John Wiley & Sons Inc. 2010. - 402 p.
This book explores the use of silver in organic synthesis. Silver and its salts and complexes have figured significantly in the history of chemistry, recognized for their special conductive properties, use in photography, and even biological activities. Notwithstanding the importance of these areas the broader use of silver in chemistry, and more specifically in synthesis, has lagged behind that of other coinage metals. That is changing. One now finds silver as a key component of much that is nano, including nano-rods, spheres, sheets, clusters, prisms, membranes, plates, pillars, cubes, bowls, fibers, wires, gels, and sensors. Increasing interest is also being directed at its use and that of other coinage metals in improving synthetic procedures and in enabling new ones. This book provides an insightful overview of how silver figures in these new developments.
CONTENTS
Foreword
Preface
Contributors
Silver Alkyls, Alkenyls, Aryls, and Alkynyls in Organic Synthesis
Rebecca H. Pouwer and Craig M. Williams
Introduction
Csp3-Ag
Synthesis, Stability, and Reactivity of Alkylsilver Compounds
Synthesis and Stability of Perfluoroalkylsilver Compounds
Reactivity of Perfluoroalkylsilver Compounds
Csp2-Ag
Synthesis and Stability of Arylsilver Compounds
Reactivity of Arylsilver Compounds
Synthesis and Stability of Perfluoroarylsilver Compounds
Reactivity of Perfluoroarylsilver Compounds
Synthesis, Stability, and Reactivity of Alkenylsilver Compounds
Synthesis and Reactivity of Allenylsilver Compounds
Synthesis of Perfluoroalkenylsilver Compounds
Reactivity of Perfluoroalkenylsilver Compounds
Synthesis and Reactivity of Silver-Substituted Diazomethyl Compounds
Csp-Ag
Synthesis of Silver Acetylides
Reactivity of Silver Acetylides
Addition to Activated Carbonyls and Iminium Ions
Nucleophilic Substitution of Activated Heteroaromatics
Reaction with Alkyl Halides
Coupling Reactions
Reactions with Non-carbon Electrophiles
Fragmentation
Desilylation
Conclusion
References
Cycloaddition Reactions
Alex M. Szpilman and Erick M. Carreira
Introduction
[2+2]Cycloadditions
[3+2]Cycloadditions
[3+2] Cycloadditions of Azomethine Ylides
Discovery and Development of the Silver-Catalyzed [3+2] Cycloaddition of Azomethine Ylides
Auxiliary-Based Asymmetric [3+2] Cycloadditions
Catalytic Asymmetric [3+2] Cycloadditions
Selected Applications and Extensions of Azomethine [3+2] Cycloadditions
Other [3+2] Cycloadditions
[3+3] Cycloadditions
[4+2] Cycloadditions
Concluding Remarks
References
Sigmatropic Rearrangements and Related Processes Promoted by Silver
Jean-Marc Weibel, Aur_elien Blanc, and Patrick Pale
Introduction
Wolff and Adt–Eistert Rearrangements and Related Reactions
Ring Rearrangements
Halogenoamines
Cyclopropane Derivatives
Cubane Derivatives
Halogenocyclopropane Derivatives
[3,3]-Sigmatropic Rearrangements
With Acyl as Migrating Groups
With Vinyl as Migrating Groups
With Migrating Groups Analogous to Acyl
[3,3]-Sigmatropic Rearrangement and Cyclization Cascades
[2,3]-Sigmatropic Rearrangements
[1,2]-Sigmatropic Rearrangements
1,2-Aryl or Alkenyl Migration
1,2-Alkyl Migration
1,2- or 1,5-Alkyl Migration
1,2 versus 3,3 Migrations
Miscellaneous
Conclusion
References
Silver(I)-Mediated Electrocyclic Processes 117
Tina N. Grant and Frederick G. West
Introduction
Ring-Opening Reactions of Halocyclopropanes
Silver(I)-Assisted Ring-Opening Reactions
Nucleophilic Trapping of Cationic Intermediates
Solvolysis Reactions
Intramolecular Trapping with Heteronucleophiles
Diastereoselective Reactions
Carbon–Carbon Bond Formation
The Silver(I)-Promoted Nazarov Reaction
Development and Initial Findings
Interrupted Nazarov Reactions
Concluding Remarks
References
Silver-Catalyzed Cycloisomerization Reactions
Philippe Belmont
Introduction
Cycloisomerization of C=O onto C=C=C
Cycloisomerization of C=O onto C?C
Cycloisomerization of C=N onto C=C=C
Cycloisomerization of C=N onto C?C
Ene–Yne Cycloisomerization: C=C onto C?C
Other Transformations
Conclusion
References
Silver-Catalyzed Nitrene Transfer Reactions
Zigang Li, David A. Capretto, and Chuan He
Introduction
Aziridination
Chloramine-T as Nitrene Precursor
Iminoiodanes as Nitrene Precursors
Heterogenous Silver Catalysis
Sulfide and Sulfoxide Imination
Amidation
Intramolecular Amidation
Intermolecular Amination with Phenanthroline Ligands
Intermolecular Amination Based on Pyrazolylborate Ligands
Conclusion
References
Silver-Catalyzed Silylene Transfer
Tom G. Driver
Introduction
Reactivity and Attributes of Metal Silylenoids and Silylmetal Complexes
Synthesis of Transition Metal Complexes of Silylenes
Reactivity of Transition Metal Silylenoids
Transition Metal Silylenoid Complex–Catalyzed Hydrosilation Reactions
Transition Metal Silylenoid–Catalyzed Atom Transfer Reactions
Silacyclopropanes as Important Synthetic Intermediates
Silver-Mediated Transfer of Di-tert-Butylsilylene to Olefins
Silver-Mediated Transfer of Di-tert-Butylsilylene to Acetylenes
Silver-Mediated Transfer of Di-tert-Butylsilylene to Carbonyl Compounds
Silver-Mediated Transfer of Di-tert-Butylsilylene to Imines
Silver-Mediated Di-tert-Butylsilylene Insertion into C – O Bonds
Conclusion
References
Silver Carbenoids
Carl J. Lovely
Introduction
Wolff Rearrangement
Carbene Transfer Reactions to п Bonds
Aziridination
Cyclopropanation
Formation and Reactions of Ylides
C – Hal Addition–Rearrangement
C – S Addition–Rearrangement
C – H Insertion
N – H Insertion
Ring Expansion Reactions
Intermediacy of Silver Carbenes
Miscellaneous Reactions Involving Silver Carbenoids
Summary
Acknowledgments
References
Aldol and Related Processes
Masanori Kawasaki and Hisashi Yamamoto
Introduction
Allylation Reaction Using Allyltributyltin
Allylation Reaction Using Allylsilanes
Aldol Reaction Using Tin Enolates
Aldol Reaction Using Silyl Enol Ethers
Mannich Reaction
Nitrosoaldol Reaction
Aldol Reaction with Azodicarboxylate
Conclusion
References
Coupling Reactions Promoted by Silver
Jean-Marc Weibel, Aur_elien Blanc, and Patrick Pale
Introduction
sp3–sp3 Coupling Reactions Promoted by Silver Salts
sp3–sp2 Coupling Reactions Promoted by Silver Salts
sp3–sp Coupling Reactions Promoted by Silver Salts
sp2–sp2 Coupling Reactions Promoted by Silver Salts
Homocoupling of Vinyl- or Arylsilver Species
Organosilver Species as Nucleophilic Reagents
Silver as a Lewis Acid Reagent
Silver as a Halogen Scavenger
Silver in Pd-Catalyzed Couplings
Silver in PdII-Promoted Electrophilic
Substitution of Arenes (C-H Activation)
Silver as Reagent for Decarboxylative Coupling
sp2–sp Coupling Reactions Promoted by Silver Salts
Organosilver Species as Nucleophilic Reagents
Organosilver Species in Transmetallations
Silver as a Lewis Acid Reagent
Organosilver Species as Intermediates in Catalyzed Enyne or Arylyne Synthesis
sp–sp Coupling Reactions Promoted by Silver Salts
Conclusion
References
Supramolecular Chemistry of Silver
Wei-Yin Sun, Zheng-Shuai Bai, and Jin-Quan Yu
Introduction
Cage-Like Complexes
Tube-Like Compounds
Polycatenanes with Silver(I)
Polyrotaxanes with Silver(I)
Silver(I) Coordination Polymers with Specific Topology
Conclusion
Acknowledgments
References
A Critical Comparison: Copper, Silver, and Gold
A. Stephen K. Hashmi
Introduction
Reactions Catalyzed by Copper, Silver, or Gold
Aldehyde–Alkyne–Amine Coupling
Carbene Insertion Reactions
In Silico Comparison of Organocopper(I), Organosilver(I), and Organogold(I) -Ate Compounds
Cyclization of ortho-alkynylbenzaldehydes
Allenyl Ketones: The Cycloisomerization to Furans
A Thiol in the Substrate: The Cyclization of ?-Thioallenes
Furans by Propargyl Claisen Reaction
Tandem Cyclization/Pinacol Rearrangement
Furanones by Domino Heterocyclization/1,2 Shift
Conia-ene Reaction
Reactions Catalyzed by Silver or Gold
Cyclization of N-Propargylcarboxamides
Dake’s Pyrrole Synthesis
Combination with Organocatalysis
Vinylallenes Deliver Cyclopentadienes
?-Pyrones by a Cascade Reaction
Dihydrofurans from Propargyl Esters
Methylene Butyrolactones by Addition of Carboxylates to Alkynes
Hydroarylation of Allenes
Different Products by Silver and Gold Catalysts
The Epoxide–Alkyne Reaction
The Carbonyl–Alkyne Reaction
Reactions Catalyzed by Copper or Silver
General Trends
Pyrroles by Hydroamination
Copper/Silver Cocatalysis
Carbonylations
Conclusion
References
Index
This book explores the use of silver in organic synthesis. Silver and its salts and complexes have figured significantly in the history of chemistry, recognized for their special conductive properties, use in photography, and even biological activities. Notwithstanding the importance of these areas the broader use of silver in chemistry, and more specifically in synthesis, has lagged behind that of other coinage metals. That is changing. One now finds silver as a key component of much that is nano, including nano-rods, spheres, sheets, clusters, prisms, membranes, plates, pillars, cubes, bowls, fibers, wires, gels, and sensors. Increasing interest is also being directed at its use and that of other coinage metals in improving synthetic procedures and in enabling new ones. This book provides an insightful overview of how silver figures in these new developments.
CONTENTS
Foreword
Preface
Contributors
Silver Alkyls, Alkenyls, Aryls, and Alkynyls in Organic Synthesis
Rebecca H. Pouwer and Craig M. Williams
Introduction
Csp3-Ag
Synthesis, Stability, and Reactivity of Alkylsilver Compounds
Synthesis and Stability of Perfluoroalkylsilver Compounds
Reactivity of Perfluoroalkylsilver Compounds
Csp2-Ag
Synthesis and Stability of Arylsilver Compounds
Reactivity of Arylsilver Compounds
Synthesis and Stability of Perfluoroarylsilver Compounds
Reactivity of Perfluoroarylsilver Compounds
Synthesis, Stability, and Reactivity of Alkenylsilver Compounds
Synthesis and Reactivity of Allenylsilver Compounds
Synthesis of Perfluoroalkenylsilver Compounds
Reactivity of Perfluoroalkenylsilver Compounds
Synthesis and Reactivity of Silver-Substituted Diazomethyl Compounds
Csp-Ag
Synthesis of Silver Acetylides
Reactivity of Silver Acetylides
Addition to Activated Carbonyls and Iminium Ions
Nucleophilic Substitution of Activated Heteroaromatics
Reaction with Alkyl Halides
Coupling Reactions
Reactions with Non-carbon Electrophiles
Fragmentation
Desilylation
Conclusion
References
Cycloaddition Reactions
Alex M. Szpilman and Erick M. Carreira
Introduction
[2+2]Cycloadditions
[3+2]Cycloadditions
[3+2] Cycloadditions of Azomethine Ylides
Discovery and Development of the Silver-Catalyzed [3+2] Cycloaddition of Azomethine Ylides
Auxiliary-Based Asymmetric [3+2] Cycloadditions
Catalytic Asymmetric [3+2] Cycloadditions
Selected Applications and Extensions of Azomethine [3+2] Cycloadditions
Other [3+2] Cycloadditions
[3+3] Cycloadditions
[4+2] Cycloadditions
Concluding Remarks
References
Sigmatropic Rearrangements and Related Processes Promoted by Silver
Jean-Marc Weibel, Aur_elien Blanc, and Patrick Pale
Introduction
Wolff and Adt–Eistert Rearrangements and Related Reactions
Ring Rearrangements
Halogenoamines
Cyclopropane Derivatives
Cubane Derivatives
Halogenocyclopropane Derivatives
[3,3]-Sigmatropic Rearrangements
With Acyl as Migrating Groups
With Vinyl as Migrating Groups
With Migrating Groups Analogous to Acyl
[3,3]-Sigmatropic Rearrangement and Cyclization Cascades
[2,3]-Sigmatropic Rearrangements
[1,2]-Sigmatropic Rearrangements
1,2-Aryl or Alkenyl Migration
1,2-Alkyl Migration
1,2- or 1,5-Alkyl Migration
1,2 versus 3,3 Migrations
Miscellaneous
Conclusion
References
Silver(I)-Mediated Electrocyclic Processes 117
Tina N. Grant and Frederick G. West
Introduction
Ring-Opening Reactions of Halocyclopropanes
Silver(I)-Assisted Ring-Opening Reactions
Nucleophilic Trapping of Cationic Intermediates
Solvolysis Reactions
Intramolecular Trapping with Heteronucleophiles
Diastereoselective Reactions
Carbon–Carbon Bond Formation
The Silver(I)-Promoted Nazarov Reaction
Development and Initial Findings
Interrupted Nazarov Reactions
Concluding Remarks
References
Silver-Catalyzed Cycloisomerization Reactions
Philippe Belmont
Introduction
Cycloisomerization of C=O onto C=C=C
Cycloisomerization of C=O onto C?C
Cycloisomerization of C=N onto C=C=C
Cycloisomerization of C=N onto C?C
Ene–Yne Cycloisomerization: C=C onto C?C
Other Transformations
Conclusion
References
Silver-Catalyzed Nitrene Transfer Reactions
Zigang Li, David A. Capretto, and Chuan He
Introduction
Aziridination
Chloramine-T as Nitrene Precursor
Iminoiodanes as Nitrene Precursors
Heterogenous Silver Catalysis
Sulfide and Sulfoxide Imination
Amidation
Intramolecular Amidation
Intermolecular Amination with Phenanthroline Ligands
Intermolecular Amination Based on Pyrazolylborate Ligands
Conclusion
References
Silver-Catalyzed Silylene Transfer
Tom G. Driver
Introduction
Reactivity and Attributes of Metal Silylenoids and Silylmetal Complexes
Synthesis of Transition Metal Complexes of Silylenes
Reactivity of Transition Metal Silylenoids
Transition Metal Silylenoid Complex–Catalyzed Hydrosilation Reactions
Transition Metal Silylenoid–Catalyzed Atom Transfer Reactions
Silacyclopropanes as Important Synthetic Intermediates
Silver-Mediated Transfer of Di-tert-Butylsilylene to Olefins
Silver-Mediated Transfer of Di-tert-Butylsilylene to Acetylenes
Silver-Mediated Transfer of Di-tert-Butylsilylene to Carbonyl Compounds
Silver-Mediated Transfer of Di-tert-Butylsilylene to Imines
Silver-Mediated Di-tert-Butylsilylene Insertion into C – O Bonds
Conclusion
References
Silver Carbenoids
Carl J. Lovely
Introduction
Wolff Rearrangement
Carbene Transfer Reactions to п Bonds
Aziridination
Cyclopropanation
Formation and Reactions of Ylides
C – Hal Addition–Rearrangement
C – S Addition–Rearrangement
C – H Insertion
N – H Insertion
Ring Expansion Reactions
Intermediacy of Silver Carbenes
Miscellaneous Reactions Involving Silver Carbenoids
Summary
Acknowledgments
References
Aldol and Related Processes
Masanori Kawasaki and Hisashi Yamamoto
Introduction
Allylation Reaction Using Allyltributyltin
Allylation Reaction Using Allylsilanes
Aldol Reaction Using Tin Enolates
Aldol Reaction Using Silyl Enol Ethers
Mannich Reaction
Nitrosoaldol Reaction
Aldol Reaction with Azodicarboxylate
Conclusion
References
Coupling Reactions Promoted by Silver
Jean-Marc Weibel, Aur_elien Blanc, and Patrick Pale
Introduction
sp3–sp3 Coupling Reactions Promoted by Silver Salts
sp3–sp2 Coupling Reactions Promoted by Silver Salts
sp3–sp Coupling Reactions Promoted by Silver Salts
sp2–sp2 Coupling Reactions Promoted by Silver Salts
Homocoupling of Vinyl- or Arylsilver Species
Organosilver Species as Nucleophilic Reagents
Silver as a Lewis Acid Reagent
Silver as a Halogen Scavenger
Silver in Pd-Catalyzed Couplings
Silver in PdII-Promoted Electrophilic
Substitution of Arenes (C-H Activation)
Silver as Reagent for Decarboxylative Coupling
sp2–sp Coupling Reactions Promoted by Silver Salts
Organosilver Species as Nucleophilic Reagents
Organosilver Species in Transmetallations
Silver as a Lewis Acid Reagent
Organosilver Species as Intermediates in Catalyzed Enyne or Arylyne Synthesis
sp–sp Coupling Reactions Promoted by Silver Salts
Conclusion
References
Supramolecular Chemistry of Silver
Wei-Yin Sun, Zheng-Shuai Bai, and Jin-Quan Yu
Introduction
Cage-Like Complexes
Tube-Like Compounds
Polycatenanes with Silver(I)
Polyrotaxanes with Silver(I)
Silver(I) Coordination Polymers with Specific Topology
Conclusion
Acknowledgments
References
A Critical Comparison: Copper, Silver, and Gold
A. Stephen K. Hashmi
Introduction
Reactions Catalyzed by Copper, Silver, or Gold
Aldehyde–Alkyne–Amine Coupling
Carbene Insertion Reactions
In Silico Comparison of Organocopper(I), Organosilver(I), and Organogold(I) -Ate Compounds
Cyclization of ortho-alkynylbenzaldehydes
Allenyl Ketones: The Cycloisomerization to Furans
A Thiol in the Substrate: The Cyclization of ?-Thioallenes
Furans by Propargyl Claisen Reaction
Tandem Cyclization/Pinacol Rearrangement
Furanones by Domino Heterocyclization/1,2 Shift
Conia-ene Reaction
Reactions Catalyzed by Silver or Gold
Cyclization of N-Propargylcarboxamides
Dake’s Pyrrole Synthesis
Combination with Organocatalysis
Vinylallenes Deliver Cyclopentadienes
?-Pyrones by a Cascade Reaction
Dihydrofurans from Propargyl Esters
Methylene Butyrolactones by Addition of Carboxylates to Alkynes
Hydroarylation of Allenes
Different Products by Silver and Gold Catalysts
The Epoxide–Alkyne Reaction
The Carbonyl–Alkyne Reaction
Reactions Catalyzed by Copper or Silver
General Trends
Pyrroles by Hydroamination
Copper/Silver Cocatalysis
Carbonylations
Conclusion
References
Index