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R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Cross-Coupling Reactions
Functionnalized Organometallic Reagents
C-N, C-O and C-S Bond Formation
Introduction to Organoboron Chemistry
Introduction to Organosilicon Chemistry
Carbometallation Reactions
R-M
R’-XR-R’
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Generalities and Nomenclature
Hydroboration of Unsaturated Systems
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Carbonylation Reactions
Allylation Reactions
Matteson Homologation
R-M
R’-XR-R’
Assembly-Line Synthesis
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Generalities and Nomenclature
R-M
R’-XR-R’
Mild Lewis Acid
Electrophile
Trigonal, Planar
Nucleophile
Tetrahedral
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Generalities and Nomenclature
R-M
R’-XR-R’
Borane Borinic Acid Boronic Acid Boric Acid
Borinic Ester Boronic Ester Boric Ester
« Borate »« Boronate »
Ate BoronComplex
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Generalities and Nomenclature
R-M
R’-XR-R’
Inductive Effects
Mesomeric Effects
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
From Boronic Acids
From Boronic Esters – Equilibrium Displacement
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Examples
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Arylboronic Acids
1) Halogen-Metal Exchange / Electrophilic Trapping
2) Orthometallation / Electrophilic Trapping
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Arylboronic Acids
3) Transmetallation from Silanes and Stannanes
4) Cross-Coupling with Diboron
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Arylboronic Acids
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Arylboronic Acids
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Arylboronic Acids
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Arylboronic Acids
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Alkenylboronic Acids
1) Halogen-Metal Exchange / Electrophilic Trapping
2) Transmetallation from Si / Zr
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Alkenylboronic Acids
3) Cross-Coupling with Diboron
4) Reduction
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Alkenylboronic Acids
5) Cis-Hydroboration of Alkynes
6) Rhodium and Iridium-Catalyzed Trans-Hydroboration
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Alkenylboronic Acids
7) Cross-Metathesis
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Alkenylboronic Acids
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Alkenylboronic Acids
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Alkenylboronic Acids
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Alkenylboronic Acids
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Alkenylboronic Acids
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
R’-XR-R’
Alkenylboronic Acids
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’-XR-R’
Syn-addition
Depends on Both Electronic and Steric Effects
Boron Adds Generally at the less Hindered Position
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’-XR-R’
Proposed Mechanism
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’-XR-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’-XR-R’
9-Borabicyclo[3.3.1]nonane
9-BBN
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’-XR-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’-XR-R’
Enantioelective Hydroboration
a-pinene
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’-XR-R’
Enantioelective Hydroboration
Steric Effects
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’-XR-R’
Enantioelective Hydroboration
Steric Effects
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’-XR-R’
Enantioelective Hydroboration
Steric Effects
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’-XR-R’
Enantioelective Hydroboration
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’-XR-R’
Enantioelective Hydroboration
Electronic Effects
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’-XR-R’
Treatment of Boranes with Aldehydes
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
R’-XR-R’
3 Different Conditions = 3 Different Products
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
R’-XR-R’
Aldehyde Synthesis
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
R’-XR-R’
Ketone Synthesis
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
R’-XR-R’
Alcohols Synthesis
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
R’-XR-R’
Examples
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
R’-XR-R’
Examples
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
R’-XR-R’
Examples
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
R’-XR-R’
Examples
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’-XR-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’-XR-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’-XR-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’-XR-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’-XR-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’-XR-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’-XR-R’
For Small R2
For Large R2
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’-XR-R’
Enhanced Reactivity
Increasing of Electron Density Around the Boron
Gives Increased Nucleophilicity to the Ligands
Allyl-substituant More Nucleophilic
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’-XR-R’
Enhanced Reactivity
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’-XR-R’
Enhanced Reactivity
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’-XR-R’
Enhanced Reactivity
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’-XR-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’-XR-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’-XR-R’
Stereospecific
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’-XR-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’-XR-R’
FAVOURED
UNFAVOURED
Steric and Electronic Factors
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’-XR-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’-XR-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’-XR-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’-XR-R’
japonilure
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’-XR-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’-XR-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’-XR-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’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation – Reagent Control ?
R-M
R’-XR-R’
Substrate Control
Reagent Control
Diastereoselective
Stereospecific
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’-XR-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’-XR-R’
Stereospecific
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’-XR-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’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
R’-XR-R’
Stereospecific Synthesis of all 4 Stereoisomers
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’-XR-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Our research group (AK Didier)
R-M
R’-XR-R’
D. Didier et al. Angew. Chem. Int. Ed. 2015, 52, 15884.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Our research group (AK Didier)
R-M
R’-XR-R’
D. Didier et al. Chem. Commun. 2016, 52, 2529.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Our research group (AK Didier)
R-M
R’-XR-R’
D. Didier et al. Chem. Eur. J. 2016, 23, 1634.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Our research group (AK Didier)
R-M
R’-XR-R’
D. Didier et al. Org. Lett., 2016, 18, 3022.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron ChemistryR-M
R’-XR-R’
First experiment
G. Zweifel et al. J. Am. Chem. Soc. 1967, 89, 3652.
Zweifel olefination
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron ChemistryR-M
R’-XR-R’
Aggarwal’s extensions for olefination
V. K. Aggarwal et al. Org. Lett. 2017, 19, 2762.
Zweifel olefination
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron ChemistryR-M
R’-XR-R’
Aggarwal’s diastereoselective method
V. K. Aggarwal et al. Angew. Chem. Int. Ed. 2016, 56, 786.
Zweifel olefination
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron ChemistryR-M
R’-XR-R’
Aggarwal’s diastereoselective method
V. K. Aggarwal et al. Angew. Chem. Int. Ed. 2016, 56, 786.
Zweifel olefination
