Cover image for Boronic Acids : Preparation and Applications in Organic Synthesis, Medicine and Materials.
Boronic Acids : Preparation and Applications in Organic Synthesis, Medicine and Materials.
Title:
Boronic Acids : Preparation and Applications in Organic Synthesis, Medicine and Materials.
Author:
Hall, Dennis G.
ISBN:
9783527332144
Personal Author:
Edition:
2nd ed.
Physical Description:
1 online resource (799 pages)
Contents:
Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials -- Foreword -- Contents to Volume 1 -- Contents to Volume 2 -- Preface -- List of Contributors -- 1 Structure, Properties, and Preparation of Boronic Acid Derivatives: Overview of Their Reactions and Applications -- 1.1 Introduction and Historical Background -- 1.2 Structure and Properties of Boronic Acid Derivatives -- 1.2.1 General Types and Nomenclature of Boronic Acid Derivatives -- 1.2.2 Boronic Acids -- 1.2.2.1 Structure and Bonding -- 1.2.2.2 Physical Properties and Handling -- 1.2.2.3 Safety Considerations -- 1.2.2.4 Acidic Character -- 1.2.2.5 Chemical Stability -- 1.2.3 Boronic Acid Derivatives -- 1.2.3.1 Boroxines (Cyclic Anhydrides) -- 1.2.3.2 Boronic Esters -- 1.2.3.3 Acyloxy- and Diacyloxyboronates -- 1.2.3.4 Dialkoxyboranes and Other Heterocyclic Boranes -- 1.2.3.5 Diboronyl Esters -- 1.2.3.6 Azaborolidines and Other Boron-Nitrogen Heterocycles -- 1.2.3.7 Dihaloboranes and Dihydroalkylboranes -- 1.2.3.8 Trifluoro- and Trihydroxyborate Salts -- 1.3 Preparation of Boronic Acids and Their Esters -- 1.3.1 Arylboronic Acids -- 1.3.1.1 Electrophilic Trapping of Arylmetal Intermediates with Borates -- 1.3.1.2 Transmetalation of Aryl Silanes and Stannanes -- 1.3.1.3 Coupling of Aryl Halides with Diboronyl Reagents -- 1.3.1.4 Direct Boronation by Transition Metal-Catalyzed Aromatic C-H Functionalization -- 1.3.1.5 Cycloadditions of Alkynylboronates -- 1.3.1.6 Other Methods -- 1.3.2 Diboronic Acids -- 1.3.3 Heterocyclic Boronic Acids -- 1.3.4 Alkenylboronic Acids -- 1.3.4.1 Electrophilic Trapping of Alkenylmetal Intermediates with Borates -- 1.3.4.2 Transmetalation Methods -- 1.3.4.3 Transition Metal-Catalyzed Coupling between Alkenyl Halides/ Triflates and Diboronyl Reagents -- 1.3.4.4 Hydroboration of Alkynes -- 1.3.4.5 Alkene Metathesis.

1.3.4.6 Diboronylation and Silaboration of Unsaturated Compounds -- 1.3.4.7 Other Methods -- 1.3.5 Alkynylboronic Acids -- 1.3.6 Alkylboronic Acids -- 1.3.7 Allylic Boronic Acids -- 1.3.8 Chemoselective Transformations of Compounds Containing a Boronic Acid (Ester) Substituent -- 1.3.8.1 Oxidative Methods -- 1.3.8.2 Reductive Methods -- 1.3.8.3 Generation and Reactions of a-Boronyl-Substituted Carbanions and Radicals -- 1.3.8.4 Reactions of a-Haloalkylboronic Esters -- 1.3.8.5 Other Transformations -- 1.3.8.6 Protection of Boronic Acids for Orthogonal Transformations -- 1.4 Isolation and Characterization -- 1.4.1 Recrystallization and Chromatography -- 1.4.2 Solid Supports for Boronic Acid Immobilization and Purification -- 1.4.2.1 Diethanolaminomethyl Polystyrene -- 1.4.2.2 Other Solid-Supported Diol Resins -- 1.4.3 Analytical and Spectroscopic Methods for Boronic Acid Derivatives -- 1.4.3.1 Melting Points, Combustion Analysis, and HPLC -- 1.4.3.2 Mass Spectrometry -- 1.4.3.3 Nuclear Magnetic Resonance Spectroscopy -- 1.4.3.4 Other Spectroscopic Methods -- 1.5 Overview of the Reactions of Boronic Acid Derivatives -- 1.5.1 Metalation and Metal-Catalyzed Protodeboronation -- 1.5.2 Oxidative Replacement of Boron -- 1.5.2.1 Oxygenation -- 1.5.2.2 Amination and Amidation -- 1.5.2.3 Halodeboronation -- 1.5.3 Carbon-Carbon Bond Forming Processes -- 1.5.3.1 Transition Metal-Catalyzed Cross-Coupling with Carbon Halides and Surrogates (Suzuki-Miyaura Cross-Coupling) -- 1.5.3.2 Transition Metal-Catalyzed Insertions, Cycloisomerizations, and C-H Functionalizations Based on Transmetalation of Boronic Acids -- 1.5.3.3 Heck-Type Coupling to Alkenes and Alkynes -- 1.5.3.4 Rhodium- and Other Transition Metal-Catalyzed Additions to Alkenes, Carbonyl Compounds, and Imine Derivatives.

1.5.3.5 Diol-Catalyzed Additions of Boronic Esters to Unsaturated Carbonyl Compounds and Acetals -- 1.5.3.6 Allylation of Carbonyl Compounds and Imine Derivatives -- 1.5.3.7 Uncatalyzed Additions of Boronic Acids to Imines and Iminiums -- 1.5.4 Carbon-Heteroatom Bond Forming Processes -- 1.5.4.1 Copper-Catalyzed Coupling with Nucleophilic Oxygen and Nitrogen Compounds -- 1.5.5 Other Reactions -- 1.6 Overview of Other Applications of Boronic Acid Derivatives -- 1.6.1 Use as Reaction Promoters and Catalysts -- 1.6.2 Use as Protecting Groups for Diols and Diamines -- 1.6.3 Use as Supports for Immobilization, Derivatization, Affinity Purification, Analysis of Diols, Sugars, and Glycosylated Proteins and Cells -- 1.6.4 Use as Receptors and Sensors for Carbohydrates and Other Small Molecules -- 1.6.5 Use as Antimicrobial Agents and Enzyme Inhibitors -- 1.6.6 Use in Neutron Capture Therapy for Cancer -- 1.6.7 Use in Transmembrane Transport -- 1.6.8 Use in Bioconjugation and Labeling of Proteins and Cell Surface -- 1.6.9 Use in Chemical Biology -- 1.6.10 Use in Materials Science and Self-Assembly -- References -- 2 Metal-Catalyzed Borylation of C-H and C-Halogen Bonds of Alkanes, Alkenes, and Arenes for the Synthesis of Boronic Esters -- 2.1 Introduction -- 2.2 Borylation of Halides and Triflates via Coupling of H-B and B-B Compounds -- 2.2.1 Borylation of Aryl Halides and Triflates -- 2.2.2 Alkenyl Halides and Triflates -- 2.2.3 Allylic Halides, Allylic Acetates, and Allylic Alcohols -- 2.2.4 Benzylic Halides -- 2.3 Borylation via C-H Activation -- 2.3.1 Aliphatic C-H Bonds -- 2.3.2 Alkenyl C-H Bonds -- 2.3.3 Aromatic C-H Bonds -- 2.4 Catalytic Cycle -- 2.5 Summary -- References -- 3 Transition Metal-Catalyzed Element-Boryl Additions to Unsaturated Organic Compounds -- 3.1 Introduction -- 3.2 Diboration -- 3.2.1 Diboron Reagents for Diboration.

3.2.2 Diboration of Alkynes -- 3.2.3 Diboration of Alkenes, Allenes, 1,3-Dienes, and Methylenecyclopropanes -- 3.2.4 Synthetic Applications of Diboration Products -- 3.3 Silaboration -- 3.3.1 Silylborane Reagents for Silaboration -- 3.3.2 Silaboration of Alkynes -- 3.3.3 Silaboration of Alkenes, Allenes, 1,3-Dienes, and Methylenecyclopropanes -- 3.3.4 Synthetic Application of Silaboration Products -- 3.4 Carboboration -- 3.4.1 Direct Addition: Cyanoboration and Alkynylboration -- 3.4.2 Transmetalative Carboboration -- 3.5 Miscellaneous Element-Boryl Additions -- 3.6 Conclusion -- References -- 4 The Contemporary Suzuki-Miyaura Reaction -- 4.1 Introduction -- 4.1.1 Preamble and Outlook -- 4.1.2 A Brief History -- 4.1.3 Mechanistic Aspects -- 4.2 Developments Made in the Coupling of Nontrivial Substrates -- 4.2.1 Rational Design of Ligands for Use in the Suzuki-Miyaura Reaction -- 4.2.1.1 Organophosphine Ligands and Properties -- 4.2.1.2 N-Heterocyclic Carbene Ligands and their Properties -- 4.2.2 The Suzuki-Miyaura Cross-Coupling of Challenging Aryl Halides -- 4.2.2.1 Overview of Challenges -- 4.2.2.2 Organophosphine-Derived Catalysts -- 4.2.2.3 NHC-Derived Catalysts -- 4.2.3 The Suzuki-Miyaura Reaction Involving Unactivated Alkyl Halides -- 4.2.3.1 Associated Difficulties -- 4.2.3.2 Cross-Couplings Promoted by Phosphines and Amine-Based Ligands -- 4.2.3.3 Cross-Coupling-Promoted NHC Ligands -- 4.3 Asymmetric Suzuki-Miyaura Cross-Couplings -- 4.3.1 Achieving Axial Chirality in the Suzuki-Miyaura Reaction -- 4.3.1.1 Axial Chirality Induced by Chiral Ligands/Catalysts -- 4.3.1.2 Axial Chirality Induced by Point Chirality -- 4.3.1.3 Axial Chirality Induced by Planar Chirality -- 4.3.2 Achieving Point Chirality in the Suzuki-Miyaura Reaction -- 4.4 Iterative Suzuki-Miyaura Cross-Couplings -- 4.4.1 ortho Metalation-Cross-coupling Iterations.

4.4.2 Triflating-Cross-Coupling Iterations -- 4.4.3 Iterative Cross-Couplings via Orthogonal Reactivity -- 4.4.3.1 Bifunctional Electrophiles -- 4.4.3.2 Bifunctional Organoboranes -- 4.5 Conclusions and Future Outlook -- References -- 5 Rhodium- and Palladium-Catalyzed Asymmetric Conjugate Additions of Organoboronic Acids -- 5.1 Introduction -- 5.2 Rh-Catalyzed Enantioselective Conjugate Addition of Organoboron Reagents -- 5.2.1 α,β-Unsaturated Unsaturated Ketones -- 5.2.1.1 A Short History -- 5.2.1.2 Mechanism -- 5.2.1.3 Model for Enantioselection -- 5.2.1.4 Organoboron Sources Other Than Boronic Acids -- 5.2.1.5 Rh Precatalysts -- 5.2.1.6 Ligand Systems -- 5.2.1.7 α,β-Unsaturated Aldehydes -- 5.2.2 Enantioselective Addition to α,β-Unsaturated Esters and Amides -- 5.2.2.1 Diastereoselective Conjugate Addition -- 5.2.2.2 Fumarate and Maleimides -- 5.2.2.3 Synthetically Useful Acceptors -- 5.2.2.4 Conjugate Additions of Boryl and Silyl Groups -- 5.2.3 Addition to Other Electron-Deficient Alkenes -- 5.2.3.1 Arylmethylene Cyanoacetates -- 5.2.3.2 Alkenylphosphonates -- 5.2.3.3 Nitroalkene -- 5.2.3.4 Sulfones -- 5.2.3.5 Addition to cis-Allylic Alcohols -- 5.2.3.6 1,4-Addition/Enantioselective Protonation -- 5.2.4 1,6-Conjugate Additions -- 5.2.5 Rh-Catalyzed Enantioselective Conjugate Addition with Other Organometallic Reagents -- 5.2.6 Rh-Catalyzed Tandem Processes -- 5.2.6.1 Tandem Enantioselective Conjugate Addition/Aldol Reaction -- 5.2.6.2 Tandem Carborhodation/Conjugate Addition -- 5.3 Pd-Catalyzed Enantioselective Conjugate Addition of Organoboron Reagents -- 5.3.1 Introduction -- 5.3.2 Addition to α,β-Unsaturated Ketones -- 5.3.3 Addition to α,β-Unsaturated Esters, Amides, and Aldehydes -- 5.3.4 Palladium-Catalyzed Tandem Processes -- 5.4 Conclusions -- References.

6 Recent Advances in Chan-Lam Coupling Reaction: Copper-Promoted C-Heteroatom Bond Cross-Coupling Reactions with Boronic Acids and Derivatives.
Abstract:
Following the huge success of the first edition, which has become THE reference source for everyone working in the field, this long-awaited, completely updated edition features almost 50% new content. The world-renowned chemist Prof Dennis Hall is joined by a select group of top authors to cover all modern aspects of boronic acid derivatives in one comprehensive handbook. The experimental procedures described make for extremely useful reading. From the reviews of the first edition: "...deserves to be on the bookshelf of all synthetic chemists, whether in discovery or process chemistry.".
Local Note:
Electronic reproduction. Ann Arbor, Michigan : ProQuest Ebook Central, 2017. Available via World Wide Web. Access may be limited to ProQuest Ebook Central affiliated libraries.
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