Boronic Acids (eBook)

Dennis Hall obtained his PhD in 1995 from Université de Sherbrooke (Canada), under the direction of Prof. Pierre Deslongchamps. Following a two-year stay at UC Berkeley as an NSERC Postdoctoral Fellow in the laboratory of Prof. Peter Schultz, he initiated his independent career in 1997 at the University of Alberta (Edmonton, Canada) where he is currently University Professor of Chemistry. The unifying theme of his research program is the development of new applications of organoboronic acid derivatives in organic synthesis, catalysis, and chemical biology. He has co-authored more than 100 publications with over 80 in the fi eld of organoboron chemistry. Recent awards include the 2008 Steacie Prize for Natural Sciences (National Research Council of Canada), and the Royal Society of Canada 2009 Rutherford Memorial Medal in Chemistry.

Introduction: Properties, Preparation, Overview of Application
Metal-Catalyzed Borylation of C-X and C-H Bonds for the Synthesis of Boronic Esters
Transition-Metal Catalyzed Sila- and Diborylation of Alkenes, Allenes, and Alkynes
The Contemporary Suzuki-Miyaura Reaction
Rhodium and Palladium-Catalyzed Asymmetric Conjugate Additions of Organoboronic Acids
Recent Advances in Chan-Lam Coupling Reaction: Copper-Promoted C-Heteroatom Bond Cross-Coupling Reactions with Boronic Acids and Derivatives
Transition-Metal Catalyzed Desulfitative Coupling of Thioorganic Compounds with Boronic Acids
Catalytic Additions of Allylic Boronates to Carbonyl and Imine Derivatives
Recent Advances in Nucleophilic Addition Reactions of Organoboronic Acids and their Derivatives to Unsaturated C?N Functionalities
Asymmetric Homologation of Boronic Esters with Lithiated Carbamates
Organotrifluoroborates: Organoboron Reagents for the 21st Century
Boronic Acids as Catalysts
Applications of boronic acids in chemical biology and medicinal chemistry
Boronic Acids in Materials Chemistry
VOLUME 1

Preface

STRUCTURE, PROPERTIES, AND PREPARATION OF BORONIC ACID DERIVATIVES: OVERVIEW OF THEIR REACTIONS AND APPLICATIONS
Introduction and Historical Background
Structure and Properties of Boronic Acid Derivatives
Preparation of Boronic Acids and Their Esters
Isolation and Characterization
Overview of the Reactions of Boronic Acid Derivatives
Overview of Other Applications of Boronic Acid Derivatives

METAL-CATALYZED BORYLATION OF C-H AND C-HALOGEN BONDS OF ALKANES, ALKENES, AND ARENES FOR THE SYNTHESIS OF BORONIC ESTERS
Introduction
Borylation of Halides and Triflates via Coupling of H-B and B-B Compounds
Borylation via C-H Activation
Catalytic Cycle
Summary

TRANSITION METAL-CATALYZED ELEMENT-BORYL ADDITIONS TO UNSATURATED ORGANIC COMPOUNDS
Introduction
Diboration
Silaboration
Carboboration
Miscellaneous Element-Boryl Additions
Conclusions

THE CONTEMPORARY SUZUKI-MIYAURA REACTION
Introduction
Developments Made in the Coupling of Nontrivial Substrates
Asymmetric Suzuki-Miyaura Cross-Couplings
Iterative Suzuki-Miyaura Cross-Couplings
Conclusions and Future Outlook

RHODIUM- AND PALLADIUM-CATALYZED ASYMMETRIC CONJUGATE ADDITIONS OF ORGANOBORONIC ACIDS
Introduction
Rh-Catalyzed Enantioselective Conjugate Addition of Organoboron Reagents
Pd-Catalyzed Enantioselective Conjugate Addition of Organoboron Reagents
Conclusions

RECENT ADVANCES IN CHAN-LAM COUPLING REACTION: COPPER-PROMOTED C-HETEROATOM BOND CROSS-COUPLING REACTIONS WITH BORONIC ACIDS AND DERIVATIVES
General Introduction
C-O Cross-Coupling with Arylboronic Acids
C-N Cross-Coupling with Arylboronic Acids
Substrate Selectivity and Reactivity in Chan-Lam Cross-Coupling Reaction
C-N and C-O Cross-Coupling with Alkenylboronic Acids
C-N and C-O Cross-Coupling with Boronic Acid Derivatives
C-S and C-Se/C-Te Cross-Coupling
Mechanistic Considerations
Other Organometalloids
Conclusion

VOLUME 2

TRANSITION METAL-CATALYZED DESULFITATIVE COUPLING OF THIOORGANIC COMPOUNDS WITH BORONIC ACIDS
General Introduction
Boronic Acid-Thioorganic C-S Desulfitative Cross-Couplings Using Catalytic Nickel or Palladium
Thioorganic C-S Desulfitative Cross-Couplings Using Only Catalytic Copper
Miscellaneous
Conclusions

CATALYTIC ADDITIONS OF ALLYLIC BORONATES TO CARBONYL AND IMINE DERIVATIVES
Introduction
Additions to Aldehydes
Additions to Ketones
Additions to Imine Derivatives
Conclusions

RECENT ADVANCES IN NUCLEOPHILIC ADDITION REACTIONS OF ORGANOBORONIC ACIDS AND THEIR DERIVATIVES TO UNSATURATED C-N FUNCTIONALITIES
Introduction
Recent Advances in the Petasis Borono-Mannich Reaction
Reactions of N-Acyliminium Ions with Organoboronic Acids and Their Derivatives
Advances in Metal-Catalyzed Additions with Organoboronic Acids and Their Derivatives
Conclusions

ASYMMETRIC HOMOLOGATION OF BORONIC ESTERS WITH LITHIATED CARBAMATES, EPOXIDES, AND AZIRIDINES
Introduction
Lithiated Primary Alkyl Carbamates for the Homologation of Boranes and Boronic Esters
Lithiated Secondary Carbamates for the Homologation of Boranes and Boronic Esters
Benzylic N-Linked Lithiated Carbamates for the Homologation of Trialkylboranes
Lithiated Epoxides for the Homologation of Boronic Esters
Lithiated Aziridines for the Homologation of Boronic Esters
Conclusions

ORGANOTRIFLUOROBORATES: ORGANOBORON REAGENTS FOR THE TWENTY-FIRST CENTURY
Introduction
Synthetic Approaches to Organotrifluoroborates
Elaboration of Organotrifluoroborates via Transformations of Pendant Functional Groups
Transition Metal-Catalyzed Processes
Miscellaneous Reactions of Organotrifluoroborates
Carbon-Carbon Bond-Forming Reactions with Activated Electrophiles
Conclusions

BORATE AND BORONIC ACID DERIVATIVES AS CATALYSTS IN ORGANIC SYNTHESIS
Introduction
Nonchiral Boron-Based Catalysis
Chiral Boron-Based Catalysis
Conclusion

APPLICATIONS OF BORONIC ACIDS IN CHEMICAL BIOLOGY AND MEDICINAL CHEMISTRY
Introduction
Boronic Acids as Potential Medicinal Agents
Probes for Detecting Reactive Oxygen Species
MRI and PET Agents for in vivo Carbohydrate Ima

"Overall, Hall's book provides an excellent starting point from which to explore the chemistry of boronic acids, but also one which gives a perspective on likely future developments. A clear positive feedback loop emerges from the material herein, whereby the take-up of new reactions and applications leads to demands for improved methods for the preparation of boronate substrates which in turn offers wider scope for further new reactivity patterns to be exploited. Hall states at the outset that his task was to provide the first comprehensive book on the chemistry and biology of boronic acids; this he has done, but at the pace of current developments, a second edition might not be so long in arriving."
Angewandte Chemie IE

"For some reason, this excellent book didn't get reviewed as soon as it was published but we would like to remedy this now...In conclusion, this excellent book deserves to be on the bookshelf of all synthetic chemists, whether in discovery or process chemistry."
Organic Process Research & Development Journal

"Da die synthetische Nützlichkeit von Boronsäuren und Derivaten im Buch eindrücklich beschrieben wird, erhält der Leser auf jeden Fall einigen Benefit für eigene Ideen, auch wenn er nicht sofort alle präsentierten Reaktionstypen nutzt."
http://www.organische-chemie.ch/

"...eine hervorragende Monographie zur Chemie der Boronsäuren, die geeignet ist, den Forschungen auf diesem Gebiet neue Impulse zu verleihen. Es war das erklärte Ziel des Herausgebers, die erste umfassende Monographie über die Chemie und biologischen Eigenschaften von Boronsäuren vorzulegen. Dies ist ihm hervorragend gelungen, und angesichts der rasanten Entwicklungen auf diesem Gebiet wird wohl bald eine zweite Ausgabe folgen."
Angewandte Chemie