R-M R-R’ R’-X Cross-Coupling Reactions

R-M Functionnalized Organometallic Reagents

R-X-R’ R-X-M 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-R’ R’-X Introduction to Organoboron Chemistry Generalities and Nomenclature R-M Synthesis of Boron Derivatives

R-X-R’ Hydroboration of Unsaturated Systems R-X-M Carbonylation Reactions

Allylation Reactions R-B(R’)2 Matteson Homologation

R-Si(R’)3 Assembly-Line Synthesis R-M R-R’ Introduction to Organoboron Chemistry R’-X Generalities and Nomenclature

R-M

R-X-R’ R-X-M

Mild Lewis Acid R-B(R’)2 Nucleophile Electrophile

R-Si(R’)3

Trigonal, Planar Tetrahedral R-M R-R’ Introduction to Organoboron Chemistry R’-X 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-R’ Introduction to Organoboron Chemistry R’-X 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-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives From Boronic Acids R-M

R-X-R’ R-X-M

R-B(R’) 2 From Boronic Esters – Equilibrium Displacement

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Examples R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Arylboronic Acids R-M 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-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Arylboronic Acids R-M 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-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Arylboronic Acids R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Arylboronic Acids R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Arylboronic Acids R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Arylboronic Acids R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Alkenylboronic Acids R-M 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-R’ Introduction to Organoboron Chemistry R’-X 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-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Alkenylboronic Acids R-M 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-R’ Introduction to Organoboron Chemistry R’-X 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-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Alkenylboronic Acids R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Alkenylboronic Acids R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Alkenylboronic Acids R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Alkenylboronic Acids R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Alkenylboronic Acids R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Synthesis of Boron Derivatives Alkenylboronic Acids R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Hydroboration of Unsaturated Systems

R-M 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-R’ Introduction to Organoboron Chemistry R’-X Hydroboration of Unsaturated Systems

Proposed Mechanism R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Hydroboration of Unsaturated Systems

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X 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-R’ Introduction to Organoboron Chemistry R’-X Hydroboration of Unsaturated Systems

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X 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-R’ Introduction to Organoboron Chemistry R’-X 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-R’ Introduction to Organoboron Chemistry R’-X 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-R’ Introduction to Organoboron Chemistry R’-X 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-R’ Introduction to Organoboron Chemistry R’-X Hydroboration of Unsaturated Systems Enantioelective Hydroboration R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X 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-R’ Introduction to Organoboron Chemistry R’-X Hydroboration of Unsaturated Systems Treatment of Boranes with Aldehydes R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Carbonylation Reactions

3 Different Conditions = 3 Different Products R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Carbonylation Reactions Aldehyde Synthesis R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Carbonylation Reactions Ketone Synthesis R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Carbonylation Reactions Alcohols Synthesis R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Carbonylation Reactions Examples R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Carbonylation Reactions Examples R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Carbonylation Reactions Examples R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Carbonylation Reactions Examples R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Allylation Reactions

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Crotylboration Reactions

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Crotylboration Reactions

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Allylboration Reactions

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Allylboration Reactions

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Allylboration Reactions

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X 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-R’ Introduction to Organoboron Chemistry R’-X Allylboration Reactions Enhanced Reactivity R-M

R-X-R’ R-X-M

R-B(R’)2

Increasing of Electron Density Around the Boron R-Si(R’)3 Gives Increased Nucleophilicity to the Ligands

Allyl-substituant More Nucleophilic R-M R-R’ Introduction to Organoboron Chemistry R’-X Allylboration Reactions Enhanced Reactivity R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Allylboration Reactions Enhanced Reactivity R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Allylboration Reactions Enhanced Reactivity R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

Stereospecific

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M FAVOURED

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

UNFAVOURED

Steric and Electronic Factors R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2 japonilure

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation – Reagent Control ?

R-M

R-X-R’ Substrate Control R-X-M Diastereoselective

R-B(R’)2

R-Si(R’)3 Reagent Control Stereospecific R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation – Hoppe’s Carbamates

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation – Hoppe’s Carbamates

R-M

R-X-R’ R-X-M Stereospecific

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Matteson Homologation

R-M

R-X-R’ R-X-M

R-B(R’)2

Stereospecific Synthesis of all 4 Stereoisomers R-M R-R’ Introduction to Organoboron Chemistry R’-X Assembly-Line Synthesis

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organoboron Chemistry R’-X Assembly-Line Synthesis

R-M

R-X-R’ R-X-M R-M R-R’ Introduction to Organoboron Chemistry R’-X Assembly-Line Synthesis

R-M

R-X-R’ R-X-M R-M R-R’ Introduction to Organoboron Chemistry R’-X Assembly-Line Synthesis

R-M

R-X-R’ R-X-M R-M R-R’ Introduction to Organoboron Chemistry R’-X Assembly-Line Synthesis

R-M

R-X-R’ R-X-M R-M R-R’ Introduction to Organoboron Chemistry R’-X Assembly-Line Synthesis

R-M

R-X-R’ R-X-M R-M R-R’ Introduction to Organoboron Chemistry R’-X Assembly-Line Synthesis

R-M

R-X-R’ R-X-M