Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 4

Name: Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 4 | Compounds of Groups 15 (As, Sb, Bi) and Silicon Compounds
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Compounds of Groups 15 (As, Sb, Bi) and Silicon Compounds

Thieme (Verlag)

1. Auflage

Erschienen am 14. Mai 2014

1060 Seiten

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1 - Science of Synthesis - Volume 4: Compounds of Group 15 (As, Sb, Bi) and Silicon Compounds [Seite 1]
1.1 - Title page [Seite 3]
1.2 - Imprint [Seite 5]
1.3 - Preface [Seite 6]
1.4 - Volume Editor's Preface [Seite 7]
1.5 - Overview [Seite 10]
1.6 - Table of Contents [Seite 14]
1.7 - Introduction [Seite 48]
1.8 - 4.1 Product Class 1: Arsenic Compounds [Seite 60]
1.8.1 - 4.1.1 Product Subclass 1: Triorganoarsenic(III) and Related Compounds [Seite 60]
1.8.1.1 - Synthesis of Product Subclass 1 [Seite 60]
1.8.1.1.1 - 4.1.1.1 Method 1: Alkylation of Metallic Arsenides [Seite 60]
1.8.1.1.2 - 4.1.1.2 Method 2: Transmetalation from Other Organometallic Reagents [Seite 61]
1.8.1.1.2.1 - 4.1.1.2.1 Variation 1: From Grignard Reagents and Arsenic(III) Halides [Seite 61]
1.8.1.1.2.2 - 4.1.1.2.2 Variation 2: From Organolithium Reagents and Arsenic(III) Halides [Seite 62]
1.8.1.1.3 - 4.1.1.3 Method 3: Direct Synthesis from Metallic Arsenic [Seite 63]
1.8.1.1.4 - 4.1.1.4 Method 4: Reduction of Arsenic(V) Oxides [Seite 63]
1.8.1.1.5 - 4.1.1.5 Method 5: Addition of Arsines to Multiple Bonds [Seite 64]
1.8.1.1.6 - 4.1.1.6 Method 6: Cleavage of Tetraorganoarsenic Derivatives [Seite 65]
1.8.1.2 - Applications of Product Subclass 1 in Organic Synthesis [Seite 65]
1.8.1.2.1 - 4.1.1.7 Method 7: Triorganoarsenic(III) Derivatives as Halogen Equivalents [Seite 65]
1.8.1.2.1.1 - 4.1.1.7.1 Variation 1: Nucleophilic Halovinylation [Seite 66]
1.8.1.2.1.2 - 4.1.1.7.2 Variation 2: Carbonyl Haloalkenation [Seite 66]
1.8.2 - 4.1.2 Product Subclass 2: Diorganoarsenic(III) and Related Compounds [Seite 66]
1.8.2.1 - Synthesis of Product Subclass 2 [Seite 67]
1.8.2.1.1 - 4.1.2.1 Method 1: Transmetalation from Other Organometallic Reagents [Seite 67]
1.8.2.1.1.1 - 4.1.2.1.1 Variation 1: From Grignard Reagents and Arsenic(III) Halides [Seite 67]
1.8.2.1.1.2 - 4.1.2.1.2 Variation 2: From Organolithium Reagents and Arsenic(III) Halides [Seite 67]
1.8.2.1.2 - 4.1.2.2 Method 2: Synthesis from Elemental Arsenic [Seite 68]
1.8.2.1.3 - 4.1.2.3 Method 3: Thermolysis of Arsenic(V) Derivatives [Seite 68]
1.8.2.1.4 - 4.1.2.4 Method 4: Redistribution Reactions [Seite 69]
1.8.3 - 4.1.3 Product Subclass 3: Monoorganoarsenic(III) and Related Compounds [Seite 69]
1.8.3.1 - Synthesis of Product Subclass 3 [Seite 70]
1.8.3.1.1 - 4.1.3.1 Method 1: Transmetalation from Other Organometallic Reagents [Seite 70]
1.8.3.1.1.1 - 4.1.3.1.1 Variation 1: From Grignard Reagents and Arsenic(III) Derivatives [Seite 70]
1.8.3.1.1.2 - 4.1.3.1.2 Variation 2: From Organolithium Reagents and Arsenic(III) Derivatives [Seite 70]
1.8.3.1.2 - 4.1.3.2 Method 2: Reduction of Arsonic Acids [Seite 71]
1.8.3.1.3 - 4.1.3.3 Method 3: Redistribution Reactions [Seite 71]
1.8.4 - 4.1.4 Product Subclass 4: Pentaorganoarsenic(V) and Related Compounds [Seite 72]
1.8.4.1 - Synthesis of Product Subclass 4 [Seite 72]
1.8.4.1.1 - 4.1.4.1 Method 1: Transmetalation from Other Organometallic Reagents [Seite 72]
1.8.4.1.2 - 4.1.4.2 Method 2: Reaction Of Arsinimines with Organolithium Reagents [Seite 73]
1.8.5 - 4.1.5 Product Subclass 5: Arsonium Ylides and Related Compounds [Seite 73]
1.8.5.1 - Synthesis of Product Subclass 5 [Seite 73]
1.8.5.1.1 - 4.1.5.1 Method 1: From Arsonium Salts by the "Salt Method" [Seite 74]
1.8.5.1.2 - 4.1.5.2 Method 2: From Reaction with Arsenic(V) Dihalides [Seite 74]
1.8.5.1.3 - 4.1.5.3 Method 3: From Arsine Oxides [Seite 75]
1.8.5.1.4 - 4.1.5.4 Method 4: From Diazonium Salts [Seite 75]
1.8.5.1.5 - 4.1.5.5 Method 5: From Other Ylides by "Transylidation" [Seite 76]
1.8.5.2 - Applications of Product Subclass 5 in Organic Synthesis [Seite 77]
1.8.5.2.1 - 4.1.5.6 Method 6: Reactions of Stabilized Arsonium Ylides with Nonconjugated Carbonyl Compounds [Seite 77]
1.8.5.2.1.1 - 4.1.5.6.1 Variation 1: Reactions of Stabilized Arsonium Ylides with a,ß-Unsaturated Carbonyl Compounds [Seite 79]
1.8.5.2.2 - 4.1.5.7 Method 7: Reactions of Semistabilized Arsonium Ylides with Carbonyl Compounds [Seite 79]
1.8.5.2.3 - 4.1.5.8 Method 8: Reactions of Reactive Arsonium Ylides with Carbonyl Compounds [Seite 83]
1.8.6 - 4.1.6 Product Subclass 6: Tetraorganoarsenic(V) and Related Compounds [Seite 84]
1.8.6.1 - Synthesis of Product Subclass 6 [Seite 84]
1.8.6.1.1 - 4.1.6.1 Method 1: By Alkylation of Organoarsenic(III) Derivatives [Seite 84]
1.8.6.1.2 - 4.1.6.2 Method 2: Reaction of Arsine Oxides with Grignard Reagents [Seite 85]
1.8.7 - 4.1.7 Product Subclass 7: Triorganoarsenic(V) and Related Compounds [Seite 85]
1.8.7.1 - Synthesis of Product Subclass 7 [Seite 85]
1.8.7.1.1 - 4.1.7.1 Method 1: Oxidation of Triorganoarsenic(III) Compounds [Seite 85]
1.8.7.1.1.1 - 4.1.7.1.1 Variation 1: Reaction With Halogens [Seite 86]
1.8.7.1.1.2 - 4.1.7.1.2 Variation 2: Reaction with "Halogen Substitute" Compounds [Seite 86]
1.8.7.1.1.3 - 4.1.7.1.3 Variation 3: Reaction with Active Oxygen Compounds [Seite 87]
1.8.7.2 - Applications of Product Subclass 7 in Organic Synthesis [Seite 88]
1.8.7.2.1 - 4.1.7.2 Method 2: Triorganoarsenic(V) Derivatives as Halogen Equivalents [Seite 88]
1.8.8 - 4.1.8 Product Subclass 8: Diorganoarsenic(V) and Related Compounds [Seite 88]
1.8.8.1 - Synthesis of Product Subclass 8 [Seite 89]
1.8.8.1.1 - 4.1.8.1 Method 1: From Diazonium Salts: The Bart Reaction [Seite 89]
1.8.8.1.2 - 4.1.8.2 Method 2: From Alkaline Alkyl Arsonate Salts: The Meyer Reaction [Seite 89]
1.8.9 - 4.1.9 Product Subclass 9: Monoorganoarsenic(V) and Related Compounds [Seite 90]
1.8.9.1 - Synthesis of Product Subclass 9 [Seite 90]
1.8.9.1.1 - 4.1.9.1 Method 1: The Bart Reaction [Seite 90]
1.8.9.1.1.1 - 4.1.9.1.1 Variation 1: The Scheller Modification of the Bart Reaction [Seite 91]
1.8.9.1.2 - 4.1.9.2 Method 2: The Béchamp Reaction [Seite 92]
1.8.9.1.3 - 4.1.9.3 Method 3: The Meyer Reaction [Seite 92]
1.8.9.1.3.1 - 4.1.9.3.1 Variation 1: The Rosenmund Reaction [Seite 93]
1.8.9.1.4 - 4.1.9.4 Method 4: Oxidative Hydrolysis [Seite 93]
1.9 - 4.2 Product Class 2: Antimony Compounds [Seite 100]
1.9.1 - 4.2.1 Product Subclass 1: Tertiary Stibines [Seite 100]
1.9.1.1 - Synthesis of Product Subclass 1 [Seite 100]
1.9.1.1.1 - 4.2.1.1 Method 1: From Alkali Metal Antimonides [Seite 100]
1.9.1.1.1.1 - 4.2.1.1.1 Variation 1: Cleavage of an Aryl--Antimony Bond [Seite 101]
1.9.1.1.1.2 - 4.2.1.1.2 Variation 2: Cleavage of an Alkyl--Antimony Bond [Seite 101]
1.9.1.1.1.3 - 4.2.1.1.3 Variation 3: Cleavage of a Halo--Antimony Bond [Seite 102]
1.9.1.1.2 - 4.2.1.2 Method 2: By Transmetalation [Seite 102]
1.9.1.1.2.1 - 4.2.1.2.1 Variation 1: Formation of Symmetrical Tertiary Stibines Using Grignard Reagents [Seite 102]
1.9.1.1.2.2 - 4.2.1.2.2 Variation 2: Formation of Nonsymmetrical Tertiary Stibines Using Organolithiums [Seite 103]
1.9.1.2 - Applications of Product Subclass 1 in Organic Synthesis [Seite 104]
1.9.1.2.1 - 4.2.1.3 Method 3: Alkenation Reactions [Seite 104]
1.9.1.2.1.1 - 4.2.1.3.1 Variation 1: Wittig-type Alkenation of Aldehydes Mediated by Tributylstibine [Seite 104]
1.9.1.2.1.2 - 4.2.1.3.2 Variation 2: Alkenation of Aldehydes with Dibromomalonates [Seite 104]
1.9.1.2.2 - 4.2.1.4 Method 4: Palladium-Catalyzed Processes [Seite 105]
1.9.2 - 4.2.2 Product Subclass 2: Di- and Monoorganostibines [Seite 105]
1.9.2.1 - Synthesis of Product Subclass 2 [Seite 105]
1.9.2.1.1 - 4.2.2.1 Method 1: By Cleavage of Distibines [Seite 106]
1.9.2.1.2 - 4.2.2.2 Method 2: By Redistribution Reactions [Seite 106]
1.9.2.1.2.1 - 4.2.2.2.1 Variation 1: Reaction of Antimony(III) Halides with Triarylstibines [Seite 106]
1.9.2.1.2.2 - 4.2.2.2.2 Variation 2: Reaction of Antimony(III) Halides with Halostibines [Seite 107]
1.9.2.1.3 - 4.2.2.3 Method 3: By Transmetalation [Seite 107]
1.9.2.1.3.1 - 4.2.2.3.1 Variation 1: From Tetraalkyllead [Seite 107]
1.9.2.1.3.2 - 4.2.2.3.2 Variation 2: From Organostannanes [Seite 108]
1.9.2.1.4 - 4.2.2.4 Method 4: From .5-Stibanes [Seite 108]
1.9.2.1.4.1 - 4.2.2.4.1 Variation 1: Thermolysis of Dihalotriorgano-.5-stibanes [Seite 108]
1.9.2.1.4.2 - 4.2.2.4.2 Variation 2: Thermolysis of Trihalodiorgano-.5-stibanes [Seite 109]
1.9.2.1.4.3 - 4.2.2.4.3 Variation 3: Reduction of .5-Stibanes [Seite 109]
1.9.3 - 4.2.3 Product Subclass 3: Pentaorgano-.5-stibanes [Seite 109]
1.9.3.1 - Synthesis of Product Subclass 3 [Seite 109]
1.9.3.1.1 - 4.2.3.1 Method 1: Synthesis of Symmetrical Pentaorgano-.5-stibanes [Seite 110]
1.9.3.1.2 - 4.2.3.2 Method 2: Synthesis of Unsymmetrical Pentaorgano-.5-stibanes [Seite 110]
1.9.3.2 - Applications of Product Subclass 3 in Organic Synthesis [Seite 110]
1.9.3.2.1 - 4.2.3.3 Method 3: Reaction of .5-Stibanes with Electrophiles [Seite 110]
1.9.4 - 4.2.4 Product Subclass 4: Stibonium Ylides and Stibimines [Seite 111]
1.9.4.1 - Synthesis of Product Subclass 4 [Seite 111]
1.9.4.1.1 - 4.2.4.1 Method 1: Use of Diazo Compounds [Seite 111]
1.9.4.1.2 - 4.2.4.2 Method 2: From Sulfonyl Azides [Seite 112]
1.9.4.2 - Applications of Product Subclass 4 in Organic Synthesis [Seite 112]
1.9.4.2.1 - 4.2.4.3 Method 3: Wittig-type Reactions of Stibonium Ylides [Seite 112]
1.9.5 - 4.2.5 Product Subclass 5: Tetraorgano-.5-stibanes [Seite 113]
1.9.5.1 - Synthesis of Product Subclass 5 [Seite 113]
1.9.5.1.1 - 4.2.5.1 Method 1: By Cleavage of Pentaorgano-.5-stibanes [Seite 113]
1.9.5.1.2 - 4.2.5.2 Method 2: From Tertiary Stibines [Seite 113]
1.9.5.1.2.1 - 4.2.5.2.1 Variation 1: By Alkylation of Trialkylstibines [Seite 113]
1.9.5.1.2.2 - 4.2.5.2.2 Variation 2: By Arylation of Triarylstibines [Seite 114]
1.9.5.2 - Applications of Product Subclass 5 in Organic Synthesis [Seite 114]
1.9.5.2.1 - 4.2.5.3 Method 3: Allylation of Aldehydes by .5-Stibanes [Seite 114]
1.9.6 - 4.2.6 Product Subclass 6: Triorgano-.5-stibanes [Seite 115]
1.9.6.1 - Synthesis of Product Subclass 6 [Seite 115]
1.9.6.1.1 - 4.2.6.1 Method 1: Oxidation of Tertiary Stibines with Bromine [Seite 115]
1.9.6.2 - Applications of Product Subclass 6 in Organic Synthesis [Seite 115]
1.9.6.2.1 - 4.2.6.2 Method 2: Formation of Diketones [Seite 115]
1.9.7 - 4.2.7 Product Subclass 7: Di- and Monoorgano-.5-stibanes [Seite 116]
1.9.7.1 - Synthesis of Product Subclass 7 [Seite 116]
1.9.7.1.1 - 4.2.7.1 Method 1: By Transmetalation [Seite 116]
1.9.7.1.2 - 4.2.7.2 Method 2: From Tertiary Stibines [Seite 117]
1.9.7.1.2.1 - 4.2.7.2.1 Variation 1: Cleavage of Triphenylstibine [Seite 117]
1.9.7.1.2.2 - 4.2.7.2.2 Variation 2: Halogenation of Halodiorganostibines [Seite 117]
1.9.7.1.3 - 4.2.7.3 Method 3: From Diazonium Salts [Seite 117]
1.9.7.1.3.1 - 4.2.7.3.1 Variation 1: Preparation of Unsymmetrical Hydroxystibine Oxides [Seite 117]
1.9.7.1.3.2 - 4.2.7.3.2 Variation 2: Preparation of Dihydroxystibine Oxides by the Scheller Reaction [Seite 118]
1.10 - 4.3 Product Class 3: Bismuth Compounds [Seite 124]
1.10.1 - Synthesis of Product Class 3 [Seite 124]
1.10.1.1 - 4.3.1 Product Subclass 1: Alkyl- and Arylbismuthines [Seite 124]
1.10.1.1.1 - 4.3.1.1 Method 1: From Grignard and Organolithium Reagents [Seite 125]
1.10.1.1.2 - 4.3.1.2 Method 2: From Alkali Bismuthides [Seite 128]
1.10.1.1.3 - 4.3.1.3 Method 3: By Transmetalation [Seite 128]
1.10.1.1.4 - 4.3.1.4 Additional Methods [Seite 129]
1.10.1.2 - 4.3.2 Product Subclass 2: Alkyl- and Arylhalobismuthines [Seite 130]
1.10.1.2.1 - 4.3.2.1 Method 1: By Bi--C Bond Cleavage and Redistribution Reactions [Seite 131]
1.10.1.2.2 - 4.3.2.2 Method 2: From Organometallic Reagents [Seite 133]
1.10.1.3 - 4.3.3 Product Subclass 3: Alkyl- and Arylbismuthines Containing Bonds between Bismuth and Group 15 or 16 Elements [Seite 134]
1.10.1.3.1 - 4.3.3.1 Method 1: From Halobismuthines [Seite 135]
1.10.1.3.2 - 4.3.3.2 Method 2: From Alkoxybismuthines [Seite 136]
1.10.1.3.3 - 4.3.3.3 Method 3: By Cleavage of Bi--C Bond(s) by Acidic Compounds [Seite 136]
1.10.1.3.4 - 4.3.3.4 Additional Methods [Seite 137]
1.10.1.4 - 4.3.4 Product Subclass 4: Dibismuthines and Dibismuthenes [Seite 138]
1.10.1.4.1 - 4.3.4.1 Method 1: From Tertiary Bismuthines [Seite 140]
1.10.1.4.2 - 4.3.4.2 Method 2: From Halodiorganobismuthines [Seite 140]
1.10.1.5 - 4.3.5 Product Subclass 5: Organobismuth Compounds with Bismuth--Transition Metal Bonds [Seite 141]
1.10.1.6 - 4.3.6 Product Subclass 6: Alkoxy- and Hydroxybismuthine Oxides [Seite 141]
1.10.1.7 - 4.3.7 Product Subclass 7: Dihalotriorganobismuth(V) and Related Compounds [Seite 142]
1.10.1.7.1 - 4.3.7.1 Method 1: Oxidative Addition of Halogen or Halogen Equivalent to Triorganobismuthines [Seite 143]
1.10.1.7.2 - 4.3.7.2 Method 2: Oxidation of Bismuthines with Ozone, Peroxy Acids, and Other Oxygen Equivalents [Seite 144]
1.10.1.7.3 - 4.3.7.3 Method 3: By Metathetical Reactions [Seite 144]
1.10.1.8 - 4.3.8 Product Subclass 8: Oxybis[triarylhalobismuth(V)] and Related Compounds [Seite 145]
1.10.1.9 - 4.3.9 Product Subclass 9: Bismuthine Imides [Seite 146]
1.10.1.9.1 - 4.3.9.1 Method 1: From Tertiary Bismuthines [Seite 146]
1.10.1.9.2 - 4.3.9.2 Method 2: From Triaryldihalobismuth(V) [Seite 147]
1.10.1.10 - 4.3.10 Product Subclass 10: Bismuthine Oxides [Seite 147]
1.10.1.11 - 4.3.11 Product Subclass 11: Bismuthonium Salts [Seite 149]
1.10.1.11.1 - 4.3.11.1 Method 1: From Pentaarylbismuth(V) Compounds [Seite 150]
1.10.1.11.2 - 4.3.11.2 Method 2: From Triaryldifluorobismuth(V) [Seite 151]
1.10.1.11.3 - 4.3.11.3 Method 3: From Tertiary Bismuthines [Seite 152]
1.10.1.12 - 4.3.12 Product Subclass 12: Bismuthonium Ylides [Seite 152]
1.10.1.12.1 - 4.3.12.1 Method 1: From Tertiary Bismuthines [Seite 152]
1.10.1.12.2 - 4.3.12.2 Method 2: From Triarylbismuth(V) Compounds [Seite 153]
1.10.1.12.3 - 4.3.12.3 Method 3: From Bismuthonium Salts [Seite 154]
1.10.1.13 - 4.3.13 Product Subclass 13: Pentaorganobismuth(V) Compounds [Seite 154]
1.10.1.14 - 4.3.14 Product Subclass 14: Hexaorganobismuthates [Seite 155]
1.10.2 - Applications of Product Class 3 in Organic Synthesis [Seite 155]
1.11 - 4.4 Product Class 4: Silicon Compounds [Seite 164]
1.11.1 - 4.4.1 Product Subclass 1: Disilenes [Seite 164]
1.11.1.1 - Synthesis of Product Subclass 1 [Seite 166]
1.11.1.1.1 - 4.4.1.1 Method 1: Photolysis of Linear Trisilanes [Seite 166]
1.11.1.1.2 - 4.4.1.2 Method 2: Photolysis of Cyclotrisilanes [Seite 167]
1.11.1.1.3 - 4.4.1.3 Method 3: Reductive Coupling of Dihalosilanes [Seite 168]
1.11.1.1.4 - 4.4.1.4 Method 4: Reduction of 1,2-Dihalodisilanes [Seite 169]
1.11.1.1.5 - 4.4.1.5 Method 5: Photolysis of 2,3-Disilabicyclo[2.2.2]octa-5,7-dienes [Seite 170]
1.11.1.1.6 - 4.4.1.6 Additional Methods [Seite 170]
1.11.2 - 4.4.2 Product Subclass 2: Silenes [Seite 172]
1.11.2.1 - Synthesis of Product Subclass 2 [Seite 174]
1.11.2.1.1 - 4.4.2.1 Method 1: By Photolysis or Thermolysis of Acylsilanes [Seite 174]
1.11.2.1.1.1 - 4.4.2.1.1 Variation 1: Photolysis of Acylsilanes [Seite 174]
1.11.2.1.1.2 - 4.4.2.1.2 Variation 2: Thermolysis of Acylpolysilanes [Seite 175]
1.11.2.1.2 - 4.4.2.2 Method 2: By 1,2-Salt Elimination from a-Lithiated Silanes [Seite 175]
1.11.2.1.2.1 - 4.4.2.2.1 Variation 1: By Metalation of the Ca--H Bond of Alkylsilanes [Seite 176]
1.11.2.1.2.2 - 4.4.2.2.2 Variation 2: By Metalation of the C--Br Bond of a-Bromoalkylsilanes [Seite 177]
1.11.2.1.2.3 - 4.4.2.2.3 Variation 3: From Halo(vinyl)silanes [Seite 177]
1.11.2.1.3 - 4.4.2.3 Method 3: Sila-Peterson Reactions [Seite 178]
1.11.2.1.3.1 - 4.4.2.3.1 Variation 1: From the Addition of Silyl Anions to Ketones [Seite 178]
1.11.2.1.3.2 - 4.4.2.3.2 Variation 2: From the Addition of Organolithium Reagents to Acylpolysilanes [Seite 179]
1.11.2.1.3.3 - 4.4.2.3.3 Variation 3: By the Deprotonation of a-Hydroxysilanes [Seite 179]
1.11.2.1.4 - 4.4.2.4 Additional Methods [Seite 180]
1.11.3 - 4.4.3 Product Subclass 3: Silylenes [Seite 182]
1.11.3.1 - Synthesis of Product Subclass 3 [Seite 184]
1.11.3.1.1 - 4.4.3.1 Method 1: Reduction of Dihalosilanes [Seite 184]
1.11.3.2 - Applications of Product Subclass 3 in Organic Synthesis [Seite 188]
1.11.3.2.1 - 4.4.3.2 Method 2: Insertion Reactions [Seite 188]
1.11.3.2.2 - 4.4.3.3 Method 3: Addition Reactions [Seite 194]
1.11.3.2.2.1 - 4.4.3.3.1 Variation 1: To Dienes [Seite 194]
1.11.3.2.2.2 - 4.4.3.3.2 Variation 2: To Aldehydes, Ketones, and Imines [Seite 195]
1.11.3.2.2.3 - 4.4.3.3.3 Variation 3: To Alkynes and Nitriles [Seite 199]
1.11.3.2.2.4 - 4.4.3.3.4 Variation 4: To Isocyanides and Azides [Seite 199]
1.11.3.2.2.5 - 4.4.3.3.5 Variation 5: To Transition Metals [Seite 200]
1.11.4 - 4.4.4 Product Subclass 4: Silyl Hydrides [Seite 206]
1.11.4.1 - Synthesis of Product Subclass 4 [Seite 207]
1.11.4.1.1 - 4.4.4.1 Method 1: From Inorganic Silanes [Seite 207]
1.11.4.1.2 - 4.4.4.2 Method 2: From Aryl- and Alkylsilyl Hydrides [Seite 210]
1.11.4.1.3 - 4.4.4.3 Method 3: From Silyl Halides [Seite 215]
1.11.4.1.4 - 4.4.4.4 Method 4: From Silyl Ethers [Seite 217]
1.11.4.1.5 - 4.4.4.5 Methods 5: Additional Methods [Seite 218]
1.11.4.2 - Applications of Product Subclass 4 in Organic Synthesis [Seite 219]
1.11.4.2.1 - 4.4.4.6 Method 6: Hydrosilylation of Alkenes, Alkynes, and Related Compounds [Seite 219]
1.11.4.2.2 - 4.4.4.7 Method 7: Silyl Hydrides as Reducing Reagents [Seite 223]
1.11.5 - 4.4.5 Product Subclass 5: Disilanes [Seite 234]
1.11.5.1 - Synthesis of Product Subclass 5 [Seite 235]
1.11.5.1.1 - 4.4.5.1 Method 1: Via Coupling of Hydrosilanes [Seite 235]
1.11.5.1.1.1 - 4.4.5.1.1 Variation 1: By Use of Transition Metal Catalysts [Seite 235]
1.11.5.1.1.2 - 4.4.5.1.2 Variation 2: By Photolysis of Alkylhydrosilanes in the Presence of Mercury [Seite 236]
1.11.5.1.2 - 4.4.5.2 Method 2: Via Photolysis of Organopolysilanes in the Presence of Hydrosilanes [Seite 237]
1.11.5.1.3 - 4.4.5.3 Method 3: Via Coupling of (Organosilyl)alkali Metal Salts with Halosilanes [Seite 237]
1.11.5.1.4 - 4.4.5.4 Method 4: Via Coupling of Halosilanes Using Metals or Metal Salts [Seite 238]
1.11.5.1.4.1 - 4.4.5.4.1 Variation 1: By Use of Alkali Metals [Seite 239]
1.11.5.1.4.2 - 4.4.5.4.2 Variation 2: By Use of Magnesium Metal [Seite 239]
1.11.5.1.4.3 - 4.4.5.4.3 Variation 3: By Use of Lithium Naphthalenide [Seite 240]
1.11.5.1.4.4 - 4.4.5.4.4 Variation 4: By Use of Samarium(II) Iodide [Seite 241]
1.11.5.1.4.5 - 4.4.5.4.5 Variation 5: By Use of Potassium--Graphite Laminate (C8K) [Seite 241]
1.11.5.1.5 - 4.4.5.5 Method 5: Via Electrochemical Reduction of Halosilanes [Seite 242]
1.11.5.1.6 - 4.4.5.6 Method 6: Via Photolysis of Organopolysilanes in the Presence of Trapping Agents [Seite 243]
1.11.5.1.6.1 - 4.4.5.6.1 Variation 1: In the Presence of Ketones [Seite 243]
1.11.5.1.6.2 - 4.4.5.6.2 Variation 2: In the Presence of Functionalized Alkenes [Seite 244]
1.11.5.1.7 - 4.4.5.7 Method 7: From Halodisilanes and Organometallic Reagents [Seite 245]
1.11.5.1.8 - 4.4.5.8 Additional Methods [Seite 245]
1.11.5.2 - Applications of Product Subclass 5 in Organic Synthesis [Seite 246]
1.11.6 - 4.4.6 Product Subclass 6: Silyltin Reagents [Seite 252]
1.11.6.1 - Synthesis of Product Subclass 6 [Seite 252]
1.11.6.1.1 - 4.4.6.1 Method 1: Synthesis of Silyltin Reagents [Seite 252]
1.11.6.2 - Applications of Product Subclass 6 in Organic Synthesis [Seite 254]
1.11.7 - 4.4.7 Product Subclass 7: Silylboron Reagents [Seite 258]
1.11.7.1 - Synthesis of Product Subclass 7 [Seite 258]
1.11.7.1.1 - 4.4.7.1 Method 1: Synthesis of Silylboron Reagents [Seite 258]
1.11.7.1.1.1 - 4.4.7.1.1 Variation 1: Synthesis of (Dimethylphenylsilyl)(pinacol)borane from Dimethylphenylsilyllithium and Pinacolborane [Seite 260]
1.11.7.1.1.2 - 4.4.7.1.2 Variation 2: Synthesis of (Dimethylphenylsilyl)(pinacol)borane from Dimethylphenylsilyllithium and Isopropoxy(pinacol)borane [Seite 261]
1.11.7.1.1.3 - 4.4.7.1.3 Variation 3: Synthesis of Lithium Triethyl(dimethylphenylsilyl)borate [Seite 261]
1.11.7.2 - Applications of Product Subclass 7 in Organic Synthesis [Seite 262]
1.11.8 - 4.4.8 Product Subclass 8: Silylaluminum Reagents [Seite 266]
1.11.8.1 - Synthesis of Product Subclass 8 [Seite 266]
1.11.8.1.1 - 4.4.8.1 Method 1: Tris(trimethylsilyl)aluminum from Bis(trimethylsilyl)mercury(II) [Seite 266]
1.11.8.1.1.1 - 4.4.8.1.1 Variation 1: Tris(trimethylsilyl)aluminum from Chlorotrimethylsilane and Aluminum, Lithium, and Mercury Metals [Seite 267]
1.11.8.1.2 - 4.4.8.2 Additional Methods [Seite 268]
1.11.8.2 - Applications of Product Subclass 8 in Organic Synthesis [Seite 268]
1.11.9 - 4.4.9 Product Subclass 9: Silylzinc Reagents [Seite 272]
1.11.9.1 - Synthesis of Product Subclass 9 [Seite 272]
1.11.9.1.1 - 4.4.9.1 Method 1: From a Triorganosilyl Anion Source and Zinc(II) Reagents [Seite 272]
1.11.9.1.1.1 - 4.4.9.1.1 Variation 1: Dialkyl(triorganosilyl)zincate Reagents from an Alkylmetal, Triorganosilylmetal Reagents, and Zinc(II) Salts [Seite 274]
1.11.9.2 - Applications of Product Subclass 9 in Organic Synthesis [Seite 274]
1.11.10 - 4.4.10 Product Subclass 10: Silylcopper Reagents [Seite 278]
1.11.10.1 - Synthesis of Product Subclass 10 [Seite 278]
1.11.10.1.1 - 4.4.10.1 Method 1: Synthesis of Triorganosilylcopper(I) Reagents [Seite 278]
1.11.10.1.2 - 4.4.10.2 Method 2: Synthesis of Mixed Alkyl(triorganosilyl)copper(I) Reagents [Seite 279]
1.11.10.2 - Applications of Product Subclass 10 in Organic Synthesis [Seite 280]
1.11.11 - 4.4.11 Product Subclass 11: Silyllithium Reagents [Seite 284]
1.11.11.1 - Synthesis of Product Subclass 11 [Seite 285]
1.11.11.1.1 - 4.4.11.1 Method 1: By Lithiation of Halotriorganosilanes [Seite 285]
1.11.11.1.1.1 - 4.4.11.1.1 Variation 1: Using Lithium Metal [Seite 285]
1.11.11.1.1.2 - 4.4.11.1.2 Variation 2: Using an Alkyllithium Reagent [Seite 286]
1.11.11.1.2 - 4.4.11.2 Method 2: Via Si--Si Bond Cleavage [Seite 286]
1.11.11.1.2.1 - 4.4.11.2.1 Variation 1: Reductive Cleavage Using Lithium Metal [Seite 287]
1.11.11.1.2.2 - 4.4.11.2.2 Variation 2: Nucleophilic Cleavage Using an Alkyllithium Reagent [Seite 287]
1.11.11.1.3 - 4.4.11.3 Method 3: Via Si--Sn Bond Cleavage [Seite 288]
1.11.11.1.4 - 4.4.11.4 Method 4: From Bis(triorganosilyl)mercury(II) Compounds [Seite 289]
1.11.11.2 - Applications of Product Subclass 11 in Organic Synthesis [Seite 289]
1.11.12 - 4.4.12 Product Subclass 12: Haloorganosilanes [Seite 294]
1.11.12.1 - Synthesis of Product Subclass 12 [Seite 296]
1.11.12.1.1 - 4.4.12.1 Method 1: Conversion of Hydridoorganosilanes into Haloorganosilanes [Seite 296]
1.11.12.1.1.1 - 4.4.12.1.1 Variation 1: By Reaction with Copper(II) Halides [Seite 296]
1.11.12.1.1.2 - 4.4.12.1.2 Variation 2: By Reaction with Hydrogen Halides, Haloalkanes, or Haloarenes [Seite 297]
1.11.12.1.1.3 - 4.4.12.1.3 Variation 3: By Reaction with Reactive Organic Halides in the Presence of Tertiary Amines [Seite 298]
1.11.12.1.1.4 - 4.4.12.1.4 Variation 4: By Reaction with Dihalogens [Seite 299]
1.11.12.1.2 - 4.4.12.2 Method 2: Halogenolysis of Disilanes [Seite 299]
1.11.12.1.3 - 4.4.12.3 Method 3: Halogenolysis of Si--C Bonds [Seite 299]
1.11.12.1.4 - 4.4.12.4 Method 4: Halogen Exchange [Seite 301]
1.11.12.1.4.1 - 4.4.12.4.1 Variation 1: Generation In Situ [Seite 302]
1.11.12.1.5 - 4.4.12.5 Method 5: Conversion of Disiloxanes into Haloorganosilanes [Seite 302]
1.11.12.1.6 - 4.4.12.6 Method 6: Direct Synthesis from Silicon and Organic Halides [Seite 303]
1.11.12.1.7 - 4.4.12.7 Method 7: Hydrosilylation of Unsaturated Bonds with Halohydridosilanes [Seite 304]
1.11.12.1.8 - 4.4.12.8 Method 8: Organometallic Exchange of Halogen in a Halosilane To Give a New Halosilane [Seite 305]
1.11.12.2 - Applications of Product Subclass 12 in Organic Synthesis [Seite 307]
1.11.12.2.1 - 4.4.12.9 Fluoroorganosilanes [Seite 307]
1.11.12.2.2 - 4.4.12.10 Chloroorganosilanes [Seite 308]
1.11.12.2.3 - 4.4.12.11 Bromoorganosilanes [Seite 309]
1.11.12.2.4 - 4.4.12.12 Iodoorganosilanes [Seite 310]
1.11.13 - 4.4.13 Product Subclass 13: Silyl Diethers [Seite 316]
1.11.13.1 - Synthesis of Product Subclass 13 [Seite 316]
1.11.13.1.1 - 4.4.13.1 Method 1: Synthesis of Symmetrical Acyclic Silyl Diethers [Seite 316]
1.11.13.1.1.1 - 4.4.13.1.1 Variation 1: From Silanes [Seite 317]
1.11.13.1.1.2 - 4.4.13.1.2 Variation 2: From Dichlorosilanes [Seite 318]
1.11.13.1.2 - 4.4.13.2 Method 2: Synthesis of Unsymmetrical Acyclic Silyl Diethers [Seite 320]
1.11.13.1.2.1 - 4.4.13.2.1 Variation 1: From Alkoxy(halo)silanes [Seite 320]
1.11.13.1.2.2 - 4.4.13.2.2 Variation 2: From Chlorosilyl Pent-4-enyl Ethers [Seite 323]
1.11.13.1.3 - 4.4.13.3 Method 3: Synthesis of Cyclic Silyl Diethers [Seite 324]
1.11.13.1.3.1 - 4.4.13.3.1 Variation 1: From Silanes [Seite 324]
1.11.13.1.3.2 - 4.4.13.3.2 Variation 2: From Dichlorosilanes or Silyl Trifluoromethanesulfonates [Seite 325]
1.11.13.1.3.3 - 4.4.13.3.3 Variation 3: From Hexamethylcyclotrisilazane [Seite 327]
1.11.13.2 - Applications of Product Subclass 13 in Organic Synthesis [Seite 328]
1.11.13.2.1 - 4.4.13.4 Method 4: Intramolecular Reactions Using Silicon-Tethered Reactants [Seite 328]
1.11.13.2.2 - 4.4.13.5 Method 5: Standard Protection of Alcohols [Seite 335]
1.11.14 - 4.4.14 Product Subclass 14: Silyl Esters [Seite 340]
1.11.14.1 - Synthesis of Product Subclass 14 [Seite 342]
1.11.14.1.1 - 4.4.14.1 Silyl Sulfates and Trifluoromethanesulfonates [Seite 342]
1.11.14.1.1.1 - 4.4.14.1.1 Method 1: Polymer-Supported Silyl Trifluoromethanesulfonates [Seite 342]
1.11.14.1.1.2 - 4.4.14.1.2 Method 2: Reaction of Tetrasubstituted Silanes with Trifluoromethanesulfonic Acid [Seite 342]
1.11.14.1.1.2.1 - 4.4.14.1.2.1 Variation 1: Using Trisubstituted Allylsilanes [Seite 343]
1.11.14.1.1.3 - 4.4.14.1.3 Method 3: Reaction of Trialkylchlorosilanes with Trifluoromethanesulfonic Acid [Seite 343]
1.11.14.1.1.4 - 4.4.14.1.4 Method 4: Reaction of Trialkylchlorosilanes with Sulfuric Acid [Seite 344]
1.11.14.1.2 - 4.4.14.2 Silyl Phosphates [Seite 344]
1.11.14.1.2.1 - 4.4.14.2.1 Method 1: Reaction of Bis(trimethylsilyl) Ether with Phosphorus Pentoxide [Seite 344]
1.11.14.1.3 - 4.4.14.3 Silyl Carboxylates [Seite 345]
1.11.14.1.3.1 - 4.4.14.3.1 Method 1: Reaction of Hydrosilanes with Carboxylic Acids [Seite 345]
1.11.14.1.3.2 - 4.4.14.3.2 Method 2: Reaction of Trialkylchlorosilanes with Carboxylic Acids [Seite 346]
1.11.14.1.3.2.1 - 4.4.14.3.2.1 Variation 1: With Sterically Hindered Trialkylchlorosilanes [Seite 347]
1.11.14.1.3.3 - 4.4.14.3.3 Method 3: Reaction of Carboxylic Acids with Trialkylsilyl Trifluoromethanesulfonates [Seite 347]
1.11.14.1.3.3.1 - 4.4.14.3.3.1 Variation 1: With Trialkylsilyl Trifluoromethanesulfonates Formed In Situ [Seite 348]
1.11.14.1.3.4 - 4.4.14.3.4 Method 4: Reaction of Carboxylic Acids with N,N'-Bis(trimethylsilyl)urea [Seite 349]
1.11.14.1.4 - 4.4.14.4 Additional Methods [Seite 349]
1.11.15 - 4.4.15 Product Subclass 15: Silyl Imidic Esters (Silylimino Ethers) [Seite 352]
1.11.15.1 - Synthesis of Product Subclass 15 [Seite 353]
1.11.15.1.1 - 4.4.15.1 Method 1: Silylation of Amide Derivatives [Seite 353]
1.11.15.1.1.1 - 4.4.15.1.1 Variation 1: With Chlorosilanes [Seite 353]
1.11.15.1.1.2 - 4.4.15.1.2 Variation 2: With Silyl Triflates [Seite 354]
1.11.15.1.1.3 - 4.4.15.1.3 Variation 3: With Trimethylsilyldimethylamine [Seite 355]
1.11.15.1.1.4 - 4.4.15.1.4 Variation 4: With Hexamethyldisilazane [Seite 355]
1.11.15.1.1.5 - 4.4.15.1.5 Variation 5: Silylamide-Based Silylation [Seite 356]
1.11.15.1.2 - 4.4.15.2 Method 2: Catalytic Silylation with Trimethyl(pentafluorophenyl)silane [Seite 357]
1.11.15.1.3 - 4.4.15.3 Method 3: Coupling of Alkali Metal Hexamethyldisilazanides with Acid Derivatives [Seite 358]
1.11.15.1.3.1 - 4.4.15.3.1 Variation 1: With Acyl Chlorides [Seite 358]
1.11.15.1.3.2 - 4.4.15.3.2 Variation 2: With Esters [Seite 359]
1.11.15.1.4 - 4.4.15.4 Method 4: Acylation of Trimethylsilylhydroxylamines and Bis(trimethylsilyl)carbodiimide [Seite 359]
1.11.15.1.4.1 - 4.4.15.4.1 Variation 1: With Acyl Chlorides [Seite 359]
1.11.15.1.4.2 - 4.4.15.4.2 Variation 2: With Ketenes [Seite 360]
1.11.15.1.5 - 4.4.15.5 Method 5: Insertion of Formaldehyde into the Si--N Bond of O,N-Bis(silyl)amides [Seite 361]
1.11.15.1.6 - 4.4.15.6 Additional Methods [Seite 361]
1.11.16 - 4.4.16 Product Subclass 16: Silyl Enol Ethers [Seite 364]
1.11.16.1 - Synthesis of Product Subclass 16 [Seite 377]
1.11.16.1.1 - 4.4.16.1 Method 1: From Carbonyl Compounds, Bases, and Electrophilic Silylating Agents [Seite 377]
1.11.16.1.1.1 - 4.4.16.1.1 Variation 1: Synthesis of Silyl Enol Ethers of Aldehydes and Ketones [Seite 378]
1.11.16.1.1.2 - 4.4.16.1.2 Variation 2: Synthesis of Silyl Ketene Acetals and Related Compounds [Seite 383]
1.11.16.1.1.3 - 4.4.16.1.3 Variation 3: Synthesis of Siloxybutadienes [Seite 388]
1.11.16.1.1.4 - 4.4.16.1.4 Variation 4: Chemoselective Synthesis of Silyl Enol Ethers [Seite 390]
1.11.16.1.1.5 - 4.4.16.1.5 Variation 5: Enantioselective Synthesis of Silyl Enol Ethers [Seite 391]
1.11.16.1.1.6 - 4.4.16.1.6 Variation 6: Synthesis of Polymer-Supported Silyl Enol Ethers [Seite 392]
1.11.16.1.2 - 4.4.16.2 Method 2: From a,ß-Unsaturated Carbonyl Compounds by Reductive Silylation [Seite 393]
1.11.16.1.2.1 - 4.4.16.2.1 Variation 1: By Metal Reduction and Subsequent Enolate Trapping [Seite 393]
1.11.16.1.2.2 - 4.4.16.2.2 Variation 2: By Conjugate Addition of Nucleophiles and Subsequent Enolate Trapping [Seite 394]
1.11.16.1.2.3 - 4.4.16.2.3 Variation 3: By Hydrosilylation [Seite 396]
1.11.16.1.3 - 4.4.16.3 Method 3: From Diesters in the Acyloin Condensation [Seite 397]
1.11.16.1.4 - 4.4.16.4 Method 4: From a-Halo Carbonyl Compounds by Reductive Silylation [Seite 397]
1.11.16.1.5 - 4.4.16.5 Method 5: From Alkenes by Hydrosilylation in the Presence of Carbon Monoxide [Seite 398]
1.11.16.1.6 - 4.4.16.6 Method 6: From Acylsilanes by Nucleophilic Addition and Brook Rearrangement [Seite 399]
1.11.16.1.6.1 - 4.4.16.6.1 Variation 1: With Alkenyl- or Alkynylmetals [Seite 399]
1.11.16.1.6.2 - 4.4.16.6.2 Variation 2: With Nucleophilic Reagents Having an a-Leaving Group [Seite 400]
1.11.16.1.7 - 4.4.16.7 Method 7: From Silyl Esters by Alkylidenation [Seite 401]
1.11.16.1.8 - 4.4.16.8 Method 8: Rearrangements of Silyl Ethers [Seite 402]
1.11.16.1.8.1 - 4.4.16.8.1 Variation 1: Via Rearrangement of ß-Siloxy Carbenoids [Seite 402]
1.11.16.1.8.2 - 4.4.16.8.2 Variation 2: Via Isomerization of Allyl and Propargyl Silyl Ethers [Seite 402]
1.11.16.1.8.3 - 4.4.16.8.3 Variation 3: Via Rearrangement of Silyl Cyclopropyl Ethers [Seite 403]
1.11.16.1.9 - 4.4.16.9 Method 9: By Oxidation of Vinyllithiums [Seite 404]
1.11.16.1.10 - 4.4.16.10 Method 10: From Ketenes by Haloalkylsilane Trapping of Lithium Enolates [Seite 404]
1.11.16.1.11 - 4.4.16.11 Method 11: Interconversion of Silyl Enol Ethers [Seite 405]
1.11.16.1.11.1 - 4.4.16.11.1 Variation 1: Introduction of Nitrogen-Based Functional Groups at the a-Position [Seite 405]
1.11.16.1.11.2 - 4.4.16.11.2 Variation 2: Introduction of Nitrogen-Based Functional Groups at the ß-Position [Seite 405]
1.11.16.1.11.3 - 4.4.16.11.3 Variation 3: Ene-like Reactions of Silyl Enol Ethers with Aldehydes [Seite 406]
1.11.16.1.11.4 - 4.4.16.11.4 Variation 4: Alkylation and Arylation of 2-Siloxyallyl Halides [Seite 407]
1.11.16.1.11.5 - 4.4.16.11.5 Variation 5: Isomerization of Silyl Enol Ethers [Seite 407]
1.11.16.1.11.6 - 4.4.16.11.6 Variation 6: Conversion of Trimethylsilyl Enol Ethers into Trichlorosilyl Enol Ethers [Seite 408]
1.11.16.1.12 - 4.4.16.12 Additional Methods [Seite 408]
1.11.17 - 4.4.17 Product Subclass 17: Silyl Ethers [Seite 418]
1.11.17.1 - 4.4.17.1 Trimethylsilyl Ethers [Seite 419]
1.11.17.1.1 - Formation [Seite 419]
1.11.17.1.1.1 - 4.4.17.1.1 Method 1: Silylation of Alcohols with Chlorotrimethylsilane [Seite 419]
1.11.17.1.1.2 - 4.4.17.1.2 Method 2: Silylation of Alcohols with Trimethylsilyl Trifluoromethanesulfonate [Seite 420]
1.11.17.1.1.3 - 4.4.17.1.3 Method 3: Silylation of Alcohols with Trimethylsilyl Cyanide [Seite 420]
1.11.17.1.1.4 - 4.4.17.1.4 Method 4: Silylation of Alcohols with N,O-Bis(trimethylsilyl)acetamide [Seite 421]
1.11.17.1.2 - Cleavage [Seite 422]
1.11.17.1.2.1 - 4.4.17.1.5 Method 5: Cleavage of Trimethylsilyl Ethers with Acidic Reagents [Seite 422]
1.11.17.1.2.2 - 4.4.17.1.6 Method 6: Cleavage of Trimethylsilyl Ethers under Basic Conditions [Seite 423]
1.11.17.2 - 4.4.17.2 Triethylsilyl Ethers [Seite 424]
1.11.17.2.1 - Formation [Seite 424]
1.11.17.2.1.1 - 4.4.17.2.1 Method 1: Silylation of Alcohols with Chlorotriethylsilane [Seite 424]
1.11.17.2.1.1.1 - 4.4.17.2.1.1 Variation 1: With Chlorotriethylsilane in Pyridine [Seite 425]
1.11.17.2.1.1.2 - 4.4.17.2.1.2 Variation 2: With Chlorotriethylsilane in the Presence of 4-(Dimethylamino)pyridine [Seite 426]
1.11.17.2.1.2 - 4.4.17.2.2 Method 2: Silylation of Alcohols with Triethylsilyl Trifluoromethanesulfonate [Seite 427]
1.11.17.2.2 - Cleavage [Seite 427]
1.11.17.2.2.1 - 4.4.17.2.3 Method 3: Cleavage of Triethylsilyl Ethers under Acidic Conditions [Seite 427]
1.11.17.2.2.1.1 - 4.4.17.2.3.1 Variation 1: In the Presence of 4-Toluenesulfonic Acid [Seite 428]
1.11.17.2.2.1.2 - 4.4.17.2.3.2 Variation 2: With Trifluoromethanesulfonic Acid [Seite 429]
1.11.17.2.2.2 - 4.4.17.2.4 Method 4: Cleavage of Triethylsilyl Ethers with Tetrabutylammonium Fluoride [Seite 429]
1.11.17.3 - 4.4.17.3 tert-Butyldimethylsilyl Ethers [Seite 430]
1.11.17.3.1 - Formation [Seite 430]
1.11.17.3.1.1 - 4.4.17.3.1 Method 1: Silylation of Alcohols with tert-Butyldimethylsilyl Chloride [Seite 430]
1.11.17.3.1.1.1 - 4.4.17.3.1.1 Variation 1: In the Presence of 4-(Dimethylamino)pyridine [Seite 431]
1.11.17.3.1.1.2 - 4.4.17.3.1.2 Variation 2: In Dichloromethane [Seite 431]
1.11.17.3.1.2 - 4.4.17.3.2 Method 2: Silylation of Alcohols with tert-Butyldimethylsilyl Trifluoromethanesulfonate [Seite 432]
1.11.17.3.1.2.1 - 4.4.17.3.2.1 Variation 1: Selective Silylation of Phenols [Seite 433]
1.11.17.3.1.2.2 - 4.4.17.3.2.2 Variation 2: Selective Silylation of Alcohols [Seite 433]
1.11.17.3.1.3 - 4.4.17.3.3 Method 3: Migration of a tert-Butyldimethylsilyl Group from a tert-Butyldimethylsilyl Ether to an Alcohol [Seite 434]
1.11.17.3.2 - Cleavage [Seite 435]
1.11.17.3.2.1 - 4.4.17.3.4 Method 4: Cleavage of tert-Butyldimethylsilyl Ethers with Tetrabutylammonium Fluoride [Seite 435]
1.11.17.3.2.2 - 4.4.17.3.5 Method 5: Cleavage of tert-Butyldimethylsilyl Ethers with Tris(dimethylamino)sulfur (Trimethylsilyl)difluoride [Seite 437]
1.11.17.3.2.3 - 4.4.17.3.6 Method 6: Cleavage of tert-Butyldimethylsilyl Ethers under Acidic Conditions [Seite 438]
1.11.17.3.2.3.1 - 4.4.17.3.6.1 Variation 1: With Hydrogen Fluoride--Pyridine Complex [Seite 438]
1.11.17.3.2.3.2 - 4.4.17.3.6.2 Variation 2: With Mineral Acid [Seite 439]
1.11.17.3.2.3.3 - 4.4.17.3.6.3 Variation 3: With Organic Acids [Seite 440]
1.11.17.3.2.3.4 - 4.4.17.3.6.4 Variation 4: With Lewis Acids [Seite 442]
1.11.17.4 - 4.4.17.4 Triisopropylsilyl Ethers [Seite 443]
1.11.17.4.1 - Formation [Seite 443]
1.11.17.4.1.1 - 4.4.17.4.1 Method 1: Silylation of Alcohols with Triisopropylsilyl Trifluoromethanesulfonate and 2,6-Lutidine [Seite 443]
1.11.17.4.1.1.1 - 4.4.17.4.1.1 Variation 1: With Triisopropylsilyl Trifluoromethanesulfonate in the Presence of 4-(Dimethylamino)pyridine [Seite 444]
1.11.17.4.2 - Cleavage [Seite 444]
1.11.17.4.2.1 - 4.4.17.4.2 Method 2: Cleavage of Triisopropylsilyl Ethers with Tetrabutylammonium Fluoride [Seite 444]
1.11.17.4.2.2 - 4.4.17.4.3 Method 3: Cleavage of Triisopropylsilyl Ethers with Tris(dimethylamino)sulfur (Trimethylsilyl)difluoride [Seite 445]
1.11.17.4.2.3 - 4.4.17.4.4 Method 4: Cleavage of Triisopropylsilyl Ethers with Hydrogen Fluoride--Pyridine Complex [Seite 446]
1.11.17.4.2.4 - 4.4.17.4.5 Method 5: Cleavage of Triisopropylsilyl Ethers under Acidic Conditions [Seite 447]
1.11.17.5 - 4.4.17.5 tert-Butyldiphenylsilyl Ethers [Seite 448]
1.11.17.5.1 - Formation [Seite 448]
1.11.17.5.1.1 - 4.4.17.5.1 Method 1: Silylation of Alcohols with tert-Butyldiphenylsilyl Chloride [Seite 448]
1.11.17.5.1.1.1 - 4.4.17.5.1.1 Variation 1: In the Presence of 4-(Dimethylamino)pyridine [Seite 449]
1.11.17.5.1.1.2 - 4.4.17.5.1.2 Variation 2: Using Butyllithium [Seite 449]
1.11.17.5.1.2 - 4.4.17.5.2 Method 2: Silylation of Alcohols with tert-Butyldiphenylsilyl Trifluoromethanesulfonate [Seite 450]
1.11.17.5.1.3 - 4.4.17.5.3 Method 3: Migration of a tert-Butyldiphenylsilyl Group to an Alcohol [Seite 450]
1.11.17.5.2 - Cleavage [Seite 451]
1.11.17.5.2.1 - 4.4.17.5.4 Method 4: Cleavage of tert-Butyldiphenylsilyl Ethers with Tetrabutylammonium Fluoride [Seite 451]
1.11.17.5.2.2 - 4.4.17.5.5 Method 5: Cleavage of tert-Butyldiphenylsilyl Ethers with Tetrabutylammonium Fluoride in Acetic Acid [Seite 453]
1.11.17.5.2.3 - 4.4.17.5.6 Method 6: Cleavage of tert-Butyldiphenylsilyl Ethers with Tris(dimethylamino)sulfur (Trimethylsilyl)difluoride [Seite 453]
1.11.17.5.2.4 - 4.4.17.5.7 Method 7: Cleavage of tert-Butyldiphenylsilyl Ethers with Hydrogen Fluoride--Pyridine Complex [Seite 454]
1.11.17.5.2.4.1 - 4.4.17.5.7.1 Variation 1: Cleavage with Hydrogen Fluoride--Triethylamine Complex [Seite 455]
1.11.17.6 - 4.4.17.6 Other Silyl Ethers [Seite 456]
1.11.18 - 4.4.18 Product Subclass 18: Silyl Peroxides [Seite 460]
1.11.18.1 - Synthesis of Product Subclass 18 [Seite 460]
1.11.18.1.1 - 4.4.18.1 Method 1: Synthesis of Silyl Peroxides [Seite 460]
1.11.18.2 - Applications of Product Subclass 18 in Organic Synthesis [Seite 461]
1.11.18.2.1 - 4.4.18.2 Method 2: Various Oxidations Using Silyl Peroxides [Seite 461]
1.11.18.2.2 - 4.4.18.3 Method 3: Synthesis of Alcohols via Silyl Peroxides [Seite 463]
1.11.18.2.2.1 - 4.4.18.3.1 Variation 1: Oxidation of Heteroatom-Substituted Organosilicon Compounds [Seite 463]
1.11.18.2.2.2 - 4.4.18.3.2 Variation 2: Oxidation of Phenyl-Substituted Organosilicon Compounds [Seite 465]
1.11.18.2.2.3 - 4.4.18.3.3 Variation 3: Oxidation of Heteroaromatic-Substituted Organosilicon Compounds [Seite 468]
1.11.18.2.2.4 - 4.4.18.3.4 Variation 4: Oxidation of Allyl-Substituted Organosilicon Compounds [Seite 469]
1.11.18.2.2.5 - 4.4.18.3.5 Variation 5: Oxidation of Alkyl-Substituted Organosilicon Compounds [Seite 469]
1.11.19 - 4.4.19 Product Subclass 19: Silyl Sulfides and Selenides [Seite 474]
1.11.19.1 - Synthesis of Product Subclass 19 [Seite 476]
1.11.19.1.1 - 4.4.19.1 Method 1: From Hydrogen Sulfide and Aminosilanes [Seite 476]
1.11.19.1.2 - 4.4.19.2 Method 2: From Thiolates and Halosilanes [Seite 477]
1.11.19.1.2.1 - 4.4.19.2.1 Variation 1: From Enethiolates and Halosilanes [Seite 478]
1.11.19.1.3 - 4.4.19.3 Method 3: From In Situ Generated Selenolates and Halosilanes [Seite 479]
1.11.19.1.3.1 - 4.4.19.3.1 Variation 1: From Lithium, Powdered Selenium, and Chlorotrimethylsilane [Seite 479]
1.11.20 - 4.4.20 Product Subclass 20: Silyl Azides [Seite 482]
1.11.20.1 - Synthesis of Product Subclass 20 [Seite 482]
1.11.20.1.1 - 4.4.20.1 Method 1: Synthesis of Silyl Azides by Substitution [Seite 482]
1.11.20.1.1.1 - 4.4.20.1.1 Variation 1: From Silyl Halides [Seite 482]
1.11.20.1.1.2 - 4.4.20.1.2 Variation 2: From N-Butyltrialkylsilanamines [Seite 483]
1.11.20.1.2 - 4.4.20.2 Method 2: Synthesis of Silyl Azides by Trans-silylations [Seite 483]
1.11.20.2 - Applications of Product Subclass 20 in Organic Synthesis [Seite 484]
1.11.20.2.1 - 4.4.20.3 Method 3: Synthesis of Heterocyclic Compounds Using Silyl Azides [Seite 484]
1.11.20.2.1.1 - 4.4.20.3.1 Variation 1: Triazoles [Seite 484]
1.11.20.2.1.2 - 4.4.20.3.2 Variation 2: Tetrazoles [Seite 485]
1.11.20.2.1.3 - 4.4.20.3.3 Variation 3: Other Heterocycles [Seite 485]
1.11.20.2.2 - 4.4.20.4 Method 4: Synthesis of Acyl Azides Using Silyl Azides [Seite 486]
1.11.20.2.2.1 - 4.4.20.4.1 Variation 1: From Carboxylic Acid Derivatives [Seite 486]
1.11.20.2.2.2 - 4.4.20.4.2 Variation 2: From Aldehydes [Seite 486]
1.11.20.2.3 - 4.4.20.5 Method 5: Synthesis of a-Azido Alcohols Using Silyl Azides [Seite 487]
1.11.20.2.4 - 4.4.20.6 Method 6: Synthesis of ß-Azido Alcohols Using Silyl Azides [Seite 487]
1.11.20.2.4.1 - 4.4.20.6.1 Variation 1: From Epoxides [Seite 487]
1.11.20.2.4.2 - 4.4.20.6.2 Variation 2: From 1,2-Diols [Seite 490]
1.11.20.2.5 - 4.4.20.7 Method 7: Synthesis of ß-Azido Amines Using Silyl Azides [Seite 490]
1.11.20.2.6 - 4.4.20.8 Method 8: Synthesis of Alkyl Azides Using Silyl Azides [Seite 491]
1.11.20.2.6.1 - 4.4.20.8.1 Variation 1: Alkyl Azides [Seite 491]
1.11.20.2.6.2 - 4.4.20.8.2 Variation 2: ß-Azido Ketones [Seite 492]
1.11.20.2.6.3 - 4.4.20.8.3 Variation 3: Aryl Azides [Seite 492]
1.11.20.2.6.4 - 4.4.20.8.4 Variation 4: Miscellaneous [Seite 492]
1.11.20.2.7 - 4.4.20.9 Method 9: Applications of Silyl Azides in Rearrangement and in Oxidation Reactions [Seite 493]
1.11.21 - 4.4.21 Product Subclass 21: Silylamines [Seite 498]
1.11.21.1 - Synthesis of Product Subclass 21 [Seite 498]
1.11.21.1.1 - 4.4.21.1 Method 1: Reaction of Chlorosilanes with Amines [Seite 498]
1.11.21.1.1.1 - 4.4.21.1.1 Variation 1: Preparation of Diethylamino- and Diisopropylamino-Substituted Silane Derivatives [Seite 499]
1.11.21.1.1.2 - 4.4.21.1.2 Variation 2: Preparation and ortho-Lithiation of N,N'-Bis[2-(dimethylamino)ethyl]-N,N'-dimethyldiphenylsilanediamine [Seite 500]
1.11.21.1.1.3 - 4.4.21.1.3 Variation 3: Reaction of Chloro{2-[chloro(dimethyl)silyl]ethyl}-dimethylsilane with Primary Amines [Seite 501]
1.11.21.1.1.4 - 4.4.21.1.4 Variation 4: Reaction of Bis(dimethylsilyl)benzene with Primary Amines [Seite 502]
1.11.21.1.2 - 4.4.21.2 Method 2: Reaction of Silyl Trichloroacetates with Amines [Seite 502]
1.11.21.1.3 - 4.4.21.3 Method 3: Reaction of Tris(2-aminoethyl)amines with Tris- and Tetrakis(dimethylamino)silanes [Seite 503]
1.11.21.1.4 - 4.4.21.4 Method 4: Reaction of Silyllithiums with Amines [Seite 504]
1.11.21.1.5 - 4.4.21.5 Method 5: Reaction of Hexamethyldisilazane [Seite 504]
1.11.21.1.5.1 - 4.4.21.5.1 Variation 1: Preparation and Reaction of N,O-Bis(trimethylsilyl)hydroxylamine [Seite 504]
1.11.21.1.5.2 - 4.4.21.5.2 Variation 2: Preparation of N,O-Bis(trimethylsilyl) Sulfamate [Seite 505]
1.11.21.1.5.3 - 4.4.21.5.3 Variation 3: Monosilylation of Anilines [Seite 506]
1.11.21.1.5.4 - 4.4.21.5.4 Variation 4: Preparation and Reaction of Lithium N,N-Bis(trimethylsilyl)(aminomethyl)acetylide [Seite 506]
1.11.21.1.5.5 - 4.4.21.5.5 Variation 5: Preparation of N-Silylaldimines [Seite 508]
1.11.21.1.5.6 - 4.4.21.5.6 Variation 6: Preparation of N,N,N'-Tris(trimethylsilyl)amidines [Seite 508]
1.11.21.1.6 - 4.4.21.6 Method 6: Preparation of 1-Aza-2-silacyclobutanes [Seite 509]
1.11.21.1.6.1 - 4.4.21.6.1 Variation 1: Aza-Brook Rearrangement of (a-Silylallyl)amines to N-Silylenamines [Seite 509]
1.11.21.1.7 - 4.4.21.7 Method 7: Preparation and Reaction of Aminosilyl Anions [Seite 510]
1.11.21.1.8 - 4.4.21.8 Method 8: Reaction of 1-(Trimethylsilyl)-1H-1,2,3-benzotriazole [Seite 511]
1.11.21.1.8.1 - 4.4.21.8.1 Variation 1: Reaction of 2-Aza-1,3-dienes with Trimethylsilyl Trifluoromethanesulfonate [Seite 512]
1.11.21.1.8.2 - 4.4.21.8.2 Variation 2: Reductive Silylation of Azaaromatic Compounds [Seite 512]
1.11.21.1.8.3 - 4.4.21.8.3 Variation 3: Synthesis of N,N'-Disilylated Enediamines [Seite 513]
1.11.21.1.8.4 - 4.4.21.8.4 Variation 4: Preparation of Diazasilacycloalkenes [Seite 513]
1.11.21.1.8.5 - 4.4.21.8.5 Variation 5: Reductive Silylation of Nitriles [Seite 514]
1.11.21.1.9 - 4.4.21.9 Method 9: Hydrosilylation of Imines [Seite 514]
1.11.21.1.9.1 - 4.4.21.9.1 Variation 1: Hydrosilylation of Carbodiimides [Seite 515]
1.11.21.1.9.2 - 4.4.21.9.2 Variation 2: Hydrosilylation of Nitriles [Seite 515]
1.11.21.1.10 - 4.4.21.10 Method 10: Preparation of Stable Silanimines [Seite 516]
1.11.21.1.11 - 4.4.21.11 Method 11: Preparation of a Lithium Silaamidide [Seite 517]
1.11.21.1.12 - 4.4.21.12 Method 12: Preparation and Reaction of Stable Cyclic Bis(amino)silylenes [Seite 517]
1.11.22 - 4.4.22 Product Subclass 22: Silyl Phosphines [Seite 520]
1.11.22.1 - Synthesis of Product Subclass 22 [Seite 521]
1.11.22.1.1 - 4.4.22.1 Method 1: From Silyl Hydrides [Seite 521]
1.11.22.1.2 - 4.4.22.2 Method 2: From Silyl Halides [Seite 522]
1.11.22.1.3 - 4.4.22.3 Method 3: From Other Silyl Phosphines [Seite 524]
1.11.22.1.4 - 4.4.22.4 Additional Methods [Seite 525]
1.11.23 - 4.4.23 Product Subclass 23: Silylmethyl Anions [Seite 528]
1.11.23.1 - 4.4.23.1 Method 1: Metalation of Alkylsilanes and Their Derivatives [Seite 532]
1.11.23.1.1 - 4.4.23.1.1 Variation 1: With Alkyllithiums [Seite 533]
1.11.23.1.2 - 4.4.23.1.2 Variation 2: With Schlosser's Base [Seite 534]
1.11.23.1.3 - 4.4.23.1.3 Variation 3: With Lithium Diisopropylamide and Similar Amide Bases [Seite 534]
1.11.23.1.4 - 4.4.23.1.4 Variation 4: With Other Bases [Seite 535]
1.11.23.2 - 4.4.23.2 Method 2: Metal--Halogen Exchange of a-Haloalkylsilanes [Seite 535]
1.11.23.2.1 - 4.4.23.2.1 Variation 1: With Magnesium [Seite 536]
1.11.23.2.2 - 4.4.23.2.2 Variation 2: With Lithium [Seite 537]
1.11.23.3 - 4.4.23.3 Method 3: Transmetalation Reactions of a-Silylalkylmetals [Seite 538]
1.11.23.3.1 - 4.4.23.3.1 Variation 1: Of a-Silylalkyllithium Compounds [Seite 538]
1.11.23.3.2 - 4.4.23.3.2 Variation 2: Of a-Silylalkylmagnesium [Seite 539]
1.11.23.3.3 - 4.4.23.3.3 Variation 3: Of a-Silylalkylstannane [Seite 539]
1.11.23.4 - 4.4.23.4 Method 4: Reductive Lithiation of a-Sulfanyl- and a-Selanylalkylsilanes [Seite 540]
1.11.23.5 - 4.4.23.5 Method 5: Addition of Organometallic Reagents to Vinylsilanes and Their Analogues [Seite 541]
1.11.23.5.1 - 4.4.23.5.1 Variation 1: Of Organolithium Reagents to Vinylsilanes [Seite 541]
1.11.23.5.2 - 4.4.23.5.2 Variation 2: Of Organomagnesium Reagents to Vinylsilanes [Seite 542]
1.11.23.6 - 4.4.23.6 Additional Methods [Seite 542]
1.11.24 - 4.4.24 Product Subclass 24: Silyl Cyanides [Seite 546]
1.11.24.1 - 4.4.24.1 Tetracoordinate Silyl Cyanides [Seite 546]
1.11.24.1.1 - 4.4.24.1.1 Method 1: From Silyl Chlorides [Seite 547]
1.11.24.1.1.1 - 4.4.24.1.1.1 Variation 1: Using Silver(I) or Mercury(II) Cyanide [Seite 548]
1.11.24.1.1.2 - 4.4.24.1.1.2 Variation 2: Using Lithium Cyanide [Seite 548]
1.11.24.1.1.3 - 4.4.24.1.1.3 Variation 3: Using Sodium or Potassium Cyanide [Seite 549]
1.11.24.1.1.4 - 4.4.24.1.1.4 Variation 4: Using Tetraethylammonium Cyanide [Seite 549]
1.11.24.1.1.5 - 4.4.24.1.1.5 Variation 5: Using Hydrogen Cyanide and Triethylamine [Seite 550]
1.11.24.1.1.6 - 4.4.24.1.1.6 Variation 6: By Transcyanation [Seite 550]
1.11.24.1.1.7 - 4.4.24.1.1.7 Variation 7: Using Acetonitrile [Seite 550]
1.11.24.1.2 - 4.4.24.1.2 Method 2: From Other Silyl Halides [Seite 551]
1.11.24.1.3 - 4.4.24.1.3 Method 3: By Cleavage of a Si--O Bond [Seite 552]
1.11.24.1.4 - 4.4.24.1.4 Method 4: By Cleavage of a Si--S Bond [Seite 553]
1.11.24.1.5 - 4.4.24.1.5 Method 5: By Cleavage of a Si--N Bond [Seite 554]
1.11.24.1.6 - 4.4.24.1.6 Method 6: By Cleavage of a Si--C Bond [Seite 554]
1.11.24.1.7 - 4.4.24.1.7 Method 7: By Cleavage of a Si--Si Bond [Seite 554]
1.11.24.1.8 - 4.4.24.1.8 Method 8: By Cleavage of a Si--H Bond [Seite 555]
1.11.24.1.9 - 4.4.24.1.9 Method 9: By Cleavage of a Si--Hg Bond [Seite 556]
1.11.24.2 - 4.4.24.2 Pentacoordinate Silyl Cyanides [Seite 556]
1.11.25 - 4.4.25 Product Subclass 25: Acylsilanes [Seite 560]
1.11.25.1 - Synthesis of Product Subclass 25 [Seite 561]
1.11.25.1.1 - 4.4.25.1 Simple Acylsilanes [Seite 561]
1.11.25.1.1.1 - 4.4.25.1.1 Method 1: Hydroboration--Oxidation of Alkynylsilanes [Seite 562]
1.11.25.1.1.2 - 4.4.25.1.2 Method 2: Hydrolysis of Acetals [Seite 562]
1.11.25.1.1.3 - 4.4.25.1.3 Method 3: From Silylmetal Intermediates [Seite 565]
1.11.25.1.1.4 - 4.4.25.1.4 Method 4: Preparation from Enol Ethers [Seite 568]
1.11.25.1.1.5 - 4.4.25.1.5 Method 5: Palladium-Catalyzed Coupling [Seite 571]
1.11.25.1.1.6 - 4.4.25.1.6 Method 6: Oxidation of a-Hydroxysilanes [Seite 571]
1.11.25.1.1.7 - 4.4.25.1.7 Method 7: Silylation of Acylmetal Species [Seite 572]
1.11.25.1.1.8 - 4.4.25.1.8 Method 8: Other Oxidative Methods [Seite 574]
1.11.25.1.1.9 - 4.4.25.1.9 Additional Methods [Seite 575]
1.11.25.1.2 - 4.4.25.2 a-Haloacylsilanes [Seite 576]
1.11.25.1.2.1 - 4.4.25.2.1 Method 1: Halogenation of Trialk-1-enyl Borates [Seite 576]
1.11.25.1.2.2 - 4.4.25.2.2 Method 2: Halogenation of the Enol Ethers of Acylsilanes [Seite 577]
1.11.25.1.2.3 - 4.4.25.2.3 Method 3: Bromination--Rearrangement of Epoxysilanes [Seite 577]
1.11.25.1.2.4 - 4.4.25.2.4 Additional Methods [Seite 578]
1.11.25.1.3 - 4.4.25.3 a-Oxoacylsilanes [Seite 578]
1.11.25.1.3.1 - 4.4.25.3.1 Method 1: Oxidation of Diols [Seite 578]
1.11.25.1.3.2 - 4.4.25.3.2 Method 2: From Allenyl Ethers [Seite 579]
1.11.25.1.3.3 - 4.4.25.3.3 Method 3: From Silyldiazoesters [Seite 579]
1.11.25.1.4 - 4.4.25.4 a,ß-Unsaturated Acylsilanes [Seite 579]
1.11.25.1.4.1 - 4.4.25.4.1 Method 1: From Allenyl Ethers [Seite 580]
1.11.25.1.4.2 - 4.4.25.4.2 Method 2: Other Enol Ether Methods [Seite 582]
1.11.25.1.4.3 - 4.4.25.4.3 Method 3: Hydroboration--Oxidation of Enynylsilanes and (Arylalkynyl)silanes [Seite 584]
1.11.25.1.4.4 - 4.4.25.4.4 Method 4: From Alk-2-ynoylsilanes [Seite 585]
1.11.25.1.4.5 - 4.4.25.4.5 Method 5: Oxidation of a-Hydroxysilanes [Seite 585]
1.11.25.1.4.6 - 4.4.25.4.6 Additional Methods [Seite 586]
1.11.25.1.5 - 4.4.25.5 a-Cyclopropylacylsilanes [Seite 587]
1.11.25.1.5.1 - 4.4.25.5.1 Method 1: From Silylmetal Species [Seite 588]
1.11.25.1.5.2 - 4.4.25.5.2 Method 2: From a-Haloacylsilanes [Seite 588]
1.11.25.1.5.3 - 4.4.25.5.3 Additional Methods [Seite 589]
1.11.25.1.6 - 4.4.25.6 a-Epoxyacylsilanes [Seite 590]
1.11.25.1.6.1 - 4.4.25.6.1 Method 1: Epoxidation of a,ß-Unsaturated Acylsilanes [Seite 590]
1.11.25.2 - Applications of Product Subclass 25 in Organic Synthesis [Seite 590]
1.11.25.2.1 - 4.4.25.7 Simple Acylsilanes [Seite 590]
1.11.25.2.1.1 - 4.4.25.7.1 Method 1: Nucleophilic Addition [Seite 590]
1.11.25.2.1.2 - 4.4.25.7.2 Method 2: Acylsilanes as Acyl Anion Precursors [Seite 597]
1.11.25.2.1.3 - 4.4.25.7.3 Method 3: Enolate and Enol Ether Reactions [Seite 598]
1.11.25.2.1.4 - 4.4.25.7.4 Method 4: Photochemistry [Seite 599]
1.11.25.2.1.5 - 4.4.25.7.5 Method 5: Biotransformations [Seite 601]
1.11.25.2.1.6 - 4.4.25.7.6 Method 6: Miscellaneous [Seite 602]
1.11.25.2.2 - 4.4.25.8 a-Haloacylsilanes [Seite 602]
1.11.25.2.3 - 4.4.25.9 a-Oxoacylsilanes [Seite 604]
1.11.25.2.4 - 4.4.25.10 a,ß-Unsaturated Acylsilanes [Seite 605]
1.11.26 - 4.4.26 Product Subclass 26: 1-Diazo-1-silylalkanes [Seite 616]
1.11.26.1 - Synthesis of Product Subclass 26 [Seite 618]
1.11.26.1.1 - 4.4.26.1 Method 1: From Trialkyl(chloromethyl)silanes by Diazo Transfer Reactions [Seite 618]
1.11.26.1.2 - 4.4.26.2 Method 2: From Acylsilanes [Seite 620]
1.11.26.1.3 - 4.4.26.3 Method 3: Silylation of a-Diazoacetates, a-Diazophosphonates, and a-Diazo Ketones [Seite 620]
1.11.26.1.4 - 4.4.26.4 Method 4: Alkylation of Diazo(trimethylsilyl)methane [Seite 621]
1.11.26.1.5 - 4.4.26.5 Method 5: Acylation of Diazo(pentamethyldisilanyl)methane [Seite 621]
1.11.26.1.6 - 4.4.26.6 Method 6: Silylation of Diazo(trimethylsilyl)methane [Seite 622]
1.11.27 - 4.4.27 Product Subclass 27: a-Haloalkylsilanes [Seite 626]
1.11.27.1 - Synthesis of Product Subclass 27 [Seite 627]
1.11.27.1.1 - 4.4.27.1 Method 1: Direct Halogenation of Alkylsilanes [Seite 627]
1.11.27.1.1.1 - 4.4.27.1.1 Variation 1: Chlorination of Alkylsilanes [Seite 628]
1.11.27.1.1.2 - 4.4.27.1.2 Variation 2: Bromination of Alkylsilanes [Seite 628]
1.11.27.1.2 - 4.4.27.2 Method 2: Substitution of a-Hydroxyalkylsilanes [Seite 629]
1.11.27.1.2.1 - 4.4.27.2.1 Variation 1: Substitution with Chloride Using Thionyl Chloride [Seite 630]
1.11.27.1.2.2 - 4.4.27.2.2 Variation 2: Chlorination of a-Hydroxyalkylsilanes with Triphenylphosphine and Carbon Tetrachloride [Seite 631]
1.11.27.1.2.3 - 4.4.27.2.3 Variation 3: Iodination of a-Hydroxyalkylsilanes with Methyl(triphenoxy)phosphonium Iodide [Seite 631]
1.11.27.1.3 - 4.4.27.3 Method 3: Haloalkylation of Halosilanes [Seite 632]
1.11.27.1.4 - 4.4.27.4 Method 4: Reaction of Halosilanes with Diazomethane [Seite 633]
1.11.27.1.5 - 4.4.27.5 Method 5: Nucleophilic Substitution of Halo(haloalkyl)silanes [Seite 634]
1.11.27.1.6 - 4.4.27.6 Method 6: Alkylation of a-Haloalkylsilanes [Seite 635]
1.11.27.2 - Applications of Product Subclass 27 in Organic Synthesis [Seite 635]
1.11.28 - 4.4.28 Product Subclass 28: a-Silyl Alcohols, Ethers, and Amines [Seite 642]
1.11.28.1 - Synthesis of Product Subclass 28 [Seite 644]
1.11.28.1.1 - 4.4.28.1 Method 1: From Silyl Hydrides and Fischer Alkoxycarbene Complexes [Seite 644]
1.11.28.1.2 - 4.4.28.2 Method 2: From Silyl Hydrides and N-Vinylamides or N-Vinylureas [Seite 644]
1.11.28.1.3 - 4.4.28.3 Method 3: From Silyl Halides and Ethers or Amines [Seite 645]
1.11.28.1.3.1 - 4.4.28.3.1 Variation 1: Deprotonative a-Silylation of Aliphatic Ethers with Lithium-free Butylpotassium and Chlorosilanes [Seite 645]
1.11.28.1.3.2 - 4.4.28.3.2 Variation 2: Deprotonative a-Silylation of Alkyl Arylmethyl Ethers with tert-Butyllithium/N,N,N',N'-Tetramethylethylenediamine and Chlorosilanes [Seite 646]
1.11.28.1.3.3 - 4.4.28.3.3 Variation 3: Deprotonative a-Silylation of Cyclic Secondary N-tert-Butoxycarbonyl Amines with sec-Butyllithium/N,N,N',N'-Tetramethylethylenediamine or sec-Butyllithium/(-)-Sparteine and Chlorosilanes [Seite 647]
1.11.28.1.3.4 - 4.4.28.3.4 Variation 4: Dehalogenative Silylation of Chloromethyl Ethers with Lithium and Chlorosilanes [Seite 648]
1.11.28.1.3.5 - 4.4.28.3.5 Variation 5: Desulfurative Silylation of a-Phenylsulfanyl Ethers with Lithium 1-(Dimethylamino)naphthalenide and Chlorosilanes [Seite 648]
1.11.28.1.4 - 4.4.28.4 Method 4: From Silyl Halides and Aldehydes or Ketones by Reductive Silylation with Magnesium [Seite 649]
1.11.28.1.5 - 4.4.28.5 Method 5: From Silyl Halides and Esters by Reductive Silylation with Magnesium or Sodium [Seite 650]
1.11.28.1.5.1 - 4.4.28.5.1 Variation 1: Reductive Silylation of tert-Butyl or Trimethylsilyl Benzoates with the Chlorotrimethylsilane/Magnesium/Hexamethyl-phosphoric Triamide System [Seite 651]
1.11.28.1.5.2 - 4.4.28.5.2 Variation 2: Reductive Silylation of Trimethylsilyl Alkanoates with the Chlorotrimethylsilane/Sodium/Tetrahydrofuran System [Seite 651]
1.11.28.1.6 - 4.4.28.6 Method 6: From Silyl Halides and Cyanides or O-Trimethylsilyl Cyanohydrins by Reductive Silylation with Lithium [Seite 652]
1.11.28.1.7 - 4.4.28.7 Method 7: From O-Silyl Ethers [Seite 653]
1.11.28.1.7.1 - 4.4.28.7.1 Variation 1: Retro-[1,2]-Brook Rearrangement of Allyl and Benzyl O-Silyl Ethers [Seite 653]
1.11.28.1.7.2 - 4.4.28.7.2 Variation 2: Retro-[1,2]-Brook Rearrangement of a-Stannyl Silyl Ethers [Seite 654]
1.11.28.1.8 - 4.4.28.8 Method 8: From Silyl Anions and Aldehydes or Ketones [Seite 655]
1.11.28.1.8.1 - 4.4.28.8.1 Variation 1: With Trimethylsilyllithium [Seite 656]
1.11.28.1.8.2 - 4.4.28.8.2 Variation 2: With Tris(trimethylsilyl)aluminum--Diethyl Ether Complex [Seite 657]
1.11.28.1.8.3 - 4.4.28.8.3 Variation 3: With Disilanes by Fluoride-Induced Catalysis [Seite 657]
1.11.28.1.8.4 - 4.4.28.8.4 Variation 4: With Dimethylphenylsilyllithium [Seite 658]
1.11.28.1.9 - 4.4.28.9 Method 9: From Silyl Anions and Esters [Seite 659]
1.11.28.1.10 - 4.4.28.10 Method 10: From (a-Haloalkyl)silanes and Nitrogen or Oxygen Nucleophiles [Seite 660]
1.11.28.1.10.1 - 4.4.28.10.1 Variation 1: N-Alkylation of Primary or Secondary Amines [Seite 660]
1.11.28.1.10.2 - 4.4.28.10.2 Variation 2: O- and N-Alkylation of Masked Hydroxy or Amino Groups [Seite 661]
1.11.28.1.11 - 4.4.28.11 Method 11: From a-Metallosilanes [Seite 662]
1.11.28.1.12 - 4.4.28.12 Method 12: From Acylsilanes [Seite 663]
1.11.28.1.12.1 - 4.4.28.12.1 Variation 1: Via Asymmetric Reduction with B-Chlorodiisopinocampheylborane [Seite 663]
1.11.28.1.12.2 - 4.4.28.12.2 Variation 2: Via Samarium(II) Iodide Promoted Reductions and Alkylations [Seite 664]
1.11.28.1.12.3 - 4.4.28.12.3 Variation 3: Via Addition of Organolithium or Organomagnesium Reagents [Seite 665]
1.11.28.1.12.4 - 4.4.28.12.4 Variation 4: Via Barbier-type Addition of Organoindium Reagents [Seite 666]
1.11.28.1.13 - 4.4.28.13 Method 13: From Vinylsilanes [Seite 667]
1.11.28.1.13.1 - 4.4.28.13.1 Variation 1: Via Hydroboration [Seite 667]
1.11.28.1.13.2 - 4.4.28.13.2 Variation 2: Via Catalytic Dihydroxylation with Osmium Tetroxide [Seite 668]
1.11.28.1.14 - 4.4.28.14 Method 14: Modification of Existing a-Silyl Alcohols or Ethers [Seite 669]
1.11.28.1.14.1 - 4.4.28.14.1 Variation 1: Via syn-Dihydroxylation of a-Silyl-a-vinyl Alcohols (a-Hydroxyallylsilanes) with Osmium Tetroxide [Seite 669]
1.11.28.1.14.2 - 4.4.28.14.2 Variation 2: Via O-Alkylation of a-Silyl Alcohols with Allyl and Benzyl Trichloroacetimidoates Catalyzed by Lewis Acids [Seite 670]
1.11.28.1.14.3 - 4.4.28.14.3 Variation 3: Via Addition of a-Lithio-a-silyl Ethers to Aldehydes or Ketones [Seite 670]
1.11.28.1.15 - 4.4.28.15 Method 15: Modification of Existing a-Silyl Amines: a-Alkylation or a-Arylation of a-Silylamines with Grignard Reagents [Seite 671]
1.11.28.1.16 - 4.4.28.16 Additional Methods [Seite 672]
1.11.28.2 - Applications of Product Subclass 28 in Organic Synthesis [Seite 673]
1.11.29 - 4.4.29 Product Subclass 29: a,ß-Epoxysilanes [Seite 680]
1.11.29.1 - Synthesis of Product Subclass 29 [Seite 680]
1.11.29.1.1 - 4.4.29.1 Method 1: By Reaction of Lithiated a-Halosilanes with Aldehydes or Ketones [Seite 680]
1.11.29.1.2 - 4.4.29.2 Method 2: By Epoxidation of a Vinylsilane [Seite 682]
1.11.29.1.2.1 - 4.4.29.2.1 Variation 1: Reaction with a Peroxy Acid [Seite 682]
1.11.29.1.2.2 - 4.4.29.2.2 Variation 2: Sharpless Epoxidation of a Silylated Allylic Alcohol [Seite 683]
1.11.29.1.3 - 4.4.29.3 Method 3: By Reaction of an a-Metalated Epoxide [Seite 683]
1.11.29.2 - Applications of Product Subclass 29 in Organic Synthesis [Seite 684]
1.11.29.2.1 - 4.4.29.4 Method 4: Reduction by Complex Hydrides [Seite 684]
1.11.29.2.2 - 4.4.29.5 Method 5: Reaction with Organometallic Reagents [Seite 685]
1.11.29.2.3 - 4.4.29.6 Method 6: Reaction with Heteroatom Nucleophiles [Seite 686]
1.11.29.2.4 - 4.4.29.7 Method 7: Ring Opening/Desilylation to Aldehydes or Ketones [Seite 687]
1.11.29.2.5 - 4.4.29.8 Method 8: Protodesilylation to Epoxides [Seite 688]
1.11.29.2.6 - 4.4.29.9 Method 9: Formation of a-Alkoxy Ketones via Allene Epoxides [Seite 688]
1.11.29.2.7 - 4.4.29.10 Method 10: Rearrangement to a-Silylaldehydes or a-Silyl Ketones [Seite 689]
1.11.29.2.8 - 4.4.29.11 Method 11: Rearrangement to Silyl Enol Ethers [Seite 690]
1.11.29.2.9 - 4.4.29.12 Method 12: Rearrangement to C-Silylated Allylic Alcohols [Seite 690]
1.11.29.2.10 - 4.4.29.13 Method 13: Rearrangement to Allylic Silanols [Seite 691]
1.11.29.2.11 - 4.4.29.14 Method 14: a-Metalation [Seite 692]
1.11.30 - 4.4.30 Product Subclass 30: Alkynyl[Ethynyl]silanes [Seite 694]
1.11.30.1 - Synthesis of Product Subclass 30 [Seite 694]
1.11.30.1.1 - 4.4.30.1 Method 1: Reaction of Alkynes with Hydrosilanes via Dehydrogenative Coupling [Seite 694]
1.11.30.1.2 - 4.4.30.2 Method 2: Reactions of Alkynylmetals with Silyl Halides [Seite 694]
1.11.30.1.2.1 - 4.4.30.2.1 Variation 1: Of Chlorosilanes with Ethynylmagnesium Reagents [Seite 695]
1.11.30.1.2.2 - 4.4.30.2.2 Variation 2: Of Chlorosilanes with Ethynyllithium Reagents [Seite 695]
1.11.30.1.2.3 - 4.4.30.2.3 Variation 3: Of Chlorosilanes with Ethynylzinc Reagents [Seite 696]
1.11.30.1.3 - 4.4.30.3 Method 3: Reactions of Ethynyl(trimethyl)silane or Bis(trimethysilyl)ethyne [Seite 696]
1.11.30.1.3.1 - 4.4.30.3.1 Variation 1: The Sonogashira--Hagihara Reaction of Ethynyl(trimethyl)silane [Seite 696]
1.11.30.1.3.2 - 4.4.30.3.2 Variation 2: Reactions of Bis(trimethylsilyl)ethyne with Various Organic Electrophiles [Seite 697]
1.11.30.1.4 - 4.4.30.4 Methods 4: Additional Methods [Seite 697]
1.11.30.2 - Applications of Product Subclass 30 in Organic Synthesis [Seite 698]
1.11.30.2.1 - 4.4.30.5 Method 5: Reactions of Ethynylsilanes with Carbonyl Compounds [Seite 698]
1.11.30.2.2 - 4.4.30.6 Method 6: Asymmetric Alkynylation of Chiral Acetals [Seite 699]
1.11.30.2.3 - 4.4.30.7 Method 7: Alkynylation of Acid Chlorides in the Presence of a Copper(I) Salt [Seite 700]
1.11.30.2.4 - 4.4.30.8 Method 8: Coupling Reactions of Ethynylsilanes in the Presence of Transition Metals [Seite 700]
1.11.31 - 4.4.31 Product Subclass 31: Silylketenes [Seite 704]
1.11.31.1 - Synthesis of Product Subclass 31 [Seite 705]
1.11.31.1.1 - 4.4.31.1 Method 1: Elimination Reactions [Seite 705]
1.11.31.1.2 - 4.4.31.2 Method 2: Thermolysis of (Alkoxyethynyl)silanes (1,5-Hydrogen Transfer) [Seite 706]
1.11.31.1.3 - 4.4.31.3 Method 3: Rearrangement by 1,3-Silyl Shift [Seite 707]
1.11.31.1.3.1 - 4.4.31.3.1 Variation 1: From Alkoxyalkynes [Seite 707]
1.11.31.1.3.2 - 4.4.31.3.2 Variation 2: From 2-Phenyl-2,3-dihydrofuran or 3-Phenylisoxazole [Seite 708]
1.11.31.1.4 - 4.4.31.4 Method 4: From Diazo Compounds via Wolff Rearrangement [Seite 709]
1.11.31.1.4.1 - 4.4.31.4.1 Variation 1: Photolysis [Seite 709]
1.11.31.1.4.2 - 4.4.31.4.2 Variation 2: Metal (Copper or Rhodium) Catalysis [Seite 709]
1.11.31.1.5 - 4.4.31.5 Method 5: Thermolysis or Photolysis of Cyclobutenediones or Cyclobutenones [Seite 710]
1.11.31.2 - Applications of Product Subclass 31 in Organic Synthesis [Seite 710]
1.11.31.2.1 - 4.4.31.6 Method 6: Formation of ß-Lactones via Lewis Acid Promoted [2 + 2]-Cycloaddition Reaction [Seite 711]
1.11.31.2.2 - 4.4.31.7 Method 7: Formation of Aza-Allenic Derivatives and Their Further Electrocyclization [Seite 711]
1.11.32 - 4.4.32 Product Subclass 32: Allenylsilanes [Seite 716]
1.11.32.1 - Synthesis of Product Subclass 32 [Seite 717]
1.11.32.1.1 - 4.4.32.1 Method 1: From Lithiated Allenes and Trialkylhalosilanes [Seite 717]
1.11.32.1.2 - 4.4.32.2 Method 2: From Allenyl Ethers [Seite 718]
1.11.32.1.3 - 4.4.32.3 Method 3: From C-Silylated Propargylic Alcohols [Seite 718]
1.11.32.1.3.1 - 4.4.32.3.1 Variation 1: Via Organocuprates [Seite 719]
1.11.32.1.3.2 - 4.4.32.3.2 Variation 2: Via Grignard Reagents [Seite 719]
1.11.32.1.3.3 - 4.4.32.3.3 Variation 3: Via Arylsulfonohydrazides [Seite 720]
1.11.32.1.4 - 4.4.32.4 Method 4: From C-Silylated Propargylic Esters and Organoheterocuprates [Seite 720]
1.11.32.1.4.1 - 4.4.32.4.1 Variation 1: From Silyl-Substituted Propargylic Sulfinates [Seite 720]
1.11.32.1.4.2 - 4.4.32.4.2 Variation 2: From Silyl-Substituted Propargylic Sulfonates [Seite 721]
1.11.32.1.5 - 4.4.32.5 Method 5: Silylcupration of Propargylic Esters [Seite 722]
1.11.32.1.5.1 - 4.4.32.5.1 Variation 1: Silylcupration of Propargylic Acetates [Seite 722]
1.11.32.1.5.2 - 4.4.32.5.2 Variation 2: Silylcupration of Propargylic Carbamates [Seite 723]
1.11.32.1.6 - 4.4.32.6 Method 6: From Propargylsilanes [Seite 724]
1.11.32.1.7 - 4.4.32.7 Method 7: From Silyl-Substituted Ynones [Seite 725]
1.11.32.1.8 - 4.4.32.8 Method 8: From Silyl-Substituted Propargylboranes [Seite 725]
1.11.32.1.9 - 4.4.32.9 Method 9: From Chloroenynes [Seite 726]
1.11.32.1.10 - 4.4.32.10 Method 10: From Bromoallenes [Seite 726]
1.11.32.1.11 - 4.4.32.11 Method 11: Via Amide Acetal Claisen Rearrangement of Propargylic Alcohols [Seite 727]
1.11.32.1.12 - 4.4.32.12 Method 12: Chain Elongation of Allenylsilanes [Seite 727]
1.11.32.1.13 - 4.4.32.13 Additional Methods [Seite 728]
1.11.33 - 4.4.33 Product Subclass 33: Arylsilanes [Seite 732]
1.11.33.1 - Synthesis of Product Subclass 33 [Seite 732]
1.11.33.1.1 - 4.4.33.1 Method 1: Via the Würtz--Fittig Reaction [Seite 732]
1.11.33.1.2 - 4.4.33.2 Method 2: Silylation of Aryl-Substituted Metals [Seite 733]
1.11.33.1.2.1 - 4.4.33.2.1 Variation 1: Via Grignard Reagents [Seite 734]
1.11.33.1.2.2 - 4.4.33.2.2 Variation 2: Via Organolithium Reagents [Seite 735]
1.11.33.1.2.3 - 4.4.33.2.3 Variation 3: Via Reductive Silylation Followed by Oxidation [Seite 736]
1.11.33.1.2.4 - 4.4.33.2.4 Variation 4: Via Halogen--Metal Exchange [Seite 736]
1.11.33.1.3 - 4.4.33.3 Method 3: Electrophilic Aromatic Substitutions [Seite 737]
1.11.33.1.4 - 4.4.33.4 Method 4: From Transition-Metal-Catalyzed Reactions [Seite 738]
1.11.33.1.4.1 - 4.4.33.4.1 Variation 1: From Palladium Reagents [Seite 738]
1.11.33.1.4.2 - 4.4.33.4.2 Variation 2: From Nickel and Rhodium Reagents [Seite 740]
1.11.33.1.5 - 4.4.33.5 Method 5: From Cycloaddition Reactions [Seite 741]
1.11.33.1.5.1 - 4.4.33.5.1 Variation 1: Via [2 + 3]-Dipolar Cycloadditions [Seite 741]
1.11.33.1.5.2 - 4.4.33.5.2 Variation 2: Via [4 + 2] Cycloadditions [Seite 742]
1.11.33.1.5.3 - 4.4.33.5.3 Variation 3: Via [2 + 2 + 2] Cycloadditions [Seite 743]
1.11.33.1.6 - 4.4.33.6 Method 6: Via Silyl Migrations [Seite 744]
1.11.33.1.6.1 - 4.4.33.6.1 Variation 1: Via [1,3] Oxygen-to-Carbon Silyl Migrations [Seite 744]
1.11.33.1.6.2 - 4.4.33.6.2 Variation 2: Via [1,4] Oxygen-to-Carbon Silyl Migrations [Seite 745]
1.11.33.1.7 - 4.4.33.7 Method 7: Via Photochemical Reactions [Seite 746]
1.11.33.1.8 - 4.4.33.8 Method 8: Via Electrochemical Reactions [Seite 747]
1.11.33.1.9 - 4.4.33.9 Methods 9: Additional Methods [Seite 748]
1.11.33.2 - Applications of Product Subclass 33 in Organic Synthesis [Seite 748]
1.11.33.2.1 - 4.4.33.10 Method 10: Ipso-Substitution Reactions [Seite 748]
1.11.33.2.2 - 4.4.33.11 Method 11: Oxidation of the C--Si Bond [Seite 749]
1.11.33.2.3 - 4.4.33.12 Method 12: Cross-Coupling Reactions [Seite 750]
1.11.33.2.4 - 4.4.33.13 Method 13: Protection of Hydroxy Groups [Seite 752]
1.11.33.2.5 - 4.4.33.14 Method 14: Use as a Blocking Group [Seite 753]
1.11.33.2.6 - 4.4.33.15 Method 15: Use as Traceless Linkers in Solid-Phase Synthesis [Seite 754]
1.11.33.2.7 - 4.4.33.16 Method 16: Use as Fluorous Labels for Fluorous Synthesis [Seite 755]
1.11.34 - 4.4.34 Product Subclass 34: Vinylsilanes [Seite 760]
1.11.34.1 - Synthesis of Product Subclass 34 [Seite 760]
1.11.34.1.1 - 4.4.34.1 Method 1: Vinylsilanes from Vinylmetal Compounds and Halosilanes [Seite 760]
1.11.34.1.1.1 - 4.4.34.1.1 Variation 1: From Vinylcopper and Trialkylhalosilanes [Seite 760]
1.11.34.1.1.2 - 4.4.34.1.2 Variation 2: From Vinylmagnesium Halides and Trialkyl- and Triarylhalosilanes [Seite 761]
1.11.34.1.1.3 - 4.4.34.1.3 Variation 3: From Vinylsodium and Trialkylhalosilanes [Seite 762]
1.11.34.1.1.4 - 4.4.34.1.4 Variation 4: From Vinyllithium and Trialkylhalosilanes [Seite 762]
1.11.34.1.1.5 - 4.4.34.1.5 Variation 5: Using Metalated Vinylsilanes [Seite 764]
1.11.34.1.2 - 4.4.34.2 Method 2: Coupling Reaction of Vinyl Halides with Silylmetal Species [Seite 766]
1.11.34.1.3 - 4.4.34.3 Method 3: Addition--Elimination of Disilane to Vinyl Halides [Seite 767]
1.11.34.1.4 - 4.4.34.4 Method 4: Coupling Reaction of (a- or ß-Halovinyl)silanes with Silylmetal Species [Seite 768]
1.11.34.1.5 - 4.4.34.5 Method 5: Stille Coupling of Vinyl Halides with Trimethyl[(E)-2-(trimethylstannyl)vinyl]silane [Seite 770]
1.11.34.1.6 - 4.4.34.6 Method 6: Reaction of Carbonyl Compounds with (Trimethylsilyl)methylmetal Species [Seite 771]
1.11.34.1.6.1 - 4.4.34.6.1 Variation 1: Reaction of Aldehydes with Bis(trimethylsilyl)methyllithium [Seite 771]
1.11.34.1.6.2 - 4.4.34.6.2 Variation 2: Reaction of Aldehydes with Bromobis(trimethylsilyl)methyllithium: Preparation of (a-Bromovinyl)silanes [Seite 772]
1.11.34.1.6.3 - 4.4.34.6.3 Variation 3: Reaction of Carbonyl Compounds with Dimetal Species Derived from (Dibromomethyl)(trimethyl)silane [Seite 774]
1.11.34.1.7 - 4.4.34.7 Method 7: By Wittig Reaction [Seite 775]
1.11.34.1.8 - 4.4.34.8 Method 8: From Allylsilane Lithium Salt [Seite 776]
1.11.34.1.9 - 4.4.34.9 Method 9: Dehydrogenative Silylation of Alkenes [Seite 776]
1.11.34.1.10 - 4.4.34.10 Method 10: Heck-type Reaction [Seite 777]
1.11.34.1.11 - 4.4.34.11 Method 11: Hydrogenation of Alkynylsilanes [Seite 778]
1.11.34.1.12 - 4.4.34.12 Method 12: Hydrometalation of Alkynylsilanes [Seite 779]
1.11.34.1.12.1 - 4.4.34.12.1 Variation 1: Hydrostannylation of Alkynylsilanes [Seite 779]
1.11.34.1.12.2 - 4.4.34.12.2 Variation 2: Hydroalumination of Alkynylsilanes [Seite 779]
1.11.34.1.12.3 - 4.4.34.12.3 Variation 3: Hydromagnesiation of Alkynylsilanes [Seite 781]
1.11.34.1.13 - 4.4.34.13 Method 13: Carbocupration of Alkynylsilanes [Seite 782]
1.11.34.1.14 - 4.4.34.14 Method 14: From Low-Valent Titanium Alkoxide--Alkynylsilane Complexes [Seite 782]
1.11.34.1.15 - 4.4.34.15 Method 15: Radical Addition of Iodoalkanes to Alkynylsilanes [Seite 783]
1.11.34.1.16 - 4.4.34.16 Method 16: [2 + 4] or [2 + 2] Cycloadditions of Alkynylsilanes [Seite 784]
1.11.34.1.17 - 4.4.34.17 Method 17: Cyclization of Alk-.-en-a-ylsilanes [Seite 784]
1.11.34.1.18 - 4.4.34.18 Method 18: Silylmetalation of Terminal Alkynes [Seite 785]
1.11.34.1.19 - 4.4.34.19 Method 19: Hydrosilylation [Seite 787]
1.11.34.1.19.1 - 4.4.34.19.1 Variation 1: Hydrosilylation of Alkynes [Seite 787]
1.11.34.1.19.2 - 4.4.34.19.2 Variation 2: Transition-Metal-Catalyzed Hydrosilylative Cyclization of Dialkynes [Seite 789]
1.11.34.1.20 - 4.4.34.20 Method 20: Birch Reduction of Arylsilanes [Seite 790]
1.11.34.2 - Applications of Product Subclass 34 in Organic Synthesis [Seite 790]
1.11.34.2.1 - 4.4.34.21 Method 21: Proto- and Deuterodesilylation [Seite 791]
1.11.34.2.2 - 4.4.34.22 Method 22: Cleavage of the Vinyl C--Si Bond with Tetrabutylammonium Fluoride [Seite 791]
1.11.34.2.3 - 4.4.34.23 Method 23: Electrophilic Substitution with Halogens [Seite 792]
1.11.34.2.4 - 4.4.34.24 Method 24: Friedel--Crafts Acylation [Seite 793]
1.11.34.2.5 - 4.4.34.25 Method 25: Formylation of Vinylsilanes [Seite 794]
1.11.34.2.6 - 4.4.34.26 Method 26: Nazarov Cyclization [Seite 794]
1.11.34.2.7 - 4.4.34.27 Method 27: Diels--Alder Reaction of (1E-Buta-1,3-dienyl)trimethylsilanes [Seite 795]
1.11.34.2.8 - 4.4.34.28 Method 28: Annulation Reaction of 3-(Trimethylsilyl)but-3-en-2-one [Seite 796]
1.11.34.2.9 - 4.4.34.29 Method 29: Preparation of Allenes [Seite 798]
1.11.34.2.10 - 4.4.34.30 Method 30: Preparation of Carboxylic Acids from Terminal Alkynes [Seite 799]
1.11.34.2.11 - 4.4.34.31 Method 31: Use as a Masked Carbonyl Group [Seite 799]
1.11.34.2.12 - 4.4.34.32 Method 32: Vinyl Heck Reaction [Seite 800]
1.11.34.2.13 - 4.4.34.33 Method 33: Palladium-Catalyzed Coupling [Seite 800]
1.11.34.2.14 - 4.4.34.34 Method 34: Generation of Vinylidene Carbene [Seite 801]
1.11.35 - 4.4.35 Product Subclass 35: a-Silyl Carbonyl Compounds [Seite 804]
1.11.35.1 - Synthesis of Product Subclass 35 [Seite 808]
1.11.35.1.1 - 4.4.35.1 Method 1: C-Silylation of Enolates and Derivatives [Seite 808]
1.11.35.1.1.1 - 4.4.35.1.1 Variation 1: Of Chiral Hydrazones [Seite 809]
1.11.35.1.2 - 4.4.35.2 Method 2: Oxidation of ß-Hydroxysilanes [Seite 810]
1.11.35.1.3 - 4.4.35.3 Method 3: Metal--Carbenoid Insertion into the Si--H Bond [Seite 810]
1.11.35.1.4 - 4.4.35.4 Method 4: Addition of Nucleophiles to a-Silyl Ketenes [Seite 811]
1.11.35.1.5 - 4.4.35.5 Method 5: Addition of a-Silyl Organometallic Reagents to Carbonyl Precursors [Seite 813]
1.11.35.1.6 - 4.4.35.6 Method 6: Rearrangements [Seite 813]
1.11.35.1.6.1 - 4.4.35.6.1 Variation 1: Isomerization of a,ß-Epoxysilanes [Seite 814]
1.11.35.1.6.2 - 4.4.35.6.2 Variation 2: [1,3]-Oxygen-to-Carbon Migration of a Silicon Group [Seite 815]
1.11.35.1.7 - 4.4.35.7 Additional Methods [Seite 816]
1.11.36 - 4.4.36 Product Subclass 36: ß-Silyl Alkyl Halides [Seite 820]
1.11.36.1 - Synthesis of Product Subclass 36 [Seite 821]
1.11.36.1.1 - 4.4.36.1 Method 1: Addition of Hydrogen Halides to Allylsilane and Vinylsilanes [Seite 821]
1.11.36.1.2 - 4.4.36.2 Method 2: Addition of Halogens to Allylsilane and Vinylsilanes [Seite 822]
1.11.36.1.3 - 4.4.36.3 Method 3: Addition of Sulfur and Selenium Halides to Vinylsilanes and Allylsilanes [Seite 823]
1.11.36.1.4 - 4.4.36.4 Method 4: Addition of Radicals [Seite 824]
1.11.36.1.5 - 4.4.36.5 Method 5: Formation of (2-Halocyclopropyl)silanes by Addition of Halocarbenes to Alkenylsilanes and Allenylsilanes [Seite 825]
1.11.36.1.6 - 4.4.36.6 Method 6: From Allylic Substitution of 1,2-Dihaloallyl Groups Using Trimethylsilyllithium and Copper(I) Iodide Reagent [Seite 827]
1.11.36.1.7 - 4.4.36.7 Method 7: From Halogenation of (2-Hydroxyalkyl)silanes [Seite 827]
1.11.36.1.8 - 4.4.36.8 Method 8: From Halogenation of ß-Silyl Carbonyl Compounds, a-Silylenol Ethers, or a-Silylenolates [Seite 828]
1.11.36.1.8.1 - 4.4.36.8.1 Variation 1: From ß-Silyl Carbonyl Compounds [Seite 829]
1.11.36.1.8.2 - 4.4.36.8.2 Variation 2: From a-Silylenol Ethers or a-Silylenolates of Acylsilanes [Seite 829]
1.11.36.1.9 - 4.4.36.9 Additional Methods [Seite 830]
1.11.36.2 - Applications of Product Subclass 36 in Organic Synthesis [Seite 831]
1.11.37 - 4.4.37 Product Subclass 37: ß-Silyl Alcohols and the Peterson Reaction [Seite 836]
1.11.37.1 - Synthesis of Product Subclass 37 [Seite 838]
1.11.37.1.1 - 4.4.37.1 Method 1: Direct Deprotonation of a Silane and Addition to a Carbonyl Compound [Seite 838]
1.11.37.1.2 - 4.4.37.2 Method 2: From Silylmethylmagnesium Halides and Carbonyl Compounds [Seite 839]
1.11.37.1.2.1 - 4.4.37.2.1 Variation 1: Grignard and Organolithium Reagents [Seite 839]
1.11.37.1.2.2 - 4.4.37.2.2 Variation 2: Use of Organocerium Reagents [Seite 840]
1.11.37.1.2.3 - 4.4.37.2.3 Variation 3: Formation of Vinyllithium Reagents [Seite 841]
1.11.37.1.3 - 4.4.37.3 Method 3: Generation of the a-Silyl Carbanion by Transmetalation [Seite 841]
1.11.37.1.3.1 - 4.4.37.3.1 Variation 1: Displacement of a Phenylsulfanyl Group by Lithium Naphthalenide [Seite 842]
1.11.37.1.3.2 - 4.4.37.3.2 Variation 2: Displacement of a Phenylsulfanyl Group by Lithium 1-(Dimethylamino)naphthalenide [Seite 842]
1.11.37.1.3.3 - 4.4.37.3.3 Variation 3: Displacement of a Tin Group [Seite 843]
1.11.37.1.4 - 4.4.37.4 Method 4: Preparation of Vinyl Ethers and Other Heteroatom-Substituted Alkenes [Seite 843]
1.11.37.1.4.1 - 4.4.37.4.1 Variation 1: Preparation of Enol Ethers [Seite 844]
1.11.37.1.4.2 - 4.4.37.4.2 Variation 2: Preparation of Vinyl Sulfides [Seite 844]
1.11.37.1.4.3 - 4.4.37.4.3 Variation 3: Preparation of Vinyl Sulfones [Seite 845]
1.11.37.1.4.4 - 4.4.37.4.4 Variation 4: Preparation of Vinylphosphonates [Seite 845]
1.11.37.1.4.5 - 4.4.37.4.5 Variation 5: Preparation of Vinylstannanes [Seite 845]
1.11.37.1.4.6 - 4.4.37.4.6 Variation 6: Preparation of Difunctional Alkenes [Seite 846]
1.11.37.1.5 - 4.4.37.5 Method 5: Preparation of a,ß-Unsaturated Carbonyl Compounds [Seite 846]
1.11.37.1.5.1 - 4.4.37.5.1 Variation 1: Formation of a,ß-Unsaturated Esters [Seite 847]
1.11.37.1.5.2 - 4.4.37.5.2 Variation 2: Formation of a,ß-Unsaturated Esters with Lithium Dicyclohexylamide as Base [Seite 847]
1.11.37.1.6 - 4.4.37.6 Method 6: Preparation of a,ß-Unsaturated Nitriles [Seite 847]
1.11.37.1.7 - 4.4.37.7 Method 7: Preparation of Enals Through Imines [Seite 848]
1.11.37.1.8 - 4.4.37.8 Method 8: Reduction of a-Silyl Carbonyl Compounds [Seite 848]
1.11.37.1.9 - 4.4.37.9 Method 9: Additions of Organometallic Reagents to a-Silyl Carbonyl Compounds [Seite 849]
1.11.37.1.9.1 - 4.4.37.9.1 Variation 1: Addition of an Organometallic Reagent to an a-Silyl Ketone [Seite 849]
1.11.37.1.9.2 - 4.4.37.9.2 Variation 2: Addition of an Organometallic Reagent to an a-Silyl Ester [Seite 850]
1.11.37.1.10 - 4.4.37.10 Method 10: Addition of a Silylmetal to an Epoxide [Seite 851]
1.11.37.1.11 - 4.4.37.11 Method 11: Vinylsilanes and Alkyllithiums with Carbonyl Compounds [Seite 851]
1.11.38 - 4.4.38 Product Subclass 38: Propargylsilanes [Seite 858]
1.11.38.1 - Synthesis of Product Subclass 38 [Seite 859]
1.11.38.1.1 - 4.4.38.1 Method 1: From Propargylmagnesium Halides and Trialkyl- and Triarylsilicon Halides [Seite 859]
1.11.38.1.1.1 - 4.4.38.1.1 Variation 1: Generation of the Grignard Reagent In Situ (Barbier Procedure) [Seite 859]
1.11.38.1.1.2 - 4.4.38.1.2 Variation 2: Silylation of a Preformed Grignard Reagent [Seite 860]
1.11.38.1.2 - 4.4.38.2 Method 2: From Alk-1-ynes [Seite 860]
1.11.38.1.2.1 - 4.4.38.2.1 Variation 1: Coupling with (Halomethyl)trimethylsilane [Seite 860]
1.11.38.1.2.2 - 4.4.38.2.2 Variation 2: Coupling with Trimethylsilylmethyl Trifluoromethanesulfonate [Seite 861]
1.11.38.1.3 - 4.4.38.3 Method 3: From Alk-2-ynes [Seite 862]
1.11.38.1.4 - 4.4.38.4 Method 4: From 1,3-Dilithiated Alk-1-ynes [Seite 862]
1.11.38.1.5 - 4.4.38.5 Method 5: From 1-(Trimethylsilyl)alk-1-ynes [Seite 863]
1.11.38.1.6 - 4.4.38.6 Method 6: From 1,3-Bis(trimethylsilyl)alk-1-ynes [Seite 864]
1.11.38.1.7 - 4.4.38.7 Method 7: From 1-Bromoalk-1-ynes [Seite 864]
1.11.38.1.7.1 - 4.4.38.7.1 Variation 1: Via Asymmetric Grignard Cross Coupling [Seite 864]
1.11.38.1.7.2 - 4.4.38.7.2 Variation 2: Via Borinate Ester Cross Coupling [Seite 865]
1.11.38.1.8 - 4.4.38.8 Method 8: From Benzyl Propargyl Ethers [Seite 865]
1.11.38.1.9 - 4.4.38.9 Method 9: From a-Silylated Aldehydes [Seite 866]
1.11.38.1.10 - 4.4.38.10 Method 10: From ß-Silylated Esters [Seite 867]
1.11.38.1.11 - 4.4.38.11 Method 11: Chain Elongation from the Propargylic Carbon of Trimethyl(propargyl)silanes [Seite 867]
1.11.38.1.12 - 4.4.38.12 Method 12: Chain Elongation from the Acetylenic Carbon of Trimethyl(propargyl)silanes [Seite 868]
1.11.38.1.13 - 4.4.38.13 Additional Methods [Seite 869]
1.11.39 - 4.4.39 Product Subclass 39: Benzylsilanes [Seite 872]
1.11.39.1 - Synthesis of Product Subclass 39 [Seite 872]
1.11.39.1.1 - 4.4.39.1 Method 1: From Benzylic Hydrogens [Seite 872]
1.11.39.1.2 - 4.4.39.2 Method 2: From Benzylic Halogens [Seite 874]
1.11.39.1.2.1 - 4.4.39.2.1 Variation 1: Via Benzylmagnesium Reagents [Seite 874]
1.11.39.1.2.2 - 4.4.39.2.2 Variation 2: Via Benzyllithium Reagents [Seite 875]
1.11.39.1.3 - 4.4.39.3 Method 3: By Substitution of Aromatic Hydrogens [Seite 875]
1.11.39.1.4 - 4.4.39.4 Method 4: By Substitution of Aromatic Halogens [Seite 876]
1.11.39.1.5 - 4.4.39.5 Method 5: By Hydrosilylation of Styrene Derivatives [Seite 877]
1.11.39.1.6 - 4.4.39.6 Method 6: By Addition of Silylmetal Reagents [Seite 878]
1.11.39.1.7 - 4.4.39.7 Methods 7: Additional Methods [Seite 879]
1.11.39.2 - Applications of Product Subclass 39 in Organic Synthesis [Seite 879]
1.11.39.2.1 - 4.4.39.8 Method 8: Benzylsilanes in Organic Synthesis [Seite 879]
1.11.40 - 4.4.40 Product Subclass 40: Allylsilanes [Seite 884]
1.11.40.1 - Synthesis of Product Subclass 40 [Seite 886]
1.11.40.1.1 - 4.4.40.1 Method 1: From Allylmagnesium Halides and Trialkylhalosilanes [Seite 886]
1.11.40.1.1.1 - 4.4.40.1.1 Variation 1: Silylation of a Preformed Grignard Reagent [Seite 887]
1.11.40.1.1.2 - 4.4.40.1.2 Variation 2: Silylation of an In Situ Generated Grignard Reagent [Seite 888]
1.11.40.1.2 - 4.4.40.2 Method 2: From Allylmagnesium Halides by Transition-Metal-Catalyzed Coupling with Hydrosilanes [Seite 888]
1.11.40.1.3 - 4.4.40.3 Method 3: From Allyl Chlorides by Zinc-Mediated Silylation [Seite 889]
1.11.40.1.4 - 4.4.40.4 Method 4: From Allyl Halides by Electroreductive Synthesis [Seite 889]
1.11.40.1.5 - 4.4.40.5 Method 5: By Silylation of Metalated Alkenes [Seite 890]
1.11.40.1.5.1 - 4.4.40.5.1 Variation 1: From Lithiated Alkenes [Seite 890]
1.11.40.1.5.2 - 4.4.40.5.2 Variation 2: From Alkenylpotassium Compounds [Seite 891]
1.11.40.1.6 - 4.4.40.6 Method 6: From Metalated Allyl Halides and Chlorotrimethylsilane [Seite 893]
1.11.40.1.7 - 4.4.40.7 Method 7: From a-Heteroalkenes by Transition-Metal-Catalyzed Cross Coupling [Seite 893]
1.11.40.1.7.1 - 4.4.40.7.1 Variation 1: From Vinyl Halides With [(Trimethylsilyl)methyl]magnesium Halides and Related Species [Seite 893]
1.11.40.1.7.2 - 4.4.40.7.2 Variation 2: From Enol Phosphates with [(Trialkylsilyl)methyl]magnesium Halides [Seite 895]
1.11.40.1.7.3 - 4.4.40.7.3 Variation 3: From Vinyl Trifluoromethanesulfonates with Tris[(trimethylsilyl)methyl]aluminum [Seite 895]
1.11.40.1.8 - 4.4.40.8 Method 8: From a-Silyl Aldehydes and Alkylidinetriphenylphosphoranes by a Wittig Reaction [Seite 896]
1.11.40.1.9 - 4.4.40.9 Method 9: From Carbonyl Compounds and Trialkyl[2-(trimethylsilyl)ethylidene]phosphoranes by a Wittig Reaction [Seite 897]
1.11.40.1.9.1 - 4.4.40.9.1 Variation 1: Via a Preformed ß-Silylated Phosphonium Salt [Seite 897]
1.11.40.1.9.2 - 4.4.40.9.2 Variation 2: Via an In Situ Generated ß-Silylated Phosphonium Salt [Seite 898]
1.11.40.1.10 - 4.4.40.10 Method 10: From Carbonyl Compounds and Ethyl 2-(Diethoxyphosphoryl)-3-(trimethylsilyl)propanoate by Horner--Wadsworth--Emmons Reaction [Seite 898]
1.11.40.1.11 - 4.4.40.11 Method 11: From Carbonyl Compounds and ß-Silyl Thioacetals by Titanium(II)-Promoted Reductive Alkenation [Seite 899]
1.11.40.1.12 - 4.4.40.12 Method 12: From Carbonyl Compounds and Trimethyl[2-(phenylsulfonyl)ethyl]silane by the Julia Reaction [Seite 900]
1.11.40.1.13 - 4.4.40.13 Method 13: Formation of Exocyclic Allylsilanes by the Ramberg--Bäcklund Reaction [Seite 901]
1.11.40.1.14 - 4.4.40.14 Method 14: From 1,3-Dienes by Hydrosilylation [Seite 902]
1.11.40.1.15 - 4.4.40.15 Method 15: From 1,3-Dienes by Carbosilylation [Seite 903]
1.11.40.1.16 - 4.4.40.16 Method 16: From Allyl Halides by Copper(I)-Catalyzed Silylation with Trichlorosilane [Seite 904]
1.11.40.1.17 - 4.4.40.17 Method 17: From Allenes by Palladium(0)-Catalyzed Carbosilylation [Seite 904]
1.11.40.1.18 - 4.4.40.18 Method 18: From Lithium Allyl Alcoholates and Hexamethyldisilane [Seite 905]
1.11.40.1.19 - 4.4.40.19 Method 19: From Allyl Esters via Allylpalladium(0) Complexes [Seite 906]
1.11.40.1.19.1 - 4.4.40.19.1 Variation 1: Using Disilanes [Seite 906]
1.11.40.1.19.2 - 4.4.40.19.2 Variation 2: Using Samarium(II) Iodide and Chlorotrimethylsilane [Seite 907]
1.11.40.1.20 - 4.4.40.20 Method 20: From Allyl Alcohols by Palladium(0)-Catalyzed Intramolecular Silylsilylation [Seite 908]
1.11.40.1.21 - 4.4.40.21 Method 21: Formation of Bis(allylsilanes) from 1,3-Dienes [Seite 909]
1.11.40.1.22 - 4.4.40.22 Method 22: From Allyl Esters or Allyl Carbamates and a Silylcuprate Reagent [Seite 910]
1.11.40.1.22.1 - 4.4.40.22.1 Variation 1: From Allyl Esters [Seite 910]
1.11.40.1.22.2 - 4.4.40.22.2 Variation 2: From Allyl Carbamates [Seite 911]
1.11.40.1.23 - 4.4.40.23 Method 23: From Allyl Halides and a Silylcopper Reagent [Seite 912]
1.11.40.1.24 - 4.4.40.24 Method 24: Formation of 2-Substituted Allylsilanes by Silylcupration of Allene [Seite 913]
1.11.40.1.25 - 4.4.40.25 Method 25: From Allyl Halides or Allyl Phosphates and a Silyllithium Reagent [Seite 914]
1.11.40.1.25.1 - 4.4.40.25.1 Variation 1: From Allyl Halides [Seite 914]
1.11.40.1.25.2 - 4.4.40.25.2 Variation 2: From Allyl Phosphates [Seite 915]
1.11.40.1.26 - 4.4.40.26 Method 26: Formation of 1,3-Disubstituted Allylsilanes by Decarboxylative Elimination [Seite 916]
1.11.40.1.27 - 4.4.40.27 Method 27: Formation of 1-Substituted Allylsilanes by Grieco Dehydration [Seite 918]
1.11.40.1.28 - 4.4.40.28 Method 28: From Alkynes and a-Silyl Organocopper Reagents [Seite 919]
1.11.40.1.28.1 - 4.4.40.28.1 Variation 1: Stoichiometric Carbocupration with a Copper(I) Salt [Seite 919]
1.11.40.1.28.2 - 4.4.40.28.2 Variation 2: Copper-Catalyzed Carbometalation of Alk-2-yn-1-ols [Seite 920]
1.11.40.1.29 - 4.4.40.29 Method 29: From Mixed Vinylcuprates and (Iodomethyl)trimethylsilane or Related Reagents [Seite 921]
1.11.40.1.30 - 4.4.40.30 Method 30: From Carboxylic Acid Derivatives and an Organocerium Reagent by a Peterson-type Reaction [Seite 921]
1.11.40.1.31 - 4.4.40.31 Method 31: From .-Silylated Allylic Alcohols by a Claisen Rearrangement [Seite 923]
1.11.40.1.31.1 - 4.4.40.31.1 Variation 1: By a Johnson Ortho Ester Claisen Rearrangement [Seite 923]
1.11.40.1.31.2 - 4.4.40.31.2 Variation 2: By an Ireland--Claisen Rearrangement [Seite 924]
1.11.40.1.31.3 - 4.4.40.31.3 Variation 3: By the Eschenmoser Variant of the Claisen Rearrangement [Seite 925]
1.11.40.1.32 - 4.4.40.32 Method 32: From 1-Trimethylsilyl-1,3-dienes by a Diels--Alder Reaction [Seite 926]
1.11.40.1.33 - 4.4.40.33 Method 33: Formation of Cyclopentanoid Allylsilanes by an Intramolecular Ene Reaction [Seite 926]
1.11.40.1.34 - 4.4.40.34 Method 34: From Alkenyl Fischer Carbene Complexes by a [2 + 1]-Insertion Reaction with Triorganosilanes [Seite 927]
1.11.40.1.35 - 4.4.40.35 Method 35: From Vinyldiazo Carbonyl Compounds by a Rhodium-Catalyzed [2 + 1]-Insertion Reaction with Triorganosilanes [Seite 928]
1.11.40.1.36 - 4.4.40.36 Method 36: Formation of Formyl-Substituted Alk-2-enylsilanes by Photolysis [Seite 929]
1.11.40.1.37 - 4.4.40.37 Method 37: From Allyl Sulfides by Reductive Silylation [Seite 930]
1.11.40.1.37.1 - 4.4.40.37.1 Variation 1: By Retro-[1,4]-Brook Rearrangement [Seite 930]
1.11.40.1.37.2 - 4.4.40.37.2 Variation 2: By Silylation of Oxyanion--Carbanionic Species [Seite 930]
1.11.40.1.38 - 4.4.40.38 Method 38: From Allyl Sulfides and Tris(trimethylsilyl)silane by a Radical Reaction [Seite 931]
1.11.40.1.39 - 4.4.40.39 Method 39: From Allyl Sulfones [Seite 932]
1.11.40.1.40 - 4.4.40.40 Method 40: Formation of 3-Substituted Allylsilanes by a Peterson-type Elimination [Seite 933]
1.11.40.1.41 - 4.4.40.41 Method 41: Formation of 3-Substituted Allylsilanes by Silicon-Directed Bamford--Stevens Reaction [Seite 933]
1.11.40.1.42 - 4.4.40.42 Method 42: From .-Silylated Allylic Esters or Allyl Carbonates by a Palladium(0)-Catalyzed Reduction [Seite 934]
1.11.40.1.42.1 - 4.4.40.42.1 Variation 1: From Allylic Esters [Seite 934]
1.11.40.1.42.2 - 4.4.40.42.2 Variation 2: From Allylic Carbonates [Seite 935]
1.11.40.1.43 - 4.4.40.43 Method 43: From Alk-2-ynylsilanes by Hydroalumination [Seite 936]
1.11.40.1.44 - 4.4.40.44 Method 44: From Prop-2-ynylsilanes by Hydroboration [Seite 937]
1.11.40.1.45 - 4.4.40.45 Method 45: From Alk-2-ynylsilanes by Catalytic Hydrogenation [Seite 937]
1.11.40.1.46 - 4.4.40.46 Method 46: Formation of Exocyclic Allylsilanes by Intramolecular Reductive Heck Cyclization of Alk-2-ynylsilanes [Seite 938]
1.11.40.1.47 - 4.4.40.47 Method 47: Formation of 3-Substituted Allylsilanes by Cross Metathesis [Seite 939]
1.11.40.1.47.1 - 4.4.40.47.1 Variation 1: By Molybdenum-Catalyzed Cross Metathesis [Seite 939]
1.11.40.1.47.2 - 4.4.40.47.2 Variation 2: By Ruthenium-Catalyzed Cross Metathesis [Seite 940]
1.11.40.1.47.3 - 4.4.40.47.3 Variation 3: By Titanium(II)-Induced Cross Metathesis [Seite 940]
1.11.40.1.48 - 4.4.40.48 Method 48: Formation of 2-Substituted Allylsilanes by the Heck Reaction [Seite 941]
1.11.40.1.49 - 4.4.40.49 Method 49: From [2-(Iodomethyl)allyl]trimethylsilane by Indium-Mediated Allylsilylation of Aldehydes or Ketones [Seite 943]
1.11.40.1.50 - 4.4.40.50 Method 50: From [2-(Silylmethyl)allyl]lithium by a Condensation Reaction [Seite 943]
1.11.40.1.51 - 4.4.40.51 Method 51: From (2-Stannylallyl)silanes by Palladium(0)-Catalyzed Cross Coupling with Acid Chlorides or Aryl Bromides [Seite 944]
1.11.40.1.52 - 4.4.40.52 Method 52: From [2-(Stannylmethyl)allyl]silanes by Radical Allylsilylation with Alkyl Halides [Seite 945]
1.11.40.1.53 - 4.4.40.53 Method 53: From [2-(Stannylmethyl)allyl]silanes by Thermal Allylsilylation with Acid Chlorides or Aldehydes [Seite 946]
1.11.40.1.54 - 4.4.40.54 Methods 54: Additional Methods [Seite 946]
1.11.40.2 - Applications of Product Subclass 40 in Organic Synthesis [Seite 948]
1.11.40.2.1 - 4.4.40.55 Method 55: Protodesilylation of Allylsilanes [Seite 948]
1.11.40.2.2 - 4.4.40.56 Method 56: Allylation of Reactive Alkyl Halides [Seite 949]
1.11.40.2.3 - 4.4.40.57 Method 57: Radical Allylation of Alkyl Halides [Seite 950]
1.11.40.2.4 - 4.4.40.58 Method 58: Addition to Epoxides and Oxetanes [Seite 950]
1.11.40.2.5 - 4.4.40.59 Method 59: Allylation of Aldehydes and Ketones [Seite 952]
1.11.40.2.5.1 - 4.4.40.59.1 Variation 1: By Lewis Acid Catalyzed Allylation [Seite 952]
1.11.40.2.5.2 - 4.4.40.59.2 Variation 2: By Lewis Base Promoted Allylation [Seite 954]
1.11.40.2.6 - 4.4.40.60 Method 60: Allylation of Acetals and Ketals [Seite 955]
1.11.40.2.7 - 4.4.40.61 Method 61: Acylation with Acid Chloride [Seite 956]
1.11.40.2.8 - 4.4.40.62 Method 62: Reaction with Iminium Ions [Seite 957]
1.11.40.2.9 - 4.4.40.63 Method 63: Epoxidation and Ring Opening [Seite 957]
1.11.40.2.10 - 4.4.40.64 Method 64: Aziridination and Ring Opening [Seite 958]
1.11.40.2.11 - 4.4.40.65 Method 65: Dihydroxylation of Allylsilanes [Seite 959]
1.11.40.2.12 - 4.4.40.66 Method 66: Conjugate Addition to a,ß-Unsaturated Carbonyl Compounds [Seite 960]
1.11.40.2.13 - 4.4.40.67 Method 67: Palladium(0)-Catalyzed [3 + 2] Cycloaddition [Seite 962]
1.11.40.2.14 - 4.4.40.68 Method 68: [3 + 4] Allyl Cation Cycloaddition [Seite 963]
1.11.40.2.15 - 4.4.40.69 Method 69: Hydroxycyclopentanes from [3 + 2] Annulation with a-Enones [Seite 964]
1.11.40.2.16 - 4.4.40.70 Method 70: Tetrahydrofurans by [3 + 2] Annulation with Aldehydes and Ketones [Seite 965]
1.11.40.2.17 - 4.4.40.71 Method 71: a-Methylenecyclopentanones from Silicon-Directed Nazarov Cyclization [Seite 965]
1.11.41 - 4.4.41 Product Subclass 41: ß-Silyl Carbonyl Compounds [Seite 974]
1.11.41.1 - 4.4.41.1 Method 1: Hydrosilylation of Alkynes and Alkenes [Seite 976]
1.11.41.1.1 - 4.4.41.1.1 Variation 1: Hydrosilylation of Propargyl Alcohols, and Oxidation or Isomerization [Seite 977]
1.11.41.1.2 - 4.4.41.1.2 Variation 2: Hydrosilylation and Dehydrogenation [Seite 977]
1.11.41.1.3 - 4.4.41.1.3 Variation 3: Hydrosilylation--Carbonylation [Seite 978]
1.11.41.2 - 4.4.41.2 Method 2: Silylmetalation of Alkynes and Alkenes [Seite 979]
1.11.41.2.1 - 4.4.41.2.1 Variation 1: Silylmetalation of a,ß-Unsaturated Carbonyl Compounds [Seite 979]
1.11.41.2.2 - 4.4.41.2.2 Variation 2: Silylmetalation and Acylation of Alkynes [Seite 981]
1.11.41.3 - 4.4.41.3 Method 3: Electrophilic Silylation of Functionalized Three-Carbon Reagents [Seite 982]
1.11.41.3.1 - 4.4.41.3.1 Variation 1: Electrophilic Silylation of Allyllithium Reagents [Seite 982]
1.11.41.3.2 - 4.4.41.3.2 Variation 2: Electrophilic Silylation at C3 of Masked a,ß-Unsaturated Aldehydes and Ketones [Seite 983]
1.11.41.3.3 - 4.4.41.3.3 Variation 3: Reductive Silylation of Anisole and Hydrolysis [Seite 985]
1.11.41.4 - 4.4.41.4 Method 4: Carbonylation or Carboxylation of Vinylsilanes [Seite 986]
1.11.41.5 - 4.4.41.5 Method 5: Trimethylsilylmethylation of Enolates and Enolate Equivalents [Seite 988]
1.11.41.6 - 4.4.41.6 Method 6: Claisen Rearrangement of Esters of 3-Silylallyl Alcohols [Seite 989]
1.11.41.7 - 4.4.41.7 Additional Methods [Seite 990]
1.11.42 - 4.4.42 Product Subclass 42: .-Silyl Alkyl Halides, Alcohols, and Esters Thereof [Seite 994]
1.11.42.1 - 4.4.42.1 Method 1: From Silyl Anions and Functionalized Three-Carbon Electrophiles [Seite 996]
1.11.42.2 - 4.4.42.2 Method 2: From Silicon Electrophiles and Functionalized Three-Carbon Nucleophiles [Seite 997]
1.11.42.2.1 - 4.4.42.2.1 Variation 1: Intermolecular Silylation of C,O-Dianions Derived from Functionalized Alcohols [Seite 997]
1.11.42.2.2 - 4.4.42.2.2 Variation 2: Silicon Transfer in 3-Siloxy Carbanions: The Retro-[1,4]-Brook Rearrangement [Seite 998]
1.11.42.3 - 4.4.42.3 Method 3: From a-Silylated Carbanions and Epoxides [Seite 1000]
1.11.42.4 - 4.4.42.4 Method 4: Hydrosilylation of Allylic Compounds [Seite 1002]
1.11.42.4.1 - 4.4.42.4.1 Variation 1: Hydrosilylation of Allylic Halides, Alcohols, and Esters [Seite 1002]
1.11.42.4.2 - 4.4.42.4.2 Variation 2: Intramolecular Hydrosilylation of Allyloxysilanes [Seite 1003]
1.11.42.5 - 4.4.42.5 Method 5: Coupling between Vinylsilanes and Aldehydes or Ketones [Seite 1005]
1.11.42.5.1 - 4.4.42.5.1 Variation 1: Carbozirconation of Vinylsilanes [Seite 1005]
1.11.42.5.2 - 4.4.42.5.2 Variation 2: Coupling Initiated by Electron Transfer [Seite 1006]
1.11.42.6 - 4.4.42.6 Method 6: Additions to Allylsilanes [Seite 1007]
1.11.42.6.1 - 4.4.42.6.1 Variation 1: Hydrometalation--Oxidation of Allylsilanes [Seite 1007]
1.11.42.6.2 - 4.4.42.6.2 Variation 2: Carbometalation of Allylsilanes [Seite 1008]
1.11.42.6.3 - 4.4.42.6.3 Variation 3: Free-Radical Addition to Allylsilanes [Seite 1009]
1.11.42.7 - 4.4.42.7 Method 7: Addition of ß-Silylated Carbanions to Aldehydes and Ketones [Seite 1010]
1.11.42.7.1 - 4.4.42.7.1 Variation 1: Addition of ß-Silyl Organometallic Reagents to Aldehydes and Ketones [Seite 1010]
1.11.42.7.2 - 4.4.42.7.2 Variation 2: Condensation of ß-Silyl Enolates with Carbonyl Compounds [Seite 1011]
1.12 - Keyword Index [Seite 1020]
1.13 - Author Index [Seite 1050]
1.14 - Abbreviations [Seite 1102]

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