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R-B(R’)2
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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
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Page 2
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
Generalities and Nomenclature
Hydroboration of Unsaturated Systems
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R-X-M
R-B(R’)2
R-Si(R’)3
Carbonylation Reactions
Allylation Reactions
Matteson Homologation
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Assembly-Line Synthesis
Page 3
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Generalities and Nomenclature
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Mild Lewis Acid
Electrophile
Trigonal, Planar
Nucleophile
Tetrahedral
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Generalities and Nomenclature
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Borane Borinic Acid Boronic Acid Boric Acid
Borinic Ester Boronic Ester Boric Ester
« Borate »« Boronate »
Ate BoronComplex
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Generalities and Nomenclature
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Inductive Effects
Mesomeric Effects
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
R-M
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From Boronic Acids
From Boronic Esters – Equilibrium Displacement
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Examples
Page 8
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Arylboronic Acids
1) Halogen-Metal Exchange / Electrophilic Trapping
2) Orthometallation / Electrophilic Trapping
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Arylboronic Acids
3) Transmetallation from Silanes and Stannanes
4) Cross-Coupling with Diboron
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Arylboronic Acids
Page 11
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Arylboronic Acids
Page 12
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Arylboronic Acids
Page 13
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Arylboronic Acids
Page 14
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Alkenylboronic Acids
1) Halogen-Metal Exchange / Electrophilic Trapping
2) Transmetallation from Si / Zr
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Alkenylboronic Acids
3) Cross-Coupling with Diboron
4) Reduction
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Alkenylboronic Acids
5) Cis-Hydroboration of Alkynes
6) Rhodium and Iridium-Catalyzed Trans-Hydroboration
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Alkenylboronic Acids
7) Cross-Metathesis
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Alkenylboronic Acids
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Alkenylboronic Acids
Page 20
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Alkenylboronic Acids
Page 21
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Alkenylboronic Acids
Page 22
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Alkenylboronic Acids
Page 23
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Synthesis of Boron Derivatives
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Alkenylboronic Acids
Page 24
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
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Syn-addition
Depends on Both Electronic and Steric Effects
Boron Adds Generally at the less Hindered Position
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
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Proposed Mechanism
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
R-M
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9-Borabicyclo[3.3.1]nonane
9-BBN
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
R-M
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Enantioelective Hydroboration
a-pinene
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
R-M
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Enantioelective Hydroboration
Steric Effects
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
R-M
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Enantioelective Hydroboration
Steric Effects
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
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Enantioelective Hydroboration
Steric Effects
Page 33
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
R-M
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Enantioelective Hydroboration
Page 34
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
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Enantioelective Hydroboration
Electronic Effects
Page 35
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Hydroboration of Unsaturated Systems
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Treatment of Boranes with Aldehydes
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
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3 Different Conditions = 3 Different Products
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
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Aldehyde Synthesis
Page 38
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
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Ketone Synthesis
Page 39
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
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Alcohols Synthesis
Page 40
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
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Examples
Page 41
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
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Examples
Page 42
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
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Examples
Page 43
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Carbonylation Reactions
R-M
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Examples
Page 44
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylation Reactions
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Page 45
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Crotylboration Reactions
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Crotylboration Reactions
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
R-M
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For Small R2
For Large R2
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
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Enhanced Reactivity
Increasing of Electron Density Around the Boron
Gives Increased Nucleophilicity to the Ligands
Allyl-substituant More Nucleophilic
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
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Enhanced Reactivity
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
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Enhanced Reactivity
Page 54
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Allylboration Reactions
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Enhanced Reactivity
Page 55
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
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Stereospecific
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
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FAVOURED
UNFAVOURED
Steric and Electronic Factors
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
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Page 63
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
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japonilure
Page 64
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
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Page 65
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
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R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
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Page 68
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation – Reagent Control ?
R-M
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Substrate Control
Reagent Control
Diastereoselective
Stereospecific
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation – Hoppe’s Carbamates
R-M
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Page 70
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation – Hoppe’s Carbamates
R-M
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Stereospecific
Page 71
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
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Page 72
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
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Page 73
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R-X-M
R-B(R’)2
Introduction to Organoboron Chemistry
Matteson Homologation
R-M
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Stereospecific Synthesis of all 4 Stereoisomers
Page 74
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
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R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
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R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
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R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
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R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
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R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
R-M
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R-X-M
Introduction to Organoboron Chemistry
Assembly-Line Synthesis
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Page 81
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Our research group (AK Didier)
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D. Didier et al. Angew. Chem. Int. Ed. 2015, 52, 15884.
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Our research group (AK Didier)
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D. Didier et al. Chem. Commun. 2016, 52, 2529.
Page 83
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Our research group (AK Didier)
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D. Didier et al. Chem. Eur. J. 2016, 23, 1634.
Page 84
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R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organoboron Chemistry
Our research group (AK Didier)
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D. Didier et al. Org. Lett., 2016, 18, 3022.
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Introduction to Organoboron ChemistryR-M
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First experiment
G. Zweifel et al. J. Am. Chem. Soc. 1967, 89, 3652.
Zweifel olefination
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R-Si(R’)3
Introduction to Organoboron ChemistryR-M
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Aggarwal’s extensions for olefination
V. K. Aggarwal et al. Org. Lett. 2017, 19, 2762.
Zweifel olefination
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R-Si(R’)3
Introduction to Organoboron ChemistryR-M
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Aggarwal’s diastereoselective method
V. K. Aggarwal et al. Angew. Chem. Int. Ed. 2016, 56, 786.
Zweifel olefination
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Introduction to Organoboron ChemistryR-M
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Aggarwal’s diastereoselective method
V. K. Aggarwal et al. Angew. Chem. Int. Ed. 2016, 56, 786.
Zweifel olefination