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Présentation Powerpoint 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 Organoboron Chemistry R-Si(R’)3 Introduction to Organosilicon 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 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 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 Alcohol 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 Ether 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 Alkenes 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.
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