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

R-Si(R’)3 Introduction to Chemistry

Carbometallation Reactions R-M R-R’ R’-X Introduction to Organosilicon Chemistry Generalities R-M Synthesis of Organosilicon Compounds

R-X-R’ Hydrosilylation of Unsaturated Systems R-X-M Hiyama Cross-Coupling

Hosomi-Sakurai Allylations R-B(R’)2 Brook Rearrangement

R-Si(R’)3 Anion-Relay Chemistry (ARC) R-M R-R’ Introduction to Organosilicon Chemistry R’-X Generalities

R-M s-Bond strengths (kcal.mol-1) Average Bond Length (Å)

Si 1,7 C-C 83 R-X-R’ C-Si 76 C-C 1,54 Si-Si 53 C-Si 1,87 R-X-M H 2,1 C-H 83 C 2,5 Si-H 76 C-O 1,43 R-B(R’)2 Si-O 1,66 Cl 3,0 C-O 86 Si-O 108 N 3,0 R-Si(R’)3 C-N 83 O 3,5 Si-N 76 C-F 116 F 4,0 Si-F 135 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Generalities

R-M Electronegativity s-Bond strengths (kcal.mol-1) Average Bond Length (Å)

Si 1,7 C-C 83 R-X-R’ C-Si 76 C-C 1,54 Si-Si 53 C-Si 1,87 R-X-M H 2,1 C-H 83 C 2,5 Si-H 76 C-O 1,43 R-B(R’)2 Si-O 1,66 Cl 3,0 C-O 86 Si-O 108 N 3,0 R-Si(R’)3 C-N 83 O 3,5 Si-N 76 C-F 116 F 4,0 Si-F 135 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Generalities

R-M Electronegativity s-Bond strengths (kcal.mol-1) Average Bond Length (Å)

Si 1,7 C-C 83 R-X-R’ C-Si 76 C-C 1,54 Si-Si 53 C-Si 1,87 R-X-M H 2,1 C-H 83 C 2,5 Si-H 76 C-O 1,43 R-B(R’)2 Si-O 1,66 Cl 3,0 C-O 86 Si-O 108 N 3,0 R-Si(R’)3 C-N 83 O 3,5 Si-N 76 C-F 116 F 4,0 Si-F 135 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Generalities

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Generalities

R-M

R-X-R’ R-X-M

R-B(R’)2 Hydrosilylation Acylations Hosomi-Sakurai Allylations Metal-Catalyzed Hiyama-Denmark R-Si(R’)3 Cross-Coupling Coordinative Non-Coordinative R-M R-R’ Introduction to Organosilicon Chemistry R’-X Generalities

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Generalities

R-M

R-X-R’ R-X-M

Sp3 3c-4e 2 x 3c-4e R-B(R’)2 Tetravalent Pentavalent Hexavalent

Tetrahedral Bipyramidal Octahedral R-Si(R’)3 Charge: Charge: Charge:

X = 0 Xax = -0,25 X = -0,33 Xeq = -0,17 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Generalities

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 Pimentel and Rundle

3c-4e R-M R-R’ Introduction to Organosilicon Chemistry R’-X Generalities Increasing the Lewis Acidity R-M

R-X-R’ Having Electron Rich Ligands R-X-M Favourizing the Geometry

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Generalities Mechanism of Deprotection R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Synthesis of Organosilicon Compounds

3. Vinyl-Silanes Formation R-M

1. Silyl-Enol Formation R-X-R’ R-X-M 4. Aryl-Silanes Formation

R-B(R’)2 2. Alcohol Protection

R-Si(R’)3 4. Hydrosilylation R-M R-R’ Introduction to Organosilicon Chemistry R’-X Synthesis of Organosilicon Compounds

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hydrosilylation of Unsaturated Systems

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

b-E selectivity b-Z selectivity a Selectivity Special cases R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hydrosilylation of Alkynes Pt R-M

Hydrometallation R-X-R’ b-E selectivity R-X-M

R-B(R’)2

Silylmetallation

R-Si(R’) 3 b-Z selectivity

Ru, Rh, Ir R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hydrosilylation of Alkynes

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hydrosilylation of Alkynes

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hydrosilylation of Alkynes

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hydrosilylation of

Late Transition Metals R-M Co(I), Rh(I), Ni(0), Pd(0), Pt(0) Electron Rich Complexes

R-X-R’ R-X-M Silylmetallation Hydrometallation

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hydrosilylation of Alkenes

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hydrosilylation of Styrenes

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hydrosilylation of Cyclic Olefins

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hydrosilylation of 1,3-dienes

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hydrosilylation of 1,3-dienes

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Intramolecular Hydrosilylation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hiyama Cross-Coupling

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hiyama Cross-Coupling

R-M Another Activation Mode

R-X-R’ R-X-M

R-B(R’)2

Nucleophily of R Nucleophily of R R-Si(R’)3 And Angle close to 90° And Lewis Acidity of Si In the hypervalent Lewis Acidity of Si Increases with Species Increases with X electronegativity Geometrical Adaptation Of the Ligand R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hiyama Cross-Coupling

R-M Another Activation Mode

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hiyama Cross-Coupling

R-M Non-Transferable Ligands

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hiyama Cross-Coupling

R-M

R-X-R’ R-X-M G. A. Molander et al. J. Org. Chem. 2011, 76, 9102.

R-B(R’)2

R-Si(R’)3

F. Y. Kwong et al. Org. Lett. 2009, 11, 317. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hiyama Cross-Coupling

R-M

R-X-R’ R-X-M G. C. Fu et al. J. Am. Chem. Soc. 2003, 125, 5616.

R-B(R’)2

R-Si(R’)3

N. K. Garg et al. Org. Lett. 2014, 16, 824. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hiyama-Denmark Cross-Coupling

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hiyama-Denmark Cross-Coupling

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

S. E. Denmark et al. J. Am. Chem. Soc. 2005, 127, 8004. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hiyama-Denmark Cross-Coupling

R-M

R-X-R’ R-X-M

S. E. Denmark et al. J. Org. Chem. 2003, 68, 9151. R-B(R’)2

R-Si(R’)3

S. E. Denmark et al. J. Am. Chem. Soc. 2008, 130, 16382. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Lewis-Acid Catalyzed R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Fleming et al. J. Chem. Soc. Chem. Commun. 1976, 182. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Lewis-Acid Catalyzed R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Jorgensen et al. J. Am. Chem. Soc. 1986, 1496. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Lewis-Acid Catalyzed R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Stereochemical Aspect R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Hayashi et al. Tetrahedron Lett. 1983, 2865. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Stereochemical Aspect R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Lewis-Acid Catalyzed R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation With Ketals R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation With Ketals R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Weinreb et al. J. Org. Chem. 1991, 56, 3210. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation With Epoxides R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation

With SO2 R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Turks et al. Tetrahedron Lett. 2015, 56, 4578. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation With Ketenes R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Conjugate Addition R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Tokoroyama et al. Tetrahedron Lett. 1987, 28, 6645. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Conjugate Addition R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Yamamoto et al. J. Org. Chem. 1990, 55, 3971. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Conjugate Addition – 1,4 R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Majetich et al. Tetrahedron. 1987, 43, 5621. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Conjugate Addition – 1,6 R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Majetich et al. Tetrahedron. 1987, 43, 5621. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Conjugate Addition – 1,6 R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Majetich et al. Tetrahedron. 1987, 43, 5621. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Conjugate Addition – 1,6 R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Majetich et al. Tetrahedron. 1987, 43, 5621. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Through Hypervalent Silicon R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Stereochemical Aspects R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Sakurai et al. Tetrahedron Lett. 1987, 28, 4081. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Through Hypervalent Silicon R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Sakurai et al. Tetrahedron Lett. 1987, 28, 4081. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Solvent-Effect - Discovery R-M From Problem Set #3

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Solvent-Effect - Discovery R-M Lewis- Assisted Allylation

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Kobayashi et al. Tetrahedron Lett. 1993, 34, 3453. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Solvent-Effect - Discovery R-M Lewis-Base Assisted Allylation

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Kobayashi et al. J. Org. Chem. 1994, 59, 6620. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Solvent-Effect - Discovery R-M Lewis-Base Assisted Asymmetric Crotylation

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Denmark et al. J. Org. Chem. 1994, 59, 6161. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Hosomi-Sakurai Allylation Solvent-Effect - Discovery R-M Lewis-Base Assisted Asymmetric Crotylation

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Allenylation and Propargylation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Kobayashi et al. J. Am. Chem. Soc. 1995, 117, 6392. Kobayashi et al. Tetrahedron 2006, 62, 496. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Allenylation and Propargylation

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Takenaka et al. Org. Lett. 2011, 13, 1654. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Trifluoromethylation – F- promoted

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Brook Rearrangement

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Brook Rearrangement

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Moser et al. Org. Lett. 2000, 717. Moser et al. Org. Lett. 2002, 1981. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Brook Rearrangement

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Smith et al. Synlett 2004, 1363. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Brook Rearrangement

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Takeda et al. J. Am. Chem. Soc. 1993, 9351. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Brook Rearrangement

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Brook Rearrangement

For a good summary on Brook rearrangements : R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Moser et al. Tetrahedron 2001, 57, 2065. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Brook Rearrangement

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Corey et al. J. Am. Chem. Soc. 2002, 11290. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Brook Rearrangement

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Corey et al. J. Am. Chem. Soc. 2002, 11290. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Brook Rearrangement

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Corey et al. J. Am. Chem. Soc. 2002, 11290. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Anion Relay Chemistry (ARC)

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Matsuda et al. Perkin Trans. 1 1979, 26. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Anion Relay Chemistry (ARC)

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Tietze et al. Synlett 1994, 511. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Anion Relay Chemistry (ARC)

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Tietze et al. Angew. Chem. Int. Ed. 1994, 217. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Anion Relay Chemistry (ARC)

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3

Smith et al. J. Am. Chem. Soc. 1997, 6295. R-M R-R’ Introduction to Organosilicon Chemistry R’-X Anion Relay Chemistry (ARC)

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Anion Relay Chemistry (ARC)

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Anion Relay Chemistry (ARC)

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3 R-M R-R’ Introduction to Organosilicon Chemistry R’-X Examples for Exercises

R-M

R-X-R’ R-X-M

R-B(R’)2

R-Si(R’)3