R-M

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

R-X-R’ Hydroboration of Unsaturated Systems

R-X-M
Allylation Reactions

R-B(R’)2 g-selective cross-coupling reactions

Matteson Homologation
R-Si(R’)3 Assembly-Line Synthesis

Zweifel olefination
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
g-selective cross-coupling reactions

R-M Classical Suzuki-Miyaura CC

R-X-R’
R-X-M

R-B(R’)2
Allylic version of the reaction

R-Si(R’)3

a g
R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
g-selective cross-coupling reactions
Buchwald’s catalytic systems
R-M

R-X-R’
R-X-M

R-B(R’)2

a g
R-Si(R’)3
R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
g-selective cross-coupling reactions
Buchwald’s catalytic systems
R-M

R-X-R’
R-X-M

R-B(R’)2

R-Si(R’)3

S. L. Buchwald et al. J. Am. Chem. Soc. 2013, 135, 10642.

R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
g-selective cross-coupling reactions
Morken’s regiodivergent systems
R-M

R-X-R’
R-X-M

R-B(R’)2

R-Si(R’)3

J. P. Morken et al. Nature Commun. 2014, 5, 5474.

R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
g-selective cross-coupling reactions
Aggarwal’s g- and stereo-selective cross-coupling
R-M

R-X-R’
R-X-M

R-B(R’)2

R-Si(R’)3

V. K. Aggarwal et al. Chem. Eur. J. 2013, 19, 17698.

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 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
R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
Our research group (AK Didier)

R-M

R-X-R’
R-X-M

R-B(R’)2

R-Si(R’)3

D. Didier et al. Angew. Chem. Int. Ed. 2015, 52, 15884.

R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
Our research group (AK Didier)

R-M

R-X-R’
R-X-M

R-B(R’)2

R-Si(R’)3

D. Didier et al. Chem. Commun. 2016, 52, 2529.

R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
Our research group (AK Didier)

R-M

R-X-R’
R-X-M

R-B(R’)2

R-Si(R’)3

D. Didier et al. Chem. Eur. J. 2016, 23, 1634.

R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
Our research group (AK Didier)

R-M

R-X-R’
R-X-M

R-B(R’)2

R-Si(R’)3

D. Didier et al. Org. Lett., 2016, 18, 3022.

R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
Zweifel olefination
First experiment
R-M

R-X-R’
R-X-M

R-B(R’)2

R-Si(R’)3

G. Zweifel et al. J. Am. Chem. Soc. 1967, 89, 3652.

R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
Zweifel olefination
Aggarwal’s extensions for olefination
R-M

R-X-R’
R-X-M

R-B(R’)2

R-Si(R’)3

V. K. Aggarwal et al. Org. Lett. 2017, 19, 2762.

R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
Zweifel olefination
Aggarwal’s diastereoselective method
R-M

R-X-R’
R-X-M

R-B(R’)2

R-Si(R’)3

V. K. Aggarwal et al. Angew. Chem. Int. Ed. 2016, 56, 786.

R-M
R-R’
Introduction to Organoboron Chemistry
R’-X
Zweifel olefination
Aggarwal’s diastereoselective method
R-M

R-X-R’
R-X-M

R-B(R’)2

R-Si(R’)3

V. K. Aggarwal et al. Angew. Chem. Int. Ed. 2016, 56, 786.