R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
Cross-Coupling Reactions
Functionnalized Organometallic Reagents
C-N, C-O and C-S Bond Formation
R-B(R’)2
Introduction to Organoboron Chemistry
R-Si(R’)3
Introduction to Organosilicon Chemistry
Carbometallation Reactions
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Generalities and Nomenclature
R-M
Synthesis of Boron Derivatives
R-X-R’
R-X-M
R-B(R’)2
Hydroboration of Unsaturated Systems
Carbonylation Reactions
Allylation Reactions
Matteson Homologation
R-Si(R’)3
Assembly-Line Synthesis
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Generalities and Nomenclature
R-M
R-X-R’
R-X-M
Mild Lewis Acid
R-B(R’)2
Electrophile
Nucleophile
R-Si(R’)3
Trigonal, Planar
Tetrahedral
R-M
R’-X
Introduction to Organoboron Chemistry
R-R’
Generalities and Nomenclature
R-M
R-X-R’
R-X-M
Borane
Borinic Acid
Boronic Acid
Boric Acid
R-B(R’)2
Ate Boron
Complex
R-Si(R’)3
Borinic Ester
Boronic Ester
Boric Ester
« Boronate »
« Borate »
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Generalities and Nomenclature
R-M
Inductive Effects
R-X-R’
R-X-M
Mesomeric Effects
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
R-M
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
From Boronic Acids
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
From Boronic Esters – Equilibrium Displacement
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Examples
R-M
R’-X
R-R’
R-M
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Arylboronic Acids
1) Halogen-Metal Exchange / Electrophilic Trapping
R-X-R’
R-X-M
R-B(R’)2
2) Orthometallation / Electrophilic Trapping
R-Si(R’)3
R-M
R’-X
R-R’
R-M
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Arylboronic Acids
3) Transmetallation from Silanes and Stannanes
R-X-R’
R-X-M
R-B(R’)2
4) Cross-Coupling with Diboron
R-Si(R’)3
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Arylboronic Acids
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Arylboronic Acids
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Arylboronic Acids
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Arylboronic Acids
R-M
R’-X
R-R’
R-M
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Alkenylboronic Acids
1) Halogen-Metal Exchange / Electrophilic Trapping
R-X-R’
R-X-M
R-B(R’)2
2) Transmetallation from Si / Zr
R-Si(R’)3
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Alkenylboronic Acids
R-M
3) Cross-Coupling with Diboron
R-X-R’
R-X-M
R-B(R’)2
4) Reduction
R-Si(R’)3
R-M
R’-X
R-R’
R-M
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Alkenylboronic Acids
5) Cis-Hydroboration of Alkynes
R-X-R’
R-X-M
R-B(R’)2
6) Rhodium and Iridium-Catalyzed Trans-Hydroboration
R-Si(R’)3
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Alkenylboronic Acids
R-M
7) Cross-Metathesis
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Alkenylboronic Acids
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Alkenylboronic Acids
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Alkenylboronic Acids
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Alkenylboronic Acids
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Alkenylboronic Acids
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Alkenylboronic Acids
R-M
R’-X
R-R’
R-M
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
Syn-addition
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Depends on Both Electronic and Steric Effects
Boron Adds Generally at the less Hindered Position
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
Proposed Mechanism
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
R-M
R-X-R’
R-X-M
R-B(R’)2
9-Borabicyclo[3.3.1]nonane
R-Si(R’)3
9-BBN
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
Enantioelective Hydroboration
R-M
R-X-R’
R-X-M
a-pinene
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
Enantioelective Hydroboration
R-M
Steric Effects
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
Enantioelective Hydroboration
R-M
Steric Effects
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
Enantioelective Hydroboration
R-M
Steric Effects
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
Enantioelective Hydroboration
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
Enantioelective Hydroboration
R-M
Electronic Effects
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
Treatment of Boranes with Aldehydes
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
3 Different Conditions = 3 Different Products
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Carbonylation Reactions
Aldehyde Synthesis
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Carbonylation Reactions
Ketone Synthesis
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Carbonylation Reactions
Alcohols Synthesis
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Carbonylation Reactions
Examples
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Carbonylation Reactions
Examples
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Carbonylation Reactions
Examples
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Carbonylation Reactions
Examples
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylation Reactions
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Crotylboration Reactions
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Crotylboration Reactions
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Allylboration Reactions
R-M
For Small R2
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
For Large R2
R-M
R’-X
R-R’
R-M
Introduction to Organoboron Chemistry
Allylboration Reactions
Enhanced Reactivity
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Increasing of Electron Density Around the Boron
Gives Increased Nucleophilicity to the Ligands
Allyl-substituant More Nucleophilic
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
Enhanced Reactivity
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
Enhanced Reactivity
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
Enhanced Reactivity
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R-X-R’
R-X-M
Stereospecific
R-B(R’)2
R-Si(R’)3
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
R-M
Introduction to Organoboron Chemistry
Matteson Homologation
FAVOURED
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
UNFAVOURED
Steric and Electronic Factors
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R-X-R’
R-X-M
R-B(R’)2
japonilure
R-Si(R’)3
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Matteson Homologation – Reagent Control ?
R-M
R-X-R’
R-X-M
Substrate Control
Diastereoselective
R-B(R’)2
R-Si(R’)3
Reagent Control
Stereospecific
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation – Hoppe’s Carbamates
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Matteson Homologation – Hoppe’s Carbamates
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Stereospecific
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-X
R-R’
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R-X-R’
R-X-M
R-B(R’)2
Stereospecific Synthesis of all 4 Stereoisomers
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-X
R-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis