Boronic Acids. Preparation and Applications in. Organic Synthesis, Edited by Dennis G. Hall. Volume 1. Second Completely Revised Edition

Transcription

1 Edited by Dennis G. Hall Boronic Acids Volume 1 Preparation and Applications in Medicine and Materials Organic Synthesis, Second Completely Revised Edition With a Foreword by Akira Suzuki WILEY- VCH WILEY-VCH Verlag GmbH & Co. KGaA

2 Contents to Volume 1 Foreword V Contents to Volume 2 XIII Preface XV List of Contributors XIX 1 Structure, Properties, and Preparation of Boronic Acid Derivatives: Overview oftheir Reactions and Applications I Dennis C. Hall 1.1 Introduction and Historical Background S tructure and Properties of Boronic Acid Derivatives General Types and Nomenclature of Boronic Acid Derivatives Boronic Acids Structure and Bonding Physical Properties and Handling Safety Considerations Acidic Character Chemical Stability Boronic Acid Derivatives Boroxines (Cyclic Anhydrides) Boronic Esters Acyloxy- and Diacyloxyboronates Dialkoxyboranes and Other Heterocyclic Boranes Diboronyl Esters Azaborolidines and Other Boron-Nitrogen Heterocycles Dihaloboranes and Dihydroallcylboranes Trifluoro- and Trihydroxyborate Salts Preparation of Boronic Acids and Their Esters Arylboronic Acids Electrophilic Trapping of Arylmetal Intermediates with Borates Transmetalation of Aryl Silanes and Stannanes 41

3 Coupling of Aiyl Halides with Diboronyl Reagents Direct Boronation by Transition Metal-Catalyzed Aromatic C-H Functionalization Cycloadditions of Alkynylboronates Other Methods Diboronic Acids Heterocyclic Boronic Acids Alkenylboronic Acids Electrophilic Trapping of Alkenylmetal Intermediates with Borates Transmetalation Methods Transition Metal-Catalyzed Coupling between Alkenyl Halides/ Triflates and Diboronyl Reagents Hydroboration of Alkynes Alkene Metathesis Diboronylation and Silaboration of Unsaturated Compounds Other Methods Alkynylboronic Acids Alleylboronic Acids Allylic Boronic Acids Chemoselective Transformations of Compounds Containing a Boronic Acid (Ester) Substituent Oxidative Methods Reductive Methods Generation and Reactions of a-boronyl-substituted Carbanions and Radicals Reactions of a-haloallcylboronic Esters Other Transformations Protection of Boronic Acids for Orthogonal Transformations Isolation and Characterization Recrystallization and Chromatography Solid Supports for Boronic Acid Immobilization and Purification Diethanolaminomethyl Polystyrene Other Solid-Supported Diol Resins Soluble Diol Approaches Analytical and Spectroscopic Methods for Boronic Acid Derivatives Melting Points, Combustion Analysis, and HPLC Mass Spectrometry Nuclear Magnetic Resonance Spectroscopy Other Spectroscopic Methods Overview of the Reactions of Boronic Acid Derivatives Metalation and Metal-Catalyzed Protodeboronation Oxidative Replacement of Boron Oxygenation Amination and Amidation Halodeboronation Carbon-Carbon Bond Forming Processes 85

4 Transition Metal-Catalyzed Cross-Coupling with Carbon Halides and Surrogates (Suzuki-Miyaura Cross-Coupling) Transition Metal-Catalyzed Insertions, Cycloisomerizations, and C-H Functionalizations Based on Transmetalation of Boronic Acids Heck-Type Coupling to Alkenes and Alkynes Rhodium- and Other Transition Metal-Catalyzed Additions to Alkenes, Carbonyl Compounds, and Imine Derivatives Diol-Catalyzed Additions of Boronic Esters to Unsaturated Carbonyl Compounds and Acetals Allylation of Carbonyl Compounds and Imine Derivatives Uncatalyzed Additions of Boronic Acids to Imines and Iminiums Carbon-Heteroatom Bond Forming Processes Copper-Catalyzed Coupling with Nucleophilic Oxygen and Nitrogen Compounds Other Reactions Overview of Other Applications of Boronic Acid Derivatives Use as Reaction Promoters and Catalysts 97 for Diols and Diamines Use as Protecting Groups Use as Supports for Immobilization, Derivatization, Affinity Purification, Analysis of Diols, Sugars, and Glycosylated Proteins and Cells Use as Receptors and Sensors for Carbohydrates and Other Small Molecules Use as Antimicrobial Agents and Enzyme Inhibitors Use in Neutron Capture Therapy for Cancer Use in Transmembrane Transport Use in Bioconjugation and Labeling Use in Chemical Biology Use in Materials Science and Self-Assembly 108 References 109 of Proteins and Cell Surface Metal-Catalyzed Borylation of C-H and C-Halogen Bonds of Alkanes, Alkenes, and Arenes for the Synthesis of Boronic Esters 135 Tatsuo Ishiyama and Norio Miyaura 2.1 Introduction Borylation of Halides and Trifiates via Coupling Compounds Borylation of Aryl Halides and Trifiates Alkenyl Halides and Trifiates 243 of H-B and B-B Allylic Halides, Allylic Acetates, and Allylic Alcohols Benzylic Halides Borylation via C-H Activation Aliphatic C-H Bonds Alkenyl C-H Bonds Aromatic C-H Bonds Catalytic Cycle 259

5 2.5 Summary 161 References Transition Metal-Catalyzed Element-Boryl Additions to Unsaturated Organic Compounds 171 Michinori Suginome and Toshimichi Ohmura 3.1 Introduction Diboration Diboron Reagents for Diboration Diboration ofalkynes Diboration ofalkenes, Allenes, 1,3-Dienes, and Methylenecyclopropanes Synthetic Applications of Diboration Products Silaboration Silylborane Reagents for Silaboration J Silaboration of Alkynes Silaboration of Alkenes, Allenes, 1,3-Dienes, and Methylenecyclopropanes Synthetic Application of Silaboration Products Carboboration Direct Addition: Cyanoboration and Alkynylboration Transmetalative Carboboration Miscellaneous Element-Boryl Additions Conclusion 208 References The Contemporary Suzuki-Miyaura Reaction 213 Corf Valente and Michael C. Organ 4.1 Introduction Preamble and Outlook A Brief History Mechanistic Aspects Developments Made in the Coupling of Nontrivial Substrates Rational Design of Ligands for Use in the Suzuki-Miyaura Reaction Organophosphine Ligands and Properties N-Heterocyclic Carbene Ligands and their Properties The Suzuki-Miyaura Cross-Coupling of Challenging Aryl Halides Overview of Challenges Organophosphine-Derived Catalysts NHC-Derived Catalysts The Suzuki-Miyaura Reaction Involving Unactivated Alkyl Halides Associated Difficulties Cross-Couplings Promoted by Phosphines and Amine-Based Ligands 235

6 Cross-Coupling-Proraoted NHC Ligands Asymmetric Suzuld-Miyaura Cross-Couplings Achieving Axial Chirality in the Suzuld-Miyaura Reaction Axial Chirality Induced by Chiral Ligands/Catalysts Axial Chirality Induced by Point Chirality Axial Chirality Induced by Planar Chirality Achieving Point Chirality in the Suzuki-Miyaura Reaction Iterative Suzuld-Miyaura Cross-Couplings ortho Metalation-Cross-coupling Iterations Triflating-Cross-Coupling Iterations Iterative Cross-Couplings via Orthogonal Reactivity Bifunctional Electrophiles Bifunctional Organoboranes Conclusions and Future Outlook 256 References Rhodium- and Palladium-Catalyzed Asymmetric Conjugate Additions of Organoboronic Acids 263 Cuillaume Berthon-Celloz and Tamio Hayashi 5.1 Introduction Rh-Catalyzed Enantioselective Conjugate Addition of Organoboron Reagents a,(3-unsaturated Unsaturated Ketones A Short History Mechanism Model for Enantioselection Organoboron Sources Other Than Boronic Acids Rh Precatalysts Ligand Systems a, 3-Unsaturated Aldehydes Enantioselective Addition to a,(3-unsaturated Esters and Amides Diastereoselective Conjugate Addition Fumarate and Maleimides Synthetically Useful Acceptors Conjugate Additions of Boryl and Silyl Groups Addition to Other Electron-Deficient Alkenes Arylmethylene Cyanoacetates Alkenylphosphonates Nitroalkene Sulfones Addition to eis-allylic Alcohols ,4-Addition/Enantioselective Protonation ,6-Conjugate Additions Rh-Catalyzed Enantioselective Conjugate Addition with Other Organometallic Reagents 296

7 5.2.6 Rh-Catalyzed Tandem Processes Tandem Enantioselective Conjugate Addition/Aldol Reaction Tandem Carborhodation/Conjugate Addition Pd-Catalyzed Enantioselective Conjugate Addition of Organoboron Reagents Introduction Addition to a, 3-Unsaturated Ketones Addition to a,p-unsaturated Esters, Amides, and Aldehydes Palladium-Catalyzed Tandem Processes Conclusions 306 References Recent Advances in Chan-Lam Coupling Reaction: Copper-Promoted C-Heteroatom Bond Cross-Coupling Reactions with Boronic Acids and Derivatives 315 Jennifer X. Qiao and Patrick Y.S. Lam 6.1 General Introduction C-0 Cross-Coupling with Arylboronic Acids Intermolecular C-0 Cross-Coupling Intramolecular C-0 Cross-Coupling C-N Cross-Coupling with Arylboronic Acids C-N (Nonheteroarene NH) Cross-Coupling Application of Chan-Lam Cross-Coupling in Solid-Phase Synthesis C-N (Heteroarene) Cross-Coupling Factor Xa Inhibitors Purines Heteroarene-Heteroarene Cross-Coupling Intramolecular C-N Cross-Coupling Catalytic Copper-Mediated C-N Cross-Coupling Additional N-Containing Substrates in Chan-Lam Cross-Coupling Substrate Selectivity and Reactivity in Chan-Lam Cross-Coupling Reaction C-N and C-0 Cross-Coupling with Alkenylboronic Acids C-N and C-0 Cross-Coupling with Boronic Acid Derivatives Boroxines, Boronic Esters, and Trifluoroborate Salts Alkylboronic Acids C-S and C-Se/C-Te Cross-Coupling Mechanistic Considerations Empirical Observations General Mechanistic Observations Mechanistic Study of the Catalytic 6.9 Other Organometalloids Conclusion 355 Reaction Note Added in Proof 355 References 357