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.