Embed Size (px)
Citation preview
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 Organosilicon Chemistry
Synthesis of Organosilicon Compounds
Generalities
Hydrosilylation of Unsaturated Systems
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Hiyama Cross-Coupling
Hosomi-Sakurai Allylations
Brook Rearrangement
Anion-Relay Chemistry (ARC)
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Generalities
R-M
R’-XR-R’
Electronegativity s-Bond strengths (kcal.mol-1) Average Bond Length (Å)
Si 1,7
H 2,1
C 2,5
Cl 3,0
N 3,0
O 3,5
F 4,0
C-C 83C-Si 76Si-Si 53
C-H 83Si-H 76
C-O 86Si-O 108
C-N 83Si-N 76
C-F 116Si-F 135
C-C 1,54C-Si 1,87
C-O 1,43Si-O 1,66
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Generalities
R-M
R’-XR-R’
Electronegativity s-Bond strengths (kcal.mol-1) Average Bond Length (Å)
Si 1,7
H 2,1
C 2,5
Cl 3,0
N 3,0
O 3,5
F 4,0
C-C 83C-Si 76Si-Si 53
C-H 83Si-H 76
C-O 86Si-O 108
C-N 83Si-N 76
C-F 116Si-F 135
C-C 1,54C-Si 1,87
C-O 1,43Si-O 1,66
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Generalities
R-M
R’-XR-R’
Electronegativity s-Bond strengths (kcal.mol-1) Average Bond Length (Å)
Si 1,7
H 2,1
C 2,5
Cl 3,0
N 3,0
O 3,5
F 4,0
C-C 83C-Si 76Si-Si 53
C-H 83Si-H 76
C-O 86Si-O 108
C-N 83Si-N 76
C-F 116Si-F 135
C-C 1,54C-Si 1,87
C-O 1,43Si-O 1,66
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Generalities
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Generalities
R-M
R’-XR-R’
Hydrosilylation
Metal-Catalyzed
Acylations
Hiyama-DenmarkCross-Coupling
Hosomi-SakuraiAllylations
CoordinativeNon-Coordinative
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Generalities
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Generalities
R-M
R’-XR-R’
Sp3
Tetravalent
Tetrahedral
Charge:X = 0
3c-4e
Pentavalent
Bipyramidal
Charge:Xax = -0,25Xeq = -0,17
2 x 3c-4e
Hexavalent
Octahedral
Charge:X = -0,33
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Generalities
R-M
R’-XR-R’
Pimentel and Rundle
3c-4e
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Generalities
R-M
R’-XR-R’
Increasing the Lewis Acidity
Having Electron Rich Ligands
Favourizing the Geometry
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Generalities
R-M
R’-XR-R’
Mechanism of Alcohol Deprotection
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Synthesis of Organosilicon Compounds
R-M
R’-XR-R’
1. Silyl-Enol Ether Formation
2. Alcohol Protection
3. Vinyl-Silanes Formation
4. Aryl-Silanes Formation
4. Hydrosilylation
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Synthesis of Organosilicon Compounds
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hydrosilylation of Unsaturated Systems
R-M
R’-XR-R’
b-E selectivity b-Z selectivity a Selectivity
Special cases
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hydrosilylation of Alkynes
R-M
R’-XR-R’
b-E selectivity
b-Z selectivity
Pt
Ru, Rh, Ir
Hydrometallation
Silylmetallation
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hydrosilylation of Alkynes
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hydrosilylation of Alkynes
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hydrosilylation of Alkynes
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hydrosilylation of Alkenes
R-M
R’-XR-R’
Co(I), Rh(I), Ni(0), Pd(0), Pt(0)Late Transition Metals
Electron Rich Complexes
HydrometallationSilylmetallation
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hydrosilylation of Alkenes
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hydrosilylation of Styrenes
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hydrosilylation of Cyclic Olefins
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hydrosilylation of 1,3-dienes
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hydrosilylation of 1,3-dienes
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Intramolecular Hydrosilylation
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hiyama Cross-Coupling
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hiyama Cross-Coupling
R-M
R’-XR-R’
Another Activation Mode
Nucleophily of RAnd
Lewis Acidity of SiIncreases with
X electronegativity
Angle close to 90°In the hypervalent
Species
Nucleophily of RAnd
Lewis Acidity of SiIncreases with
Geometrical AdaptationOf the Ligand
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hiyama Cross-Coupling
R-M
R’-XR-R’
Another Activation Mode
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hiyama Cross-Coupling
R-M
R’-XR-R’
Non-Transferable Ligands
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hiyama Cross-Coupling
R-M
R’-XR-R’
G. A. Molander et al. J. Org. Chem. 2011, 76, 9102.
F. Y. Kwong et al. Org. Lett. 2009, 11, 317.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hiyama Cross-Coupling
R-M
R’-XR-R’
G. C. Fu et al. J. Am. Chem. Soc. 2003, 125, 5616.
N. K. Garg et al. Org. Lett. 2014, 16, 824.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hiyama-Denmark Cross-Coupling
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hiyama-Denmark Cross-Coupling
R-M
R’-XR-R’
S. E. Denmark et al. J. Am. Chem. Soc. 2005, 127, 8004.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hiyama-Denmark Cross-Coupling
R-M
R’-XR-R’
S. E. Denmark et al. J. Org. Chem. 2003, 68, 9151.
S. E. Denmark et al. J. Am. Chem. Soc. 2008, 130, 16382.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Lewis-Acid Catalyzed
Fleming et al. J. Chem. Soc. Chem. Commun. 1976, 182.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Lewis-Acid Catalyzed
Jorgensen et al. J. Am. Chem. Soc. 1986, 1496.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Lewis-Acid Catalyzed
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Hayashi et al. Tetrahedron Lett. 1983, 2865.
Stereochemical Aspect
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Stereochemical Aspect
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Lewis-Acid Catalyzed
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
With Ketals
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
With Ketals
Weinreb et al. J. Org. Chem. 1991, 56, 3210.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
With Epoxides
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
With SO2
Turks et al. Tetrahedron Lett. 2015, 56, 4578.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
With Ketenes
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Conjugate Addition
Tokoroyama et al. Tetrahedron Lett. 1987, 28, 6645.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Conjugate Addition
Yamamoto et al. J. Org. Chem. 1990, 55, 3971.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Conjugate Addition – 1,4
Majetich et al. Tetrahedron. 1987, 43, 5621.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Conjugate Addition – 1,6
Majetich et al. Tetrahedron. 1987, 43, 5621.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Conjugate Addition – 1,6
Majetich et al. Tetrahedron. 1987, 43, 5621.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Majetich et al. Tetrahedron. 1987, 43, 5621.
Conjugate Addition – 1,6
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Through Hypervalent Silicon
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Stereochemical Aspects
Sakurai et al. Tetrahedron Lett. 1987, 28, 4081.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Through Hypervalent Silicon
Sakurai et al. Tetrahedron Lett. 1987, 28, 4081.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Solvent-Effect - Discovery
From Problem Set #3
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Solvent-Effect - Discovery
Lewis-Base Assisted Allylation
Kobayashi et al. Tetrahedron Lett. 1993, 34, 3453.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Solvent-Effect - Discovery
Lewis-Base Assisted Allylation
Kobayashi et al. J. Org. Chem. 1994, 59, 6620.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Solvent-Effect - Discovery
Lewis-Base Assisted Asymmetric Crotylation
Denmark et al. J. Org. Chem. 1994, 59, 6161.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Hosomi-Sakurai Allylation
R-M
R’-XR-R’
Solvent-Effect - Discovery
Lewis-Base Assisted Asymmetric Crotylation
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Allenylation and Propargylation
R-M
R’-XR-R’
Kobayashi et al. J. Am. Chem. Soc. 1995, 117, 6392.
Kobayashi et al. Tetrahedron 2006, 62, 496.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Allenylation and Propargylation
R-M
R’-XR-R’
Takenaka et al. Org. Lett. 2011, 13, 1654.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Trifluoromethylation – F- promoted
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Brook Rearrangement
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Brook Rearrangement
R-M
R’-XR-R’
Moser et al. Org. Lett. 2002, 1981.
Moser et al. Org. Lett. 2000, 717.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Brook Rearrangement
R-M
R’-XR-R’
Smith et al. Synlett 2004, 1363.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Brook Rearrangement
R-M
R’-XR-R’
Takeda et al. J. Am. Chem. Soc. 1993, 9351.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Brook Rearrangement
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Brook Rearrangement
R-M
R’-XR-R’
For a good summary on Brook rearrangements :
Moser et al. Tetrahedron 2001, 57, 2065.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Brook Rearrangement
R-M
R’-XR-R’
Corey et al. J. Am. Chem. Soc. 2002, 11290.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Brook Rearrangement
R-M
R’-XR-R’
Corey et al. J. Am. Chem. Soc. 2002, 11290.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Brook Rearrangement
R-M
R’-XR-R’
Corey et al. J. Am. Chem. Soc. 2002, 11290.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Anion Relay Chemistry (ARC)
R-M
R’-XR-R’
Matsuda et al. Perkin Trans. 1 1979, 26.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Anion Relay Chemistry (ARC)
R-M
R’-XR-R’
Tietze et al. Synlett 1994, 511.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Anion Relay Chemistry (ARC)
R-M
R’-XR-R’
Tietze et al. Angew. Chem. Int. Ed. 1994, 217.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Anion Relay Chemistry (ARC)
R-M
R’-XR-R’
Smith et al. J. Am. Chem. Soc. 1997, 6295.
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Anion Relay Chemistry (ARC)
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Anion Relay Chemistry (ARC)
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Anion Relay Chemistry (ARC)
R-M
R’-XR-R’
R-M
R-X-R’
R-X-M
R-B(R’)2
R-Si(R’)3
Introduction to Organosilicon Chemistry
Examples for Exercises
R-M
R’-XR-R’
