Оглавление
Группа авторов. Polar Organometallic Reagents
Table of Contents
List of Tables
List of Illustrations
Guide
Pages
Polar Organometallic Reagents. Synthesis, Structure, Properties and Applications
Preface
List of Contributors
Acknowledgements
1 The Road to Aromatic Functionalization by Mixed‐metal Ate Chemistry
1.1 Introduction
1.2 Deprotonation of Aromatics. 1.2.1 Monometallic Bases
1.2.2 Bimetallic Bases. 1.2.2.1 Group 1/1 Reagents
1.2.2.2 Group 1/2 Reagents
1.3 Aromatic Ate Complex Chemistry: Metal/Halogen Exchange. 1.3.1 Introduction
1.3.2 Zincates
1.3.3 Cuprates
1.3.4 Solid‐phase Synthesis
1.4 Deprotonation Using Ate Complexes. 1.4.1 Introduction
1.4.2 Zincates
1.4.3 Cadmates
1.4.4 Aluminates
1.4.5 Cuprates
1.4.6 Argentates
1.5 Concluding Remarks
References
2 Structural Evidence for Synergistic Bimetallic Main Group Bases
2.1 General Introduction
2.2 Homometallic Bases
2.2.1 Carbanionic Lithium Reagents
2.2.2 Heavier Carbanionic Alkali Metal Reagents
2.2.3 Alkali Metal Amides
2.3 Heterometallic Bases
2.3.1 Heteroalkali Metal Bases
2.3.2 Alkali Metal Magnesiate Chemistry
2.3.3 Early Signs of Synergistic Behaviour in Zincate Chemistry
2.3.4 Lithium TMP–Zincate Chemistry
2.3.5 Sodium TMP–Zincate Chemistry
2.3.6 Lithium Chloride (Turbo Charged) TMP–Zinc Chemistry
2.3.7 Indirect TMP Zincation
2.3.8 Alkali Metal Group 13 Ates
2.3.9 Bimetallic Complexes Without an Alkali Metal Component
2.4 Outlook
References
3 Turbo Charging Group 2 Reagents for Metathesis, Metalation, and Catalysis
3.1 Introduction and Historical Context: Monometallic s‐block Reagents and Their Utility
3.2 Heterobimetallic Reagents for Selective Metalation. 3.2.1 Ate Complexes and Superbases
3.2.2 Lithium, Sodium, Potassium Magnesiates, MMgX3
3.2.3 Salt Effects and Magnesiate Formation
3.2.3.1 ‘Turbo‐Grignards’ for Selective Metalation
3.2.3.2 Turbo–Hauser Bases
3.2.4 Ate Complexes of the Heavier Alkaline Earth Elements Ca, Sr, and Ba
3.2.4.1 Alkyl Calciate, Strontiate, and Bariate Derivatives, MM′R3 (M = Li, Na, K; M′ = Ca, Sr, Ba; R = alkyl)
3.2.4.2 Alkoxo and Aryloxo Calciate, Strontiate, and Bariate Derivatives, MM′(OR/Ar)3 (M = Li, Na, K; M′ = Ca, Sr, Ba)
3.2.4.3 Amido Calciate, Strontiate, and Bariate Derivatives, MM′(OR/Ar)3 (M = Li, Na, K; M′ = Ca, Sr, Ba)
3.3 Homogeneous Catalysis by s‐block Reagents
3.4 Outlook: Turbo Charging the Turbo Reagents and Prospects for Catalysis
References
4 Mechanisms in Heterobimetallic Reactivity: Experimental and Computational Insights for Catalyst Design in Small Molecule Activation and Polymer Synthesis
4.1 Introduction and Scope of the Chapter
4.2 Small Molecule Activation and Catalysis
4.2.1 Hydrogen Activation
4.2.2 Dinitrogen Activation
4.2.3 CO2 Activation
4.3 Polymerization Catalysis. 4.3.1 Olefin Polymerization
4.3.1.1 Metallocene‐based Heterobimetallic Catalysts
4.3.1.2 Constrained Geometries Heterobimetallic Catalysts
4.3.1.3 Late Transition Metal Heterobimetallic Catalysts
4.3.2 Ring‐opening Polymerization
4.3.2.1 ROP M1–O–M2 Heterobimetallic Catalysts
4.3.2.2 Other Heterobimetallic Catalysts for ROP
4.3.3 Ring‐opening Copolymerization of Epoxides and Carbon Dioxide
4.3.3.1 Mechanistic Insight into Homobimetallic Catalysts
4.3.3.2 ROCOP Heterobimetallic Catalysts
4.4 Conclusion
References
5 Cationic Compounds of Group 13 Elements: Entry Point to the p‐block for Modern Lewis Acid Reagents
5.1 Introduction
5.2 General Considerations
5.2.1 Classification of Cationic Group 13 Complexes
5.2.2 General Methods for the Syntheses of Cationic Group 13 Complexes
5.2.3 Characteristics of Counter‐anions and Solvents
5.2.4 Quantification of LA of Cationic Group 13 Complexes
5.2.4.1 Experimental Methods to Quantify Lewis Acidity. 5.2.4.1.1 Gutmann–Beckett Method (Adduct Formation with Triethyl Phosphine Oxide)
5.2.4.1.2 Childs Method
5.2.4.1.3 Adduct Formation with Acetonitrile
5.2.4.2 Computational Approaches to Determine Lewis Acidity
5.3 Recent Developments in Cationic Group 13 Complexes. 5.3.1 Advances in the Synthesis and Characterization of Borocations
5.3.1.1 Borinium Cations: Two‐coordinate Cationic Boron Complexes
5.3.1.2 Borenium Cations: Three‐coordinate Cationic Boron Complexes
5.3.1.3 Borenium Cations Stabilized by NHC and MIC as Neutral C‐donor Ligand
5.3.1.4 Phosphine‐coordinated Borenium Cations
5.3.1.5 Borenium Cations Coordinated with N‐donor Ligands
5.3.1.6 Boronium Cations: Four‐coordinate Cationic Boron Complexes
5.3.1.7 Miscellaneous Borocations
5.3.2 Advances in the Synthesis and Characterization of Aluminium Cations
5.3.2.1 Organoaluminium Cations
5.3.2.2 Aluminium Cations Supported by N,N′‐donor Monoanionic Bidentate Ligands
5.3.2.3 An Aluminium Cationic Complex Supported by a Neutral Bidentate N,N′‐donor Ligand
5.3.2.4 Miscellaneous Aluminium Cations that Appeared Since 2010
5.3.3 Advances in the Synthesis and Characterization of Heavier Group 13 (Ga, In, and Tl) Cations
5.3.3.1 Low Oxidation State Univalent Heavier Group 13 Cations (Ga, In, and Tl)
5.4 Recent Advancements in Catalytic Applications of Cationic Group 13 Complexes. 5.4.1 Borocation in Catalysis. 5.4.1.1 Cationic Boron Complexes in Catalysis
5.4.1.2 Hydroboration Reaction
5.4.1.3 Hydrosilylation Reaction
5.4.1.4 Hydrogenation Reaction
5.4.1.5 Use of Chiral NHC
5.4.1.6 Use of Chiral Borane
5.4.2 Cationic Al Complexes in Catalysis
5.4.2.1 Hydroboration Reaction
5.4.2.2 Cyanosilylation Reaction
5.4.2.3 Hydrosilylation Reaction
5.4.2.4 Hydroamination Reaction
5.4.2.5 ROP of rac‐Lactide, Epoxides and ε‐Caprolactone
5.4.3 Cationic Heavier Group 13 Complexes in Catalysis. 5.4.3.1 Cationic Gallium Complexes in Catalysis
5.4.3.2 Activation of Alcohols
5.4.3.3 Olefin Epoxidation in Water
5.4.3.4 Transfer Hydrogenation of Alkene
5.4.3.5 Hydroarylation Reaction
5.4.3.6 Cycloisomerization of Enyne
5.4.3.7 Tandem Carbonyl–Olefin Metathesis
5.4.3.8 Polymerization of Propylene Oxide and Isobutylene
5.4.3.9 Cationic Indium and Thallium Complexes in Catalysis
5.4.3.10 Coupling of Epoxides and Lactones
5.4.3.11 ROP of Epoxides, Lactide, and ε‐Caprolactone
5.5 Concluding Remarks
References
6 Recent Development in the Solution Structural Chemistry of Main Group Organometallics
6.1 Introduction
6.2 Monometallic Systems. 6.2.1 Introduction
6.2.2 Organo(s‐block Metal) Aggregation and Reactivity
6.2.3 DOSY on s‐block Organometallics. 6.2.3.1 Development and Early Applications
6.2.3.2 Recent Refinements to Diffusion Techniques
6.3 Heteropolymetallic Systems. 6.3.1 Introduction
6.3.2 s/s‐block Systems. 6.3.2.1 Alkali Metal/Magnesium
6.3.2.2 Turbo–Hauser Chemistry
6.3.3 s/p‐block Systems. 6.3.3.1 Lithium/Aluminium Chemistry and Trans‐metal‐trapping
6.3.3.2 Alkali Metal/Gallium Systems
6.3.4 s/d‐block Systems. 6.3.4.1 Lithium/Cadmium
6.3.4.2 Lithium/Copper
6.3.4.3 Alkali Metal/Zinc
6.3.4.4 Magnesium/Zinc
6.4 Concluding Remarks
References
7 Chemistry of Boryl Anions: Recent Developments
7.1 Introduction
7.2 Boryl Anions as a Salt of Alkali Metals. 7.2.1 Early Examples of Base‐stabilized Boryl Anions and Borylcopper Species
7.2.2 Diaminoboryl Anions as a Lithium Salt
7.2.3 Base‐stabilized Boryl Anion with π‐delocalization. 7.2.3.1 Lewis Base‐stabilized Borole Anion
7.2.3.2 Carbene‐stabilized Boryl Anion
7.2.3.3 Stabilization with Cyanide
7.2.3.4 Metal‐substituted Boryl Anion
7.3 Boryl Anions as a Salt of Magnesium, Zinc, and Copper as Relatives of Carbanions
7.3.1 Transmetalation of Boryllithium to Magnesium, Copper, and Zinc to Form Borylmetals
7.3.2 Transmetalation of Diborane(4) to Magnesium and Zinc to Form Borylmetals
7.4 Application of Borylcopper and Borylzinc Species for Synthetic Organic Chemistry
7.5 Summary
References
8 Novel Chemical Transformations in Organic Synthesis with Ate Complexes
8.1 Introduction
8.2 Ate Complexes
8.3 Di‐anion‐type Zincate. 8.3.1 Mono‐anion‐type Zincates and Di‐anion‐type Zincates
8.3.2 Highly Bulky Di‐anion‐type Zincate: Li2[Znt‐Bu4] 8.3.2.1 Halogen–Zinc Exchange in the Presence of Proton Sources
8.3.2.2 Anionic Polymerization in Water
8.3.3 Cross‐coupling Reaction via C–O Bond Cleavage
8.4 Heteroleptic Zinc Ate Complexes. 8.4.1 Deprotonative Metalation of Aromatic C–H Bonds
8.4.1.1 Amidozincate Base: Li[(TMP)ZnR2]
8.4.1.2 Amidoaluminate Base: Li[(TMP)Ali‐Bu3]
8.4.1.3 Amidocuprate Base: Li2[(TMP)Cu(CN)R]
8.4.2 Hydridozincate: M[HZnMe2]
8.4.3 Silylzincates
8.4.3.1 Silylzincation of Alkynes
8.4.3.2 Silylzincation of Alkynes via Si–B Activation
8.4.3.3 Silylzincation of Alkenes (1): Synthesis of Allylsilanes
8.4.3.4 Silylzincation of Alkenes (2): Synthesis of Alkylsilanes
8.4.4 Perfluoroalkylzincates Li[RFZnMeCl] and RFZnR
8.4.5 Design of Boryl Anion Equivalents and Applications in Synthetic Chemistry
8.4.5.1 Borylzincate: M[(pinB)ZnEt2]
8.4.5.2 Trans‐Diboration of Alkynes via pseudo‐Intramolecular Activation
8.4.5.3 Trans‐Alkynylboration of Alkynes
8.5 Conclusion
References
9 Isolable Alkenylcopper Compounds: Synthesis, Structure, and Reaction Chemistry
9.1 Introduction
9.2 Well‐defined Alkenylcopper Compounds
9.2.1 Mono‐alkenyl Organocopper Compounds with Intramolecular Coordination
9.2.2 Mono‐alkenyl Organocopper Compounds Stabilized by N‐heterocyclic Carbene
9.2.3 Butadienyl Copper Compounds
9.3 Summary
References
Index. a
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