1.0 C-C CROSS COUPLING REACTIONS (C-C XCOUPL)

1.1 Historical

Aryl-Aryl Cross Coupling (X-Coupl) Grid
Name XCOUPL Reactions: Reviews and Historical Origins

1.2 Mechanism. General Considerations

General Catalytic Pathway for Pd Catalyzed Reactions
Monophosphine and Diphosphine Ligands: step by step analysis of mechanism

1.3 Kumada – Corriu – Tamao Cross Coupling Reaction

Mechanism
Methodology and Scope

1.4 The Negishi Cross Coupling Reaction

Negishi/Sonogoshira Comparison
Methodology and Scope

1.5 The Suzuki-Miyaura Cross Coupling Reaction

Alkyl Boranes. Mechanism
Advantages/Disadvantages
Methodology and Scope

1.6 The Stille Cross Coupling Reaction

Mechanism
Hiyama Modification
Methodology and Scope

1.7 The Hiyama Cross Coupling Reaction

Mechanism and Stereochemistry
Silanols, Hypervalent Siloxane
Methodology and Scope

1.8 α-Enolate Cross Coupling

Mechanism
Methodology and Scope

1.9 C-C Cross Coupling Comparisons

Mg-Ni/Mg/Pd vs. Zn-Ni, Zn-Pd vs. B-Pd
Steric Considerations
Methodology and Scope

2.0 C-N CROSS COUPLING REACTIONS

The Catalytic Cycle
ArX + Amine. Copper Catalysis in Air
ArX + Amine. Pd Catalysis
ArX + HetcycleArB(OH)2 + Amine, Phenol
ArB(OH)2 + Hetcycle
ArX +Imine: N-Arylation. An Ammonia Equivalent
Classical and Modern Ullmann Comparisons

3.0 C-O CROSS COUPLING

Cu Catalysis
Cu Catalysis. B(OH)2 + Phenols
Cu Catalyst: Solid Phase Ullmann
Pd Catalysis
Intermolecular Alkyl-Aryl Ether Ullmann
Intramolecular Alkyl-Aryl Ether Ullmann

4.0 C-S AND C-P CROSS COUPLING REACTIONS

Mechanism
Substrates

5.0 CROSS COUPLING STRATEGIES IN BIOACTIVE MOLECULE CONSTRUCTION

A selection of structures in modern med.chem. Indications, e.g. antihypertensive, antitumour, antiviral

6.0 CROSS COUPLING STRATEGIES IN NATURAL PRODUCT CONSTRUCTION

A selection of aromatics and heteroaromatics derived from terrestrial, marine and fungal sources.

7.0 THE DoM/CROSS COUPLING NEXUS

The DoM-Suzuki XCoupl
The O-Aryl Carbamate – Grignard XCoupl
Aryl S-Thiocarbamate – Grignard Cross Coupling Reaction
The DoM – Negishi XCoupl
Comparisons of ArMgX, ArZnX, ArB(OH)2 + ArOTf Efficacies
The Arsulfonamides + Grignard XCoupl
Applications

8.0 THE HECK CROSS COUPLING REACTION

Mechanism
Polymer Supported and Nanoparticle Catalysis
Heck versus Suzuki
Domino-Heck
Asymmetric Induction
Applications

9.0 THE SONOGOSHIRA – HAGIHARA CROSS COUPLING REACTION

Catalytic Cycle
Comparison with Zn,Sn, Mg Equivalents
Applications

10.0 THE GRUBBS METATHESIS REACTION

Mechanistic considerations
The catalysts (1st, 2nd generation and beyond)
Alkyne metathesis
Applications