- 6.2.1.1 Purification of pinylboranes.- 6.2.1.2 Recovery of ?-pinene.- 6.2.1.3 Alternative chiral directors.- 6.2.2 Hydroboration with Diisopinocampheylborane.- 6.2.3 Hydroboration with Monoisopinocampheylborane.- 6.3 Transformations of Asymmetric Organoboranes.- 6.3.1 Overview.- 6.3.1.1 General summary of transformations.- 6.3.1.2 Interconversions of boron oxidation states.- 6.3.2 Carbon-Carbon Bond Formation.- 6.3.2.1 Introduction.- 6.3.2.2 Methylene insertion routes.- 6.3.2.3 Borinic ester intermediates.- 6.3.2.4 Enolate insertions.- 6.3.2.5 Thexylborane and pinylborane intermediates.- 6.3.3 Carbon-Nitrogen Bond Formation.- 6.4 Substrate Directed Hydroboration.- 6.4.1 Noncatalytic methods.- 6.4.1.1 Introduction.- 6.4.1.2 Isopropenyl group hydroboration.- 6.4.1.3 Cyclic borane intermediates.- 6.5 Catalytic Asymmetric Hydroboration.- 6.5.1 Catalyst Effects in Substrate Directed Hydroboration.- 6.5.2 Hydroboration with Asymmetric Catalysts.- 6.6 References.- 7 Allylboron and Boron Enolate Chemistry.- 7.1 Introduction.- 7.2 Allylic Boronic Esters.- 7.2.1 General Advantages.- 7.2.2 Sources of Allylic Boronic Esters.- 7.2.2.1 Allylic metal compounds.- 7.2.2.2 Retroracemization of a Grignard reagent.- 7.2.2.3 Via (alkenyl)(halomethyl)borate rearrangement.- 7.2.2.4 Catalyzed hydroboration.- 7.2.3 Diastereoselection with Racemates.- 7.2.3.1 Mechanism.- 7.2.3.2 Range of useful substituents.- 7.2.3.3 Imines.- 7.2.3.4 Ketones.- 7.2.3.5 Cyclizations.- 7.2.4 Asymmetric Reactions of Boronic Esters.- 7.2.4.1 Boronic esters of chiral diols with achiral aldehydes.- 7.2.4.2 A chiral boron amide.- 7.2.4.3 Chiral Aldehydes.- 7.2.4.4 Chiral allylic groups.- 7.2.5 Asymmetric Syntheses with Boronic Esters.- 7.2.5.1 Insect pheromones.- 7.2.5.2 Macrolide and ionophore antibiotic syntheses.- 7.2.6 Allenyl and Propargyl Boronic Esters and 1,3,2-Diaza borolidines.- 7.2.7 Borinic Acids.- 7.3 Allyldialkylboranes.- 7.3.1 From ?-pinene and other terpenes.- 7.3.1.1 Unsubstituted allyl groups.- 7.3.1.2 Methyl-substituted allyl groups.- 7.3.1.3 Other substituted allyl groups.- 7.3.2 Borolanes as Chiral Directors.- 7.4 Boron Enolates.- 7.4.1 Introduction.- 7.4.2 Chiral Enolate Carbon Skeletons.- 7.4.2.1 Silylated hydroxy ketone enolates.- 7.4.2.2 Chiral amide enolates.- 7.4.3 Chiral Boryl Groups.- 7.4.3.1 2,5-Dimethylborolanes.- 7.4.3.2 Chiral 1,3,2-diazaborolidines.- 7.4.4 Catalytic Boron Enolate Reactions.- 7.4.4.1 Silyl enol ethers.- 7.4.4.2 Allylsilanes.- 7.4.5 New Routes to Boron Enolates.- 7.4.5.1 Dialkylboron halides.- 7.4.5.2 Other routes.- 7.5 References.- 8 Diels-Alder Reactions.- 8.1 Introduction.- 8.2 Alkenylboranes.- 8.2.1 Dialkylalkenylboranes.- 8.2.2 Dichloroalkenylboranes.- 8.2.3 Electronegatively Substituted Alkenylboronic Esters.- 8.2.4 (Silylalkenyl)boranes and Related Compounds.- 8.3 Butadienylboranes.- 8.4 Catalyzed Diels-Alder Reactions.- 8.4.1 Catalysts Derived from Tartaric Acid.- 8.4.2 Catalysts Containing Naphthyl Groups.- 8.4.3 Catalysts Derived from Amino Acids.- 8.5 References.- 9 Asymmetric Reductions and Miscellaneous Reactions.- 9.1 Introduction.- 9.2 Reductions with Alkylboranes.- 9.2.1 Introduction.- 9.2.2 Pinylboranes.- 9.3 Reductions with Asymmetric B-H Compounds.- 9.3.1 Introduction.- 9.3.2 Dimethylborolane.- 9.3.3 1,3,2-Oxazaborolidine Catalyzed Asymmetric Reductions.- 9.3.4 Remote Asymmetric Induction in ?-Keto Boronic Esters.- 9.3.5 Borohydride Type Reducing Agents.- 9.4 Other Borane Catalyzed Reactions.- 9.4.1 Alkynylation of Aldehydes.- 9.4.2 Addition of Diethylzinc to Aldehydes.- 9.4.3 Enantioselective Epoxide Opening by a Chiral Borane.- 9.4.4 Asymmetric Epoxidation.- 9.5 Asymmetric Hydrozirconation.- 9.6 References.- Author Index.