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Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 42 (eBook)

Organophosphorus Compounds (incl. RO-P and RN-P)

Francois Mathey (Herausgeber)

eBook Download: PDF | EPUB

2014 | 1. Auflage
1126 Seiten
Thieme (Verlag)
978-3-13-172211-9 (ISBN)

Lese- und Medienproben

Ebook-Leseprobe (PDF)

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Science of Synthesis – Volume 42: Organophosphorus Compounds (incl. RO---P and RN---P) 1
Title page 3
Imprint 5
Preface 6
Volume Editor's Preface 8
Overview 10
Table of Contents 12
Introduction 48
42.1 Product Class 1: Phosphinidenes and Terminal Phosphinidene Complexes 62
42.1.1 Product Subclass 1: Free Phosphinidenes 62
42.1.1.1 Synthesis of Product Subclass 1 63
42.1.1.1.1 Method 1: Elimination 63
42.1.1.1.1.1 Variation 1: Thermal Generation 63
42.1.1.1.1.2 Variation 2: Photolytic Generation 63
42.1.1.1.2 Method 2: Reduction 64
42.1.1.1.3 Method 3: Phospha-Wittig Reagents 64
42.1.1.2 Applications of Product Subclass 1 in Organic Synthesis 65
42.1.1.2.1 Method 1: Trapping Reactions 65
42.1.2 Product Subclass 2: Neutral Electrophilic Phosphinidene Complexes 66
42.1.2.1 Synthesis of Product Subclass 2 67
42.1.2.1.1 Method 1: Cheletropic Elimination 67
42.1.2.1.1.1 Variation 1: From 7-Phosphanorbornadienes 67
42.1.2.1.1.2 Variation 2: From Phosphiranes 69
42.1.2.1.1.3 Variation 3: From Phosphirenes 69
42.1.2.1.2 Method 2: Salt Metathesis 70
42.1.2.2 Applications of Product Subclass 2 in Organic Synthesis 71
42.1.2.2.1 Method 1: Trapping Reactions 71
42.1.3 Product Subclass 3: Cationic Electrophilic Phosphinidene Complexes 71
42.1.3.1 Synthesis of Product Subclass 3 71
42.1.3.1.1 Method 1: Chloride Abstraction 71
42.1.4 Product Subclass 4: Nucleophilic Phosphinidene Complexes 72
42.1.4.1 Synthesis of Product Subclass 4 72
42.1.4.1.1 Method 1: Salt Metathesis/Elimination 72
42.1.4.1.1.1 Variation 1: Of Metal Hydrides 73
42.1.4.1.1.2 Variation 2: Of Alkali Metal Phosphides 73
42.1.4.1.1.3 Variation 3: Of Transition Metal Phosphides 75
42.1.4.1.2 Method 2: Addition/Elimination 76
42.1.4.1.3 Method 3: Dehydrohalogenation/Ligation 77
42.1.4.1.4 Method 4: a-Hydrogen Migration 78
42.1.4.1.5 Method 5: Oxidation/Deprotonation 79
42.1.4.2 Applications of Product Subclass 4 in Organic Synthesis 80
42.1.4.2.1 Method 1: Phosphinidene-Transfer Reactions 80
42.2 Product Class 2: Oxo-, Thioxo-, Selenoxo-, and Iminophosphines and Diphosphenes 84
42.2.1 Product Subclass 1: Oxophosphines 84
42.2.1.1 Synthesis of Product Subclass 1 84
42.2.1.1.1 Method 1: Elimination Reactions 84
42.2.1.1.2 Method 2: Cycloreversion Reactions 85
42.2.2 Product Subclass 2: Thioxophosphines and Selenoxophosphines 86
42.2.2.1 Synthesis of Product Subclass 2 87
42.2.2.1.1 Method 1: Elimination Reactions 87
42.2.2.1.2 Method 2: Cycloreversion Reactions 87
42.2.2.1.3 Methods 3: Miscellaneous Reactions 89
42.2.3 Product Subclass 3: Iminophosphines 91
42.2.3.1 Synthesis of Product Subclass 3 91
42.2.3.1.1 Method 1: Elimination Reactions 91
42.2.3.1.2 Method 2: Substitution Reactions 92
42.2.3.1.3 Method 3: Cycloreversion Reactions 93
42.2.4 Product Subclass 4: Diphosphenes 94
42.2.4.1 Synthesis of Product Subclass 4 94
42.2.4.1.1 Method 1: Elimination and/or Condensation Reactions 94
42.2.4.1.2 Method 2: Rearrangement Reactions 98
42.2.4.1.3 Method 3: Substitution Reactions 99
42.2.5 Product Subclass 5: Heteroatom-Substituted Diphosphenes 100
42.2.6 Product Subclass 6: Stereodefined Diphosphenes 101
42.2.7 Product Subclass 7: Heteroatom-Substituted Iminophosphines 103
42.2.7.1 Synthesis of Product Subclass 7 103
42.2.7.1.1 Method 1: Elimination Reactions 103
42.2.7.1.2 Method 2: Substitution Reactions 105
42.2.8 Product Subclass 8: Tetraphosphenes 105
42.2.8.1 Synthesis of Product Subclass 8 105
42.2.8.1.1 Method 1: Activation of White Phosphorus 105
42.3 Product Class 3: Phosphenium Salts 110
42.3.1 Synthesis of Product Class 3 110
42.3.1.1 Method 1: Halogen Abstraction of Halophosphines 110
42.3.1.2 Method 2: Alkylation or Protonation of Diphosphenes 113
42.3.2 Applications of Product Class 3 in Organic Synthesis 114
42.3.2.1 Method 1: Reactions of Phosphenium Cations with Unsaturated Hydrocarbons 114
42.4 Product Class 4: Alkylphosphines 118
42.4.1 Synthesis of Product Class 4 119
42.4.1.1 Method 1: Synthesis from Phosphine, or Primary or Secondary Phosphines, and Alkyl Halides 120
42.4.1.1.1 Variation 1: From Phosphine and Alkyl Halides 120
42.4.1.1.2 Variation 2: From Primary Phosphines and Alkyl Halides 121
42.4.1.1.3 Variation 3: From Secondary Phosphines and Alkyl or Acyl Halides 122
42.4.1.2 Method 2: Synthesis from Metal Organophosphides and Electrophiles 122
42.4.1.2.1 Variation 1: Synthesis from Metal Organophosphides and Alkyl Halides 122
42.4.1.2.2 Variation 2: Synthesis from Metal Organophosphides and Esters 126
42.4.1.2.3 Variation 3: Ring Opening of Tetrahydrofuran 127
42.4.1.3 Method 3: Addition of Phosphines to C--X Multiple Bonds 128
42.4.1.3.1 Variation 1: Addition to Alk-1-enes or Cyclic Alkenes 128
42.4.1.3.2 Variation 2: Addition to Carbonyl Groups 130
42.4.1.3.3 Variation 3: Mannich-Type Reactions of Phosphines, Formaldehyde, and Amines 130
42.4.1.4 Method 4: Synthesis from Halophosphines 130
42.4.1.4.1 Variation 1: From Phosphorus Trihalides or Trialkyl Phosphites and Organometallic Alkali Metal Compounds or Grignard Reagents 130
42.4.1.4.2 Variation 2: From Alkyldihalophosphines and Organometallic Alkali Metal Compounds or Grignard Reagents 133
42.4.1.4.3 Variation 3: From Dialkylhalophosphines and Organometallic Alkali Metal Compounds or Grignard Reagents 134
42.4.1.4.4 Variation 4: From Chlorophosphines and Other Organometallic Reagents 137
42.4.1.5 Method 5: Cleavage of Diphosphines 137
42.4.1.6 Method 6: Synthesis from Elemental Phosphorus and Alkyl Halides, Alcohols, or Alkenes 138
42.4.1.7 Method 7: Reduction of Halophosphines, Phosphinic Acids, Phosphinic Acid Esters or Halides, and Trialkyl- and Dialkylphosphine Oxides 140
42.4.1.7.1 Variation 1: Reduction of Halophosphines with Lithium Aluminum Hydride or Other Metal Hydrides 140
42.4.1.7.2 Variation 2: Reduction of Alkylphosphonates with Lithium Aluminum Hydride 141
42.4.1.7.3 Variation 3: Reduction of Dialkylphosphine Oxides, Dialkylphosphinates, or Alkylphosphonates with Aluminum Derivatives 141
42.4.1.7.4 Variation 4: Reduction of Trialkylphosphine Oxides with Lithium Aluminum Hydride 144
42.4.1.7.5 Variation 5: Reduction of Dialkylphosphine Oxides, Dialkylphosphinates, or Alkylphosphinates with Silanes 144
42.4.1.8 Method 8: Reduction of Trialkylphosphine Sulfides and P-Chiral Phosphine--Borane Complexes Bearing an Alkylsulfanyl Group 145
42.4.1.8.1 Variation 1: With Alkali Metals 145
42.4.1.8.2 Variation 2: With Lithium Aluminum Hydride 146
42.4.1.9 Method 9: Synthesis from Quaternary Phosphonium Salts 147
42.4.1.9.1 Variation 1: Synthesis from Tetrakis(hydroxymethyl)phosphonium Halides 147
42.4.1.10 Method 10: Disproportionation of Dialkylphosphine Oxides 148
42.4.1.11 Method 11: Addition Reactions of Unsaturated Tertiary Vinylphosphines 148
42.4.1.12 Method 12: Enantioselective Cleavage of a P--C Bond in Alkyldimethyl-phosphine--Borane Complexes 149
42.5 Product Class 5: Bis(alkylphosphino)- and Poly(alkylphosphino)alkanes, and Di- and Polyphosphines with a P--P Bond 156
42.5.1 Product Subclass 1: Bis(alkylphosphino)- and Poly(alkylphosphino)alkanes 156
42.5.1.1 Synthesis of Product Subclass 1 157
42.5.1.1.1 Method 1: Synthesis from Metal Dialkylphosphides and Aliphatic Electrophiles 157
42.5.1.1.1.1 Variation 1: Synthesis from Dialkylphosphides or Dialkylphosphines and Polyhaloalkanes 157
42.5.1.1.1.2 Variation 2: Synthesis from Dialkylphosphides and Cyclic Sulfates 162
42.5.1.1.1.3 Variation 3: Synthesis from Dialkylphosphides and (Dialkylphosphino)alkyl Sulfonates 163
42.5.1.1.1.4 Variation 4: Synthesis from Dialkylphosphines and Polyhaloalkanes, Alkylamines, and Alcohols 165
42.5.1.1.1.5 Variation 5: Synthesis from Alkylphosphides and Dihaloalkanes 166
42.5.1.1.1.6 Variation 6: Synthesis from Bis(alkylphosphides) and Alkyl Halides 167
42.5.1.1.2 Method 2: Synthesis from Metal Phosphinomethanides and Electrophiles Containing Phosphino Groups 167
42.5.1.1.2.1 Variation 1: Synthesis from (Dialkylphosphino)methanides and Dialkylhalophosphines 167
42.5.1.1.2.2 Variation 2: Enantioselective Synthesis from Lithium (Dialkylphosphino)methanide--Borane Complexes and Alkylhalophosphines 169
42.5.1.1.2.3 Variation 3: Synthesis from Poly(dialkylphosphino)methanides and Dialkylhalophosphines 170
42.5.1.1.2.4 Variation 4: Synthesis from [(Dialkylphosphino)methyl]silanes or -stannanes and Dialkylhalophosphines 171
42.5.1.1.2.5 Variation 5: Oxidative Coupling of (Dialkylphosphino)methanides 172
42.5.1.1.2.6 Variation 6: Synthesis from (Dialkylphosphino)methanides and Polyhaloalkanes or Analogues 174
42.5.1.1.3 Method 3: Synthesis from Halophosphines and Organometallic Compounds 176
42.5.1.1.3.1 Variation 1: Synthesis from Dialkylhalophosphines and Dimetalated Alkanes, Alkenes, or Alkynes 176
42.5.1.1.3.2 Variation 2: Synthesis from Bis(halophosphino)alkanes and Organometallic Compounds 177
42.5.1.1.4 Method 4: Reduction of Phosphine Oxides 179
42.5.1.1.4.1 Variation 1: Reduction of Bis(dialkylphosphoryl)alkanes with Silanes 179
42.5.1.1.4.2 Variation 2: Reduction of Bis(dialkylphosphoryl)alkanes with Lithium Aluminum Hydride 180
42.5.1.1.5 Method 5: Addition to Double Bonds 182
42.5.1.1.5.1 Variation 1: Addition of Phosphines to Polyenes and Their Heteroatom Analogues 182
42.5.1.1.5.2 Variation 2: Addition of Dialkylphosphines to Vinyl- or Allylphosphines 184
42.5.1.1.5.3 Variation 3: Addition of Polyphosphinoalkanes to C==C or C==X Bonds 186
42.5.1.1.5.4 Variation 4: Addition of Diphosphines to Alkynes 188
42.5.1.1.6 Method 6: Decomposition of Phosphonium Salts 189
42.5.1.1.6.1 Variation 1: Reductive Cleavage of Quaternary Phosphonium Salts 189
42.5.1.1.6.2 Variation 2: Alcoholysis of Quaternary Phosphonium Salts 190
42.5.1.1.7 Method 7: Interconversion of Poly(alkylphosphino)alkanes 190
42.5.1.1.7.1 Variation 1: From Diphosphinomethanides 190
42.5.1.1.8 Method 8: Di- and Oligomerization by Interaction of Functional Groups of Phosphines 191
42.5.1.1.8.1 Variation 1: Di- and Oligomerization of Phosphino Alcohols 191
42.5.2 Product Subclass 2: Tetraalkyldiphosphines and Polyalkylpolyphosphines with a P--P Bond 192
42.5.2.1 Synthesis of Product Subclass 2 193
42.5.2.1.1 Method 1: Synthesis from Dialkylphosphides or Dialkylphosphines and Dialkylhalophosphines 193
42.5.2.1.2 Method 2: Coupling of Dialkylphosphine Derivatives 194
42.5.2.1.2.1 Variation 1: Oxidative Coupling of Dialkylphosphines by Transition-Metal Complexes 194
42.5.2.1.2.2 Variation 2: Reductive Coupling of Dialkylhalophosphines by Alkali Metals 195
42.5.2.1.3 Method 3: Interconversion of Alkylpolyphosphines 195
42.5.2.1.3.1 Variation 1: Alkylation of Polyphosphide Anions 195
42.5.2.1.3.2 Variation 2: Insertion into P--P Bonds 196
42.6 Product Class 6: Cyclic Phosphines 202
42.6.1 Product Subclass 1: Phosphiranes 202
42.6.1.1 Synthesis of Product Subclass 1 203
42.6.1.1.1 Method 1: P-Alkylation of Primary Phosphines 203
42.6.1.1.1.1 Variation 1: From Phosphines or Metal Phosphides and 1,2-Dihalides or 1,2-Bis(toluenesulfonates) 204
42.6.1.1.1.2 Variation 2: From Metal Phosphides and Oxiranes 206
42.6.1.1.2 Method 2: P-Alkylation of Dichlorophosphines 207
42.6.1.1.3 Method 3: Cycloaddition Reactions 208
42.6.1.1.3.1 Variation 1: From Electrophilic Phosphinidene Complexes and Alkenes 208
42.6.1.1.3.2 Variation 2: From Phosphaalkenes and Diazoalkanes 209
42.6.1.1.3.3 Variation 3: From Phosphaalkenes or Phosphacumulenes and Carbenes or Carbenoids 211
42.6.1.1.4 Methods 4: Miscellaneous Reactions 213
42.6.2 Product Subclass 2: Phosphetanes 213
42.6.2.1 Synthesis of Product Subclass 2 214
42.6.2.1.1 Method 1: P-Alkylation of Primary Phosphines 214
42.6.2.1.1.1 Variation 1: From Phosphines and 1,3-Dihalides or Derivatives of 1,3-Diols 214
42.6.2.1.1.2 Variation 2: From Phosphines and Cyclic Sulfates 216
42.6.2.1.2 Method 2: P-Alkylation of Dichlorophosphines 218
42.6.2.1.2.1 Variation 1: Lewis Acid Induced Cyclization of Dichlorophosphines with Alkenes and Subsequent Reduction 218
42.6.2.1.2.2 Variation 2: P-Alkylation of Dichlorophosphines 220
42.6.2.1.3 Method 3: Transformation of Phosphetanes 220
42.6.2.1.3.1 Variation 1: P-Substitution of P-Halophosphetanes 221
42.6.2.1.3.2 Variation 2: C-Substitution of Protected Phosphetanes and Subsequent Deprotection 221
42.6.2.1.4 Methods 4: Miscellaneous Reactions 223
42.6.3 Product Subclass 3: 1,3-Diphosphetanes 223
42.6.3.1 Synthesis of Product Subclass 3 224
42.6.3.1.1 Method 1: Cycloaddition Reactions 224
42.6.3.1.1.1 Variation 1: Cyclodimerization of Phosphaalkenes 224
42.6.3.1.1.2 Variation 2: Cyclooligomerization of Phosphaalkynes 225
42.6.3.1.1.3 Variation 3: Oxidative Coupling of Polyphospholides 226
42.6.3.1.2 Methods 2: Miscellaneous Reactions 227
42.6.4 Product Subclass 4: Five- and Six-Membered Rings: Phospholanes, Phosphinanes, 2,5-Dihydrophospholes, and 1,2,5,6-Tetrahydrophosphinines 227
42.6.4.1 Synthesis of Product Subclass 4 228
42.6.4.1.1 Method 1: P-Alkylation of Primary Phosphines 228
42.6.4.1.1.1 Variation 1: From Phosphines and a,.-Dihalides or Disulfonates of a,.-Diols 228
42.6.4.1.1.2 Variation 2: From Phosphines and Cyclic Sulfates 230
42.6.4.1.2 Method 2: Alkylation of Dichlorophosphines or Phosphinic Acid O,S-Diesters 233
42.6.4.1.2.1 Variation 1: From Dichlorophosphines or Phosphinic Acid O,S-Diesters and a,.-Di-Grignard or Dilithium Reagents 233
42.6.4.1.2.2 Variation 2: From Dichlorophosphines, Alkenes, and Organometallic Reagents 234
42.6.4.1.3 Method 3: Hydrophosphination of Double Bonds 235
42.6.4.1.3.1 Variation 1: Addition of Phosphines to Alkenes 236
42.6.4.1.3.2 Variation 2: Addition of Phosphine and Primary Phosphines to 1,4-Dien-3-ones 237
42.6.4.1.3.3 Variation 3: Addition of Phosphines to Carbonyl Compounds 239
42.6.4.1.4 Method 4: Cycloaddition or Metathesis Reactions 239
42.6.4.1.4.1 Variation 1: 2,5-Dihydrophospholes from Dihalophosphines and Dienes via [4 + 1] Cycloaddition and Reduction 240
42.6.4.1.4.2 Variation 2: 1,2,5,6-Tetrahydrophosphinines from Phosphaalkenes and 1,3-Dienes via [4 + 2] Cycloaddition 242
42.6.4.1.4.3 Variation 3: 7-Phosphanorbornenes from [4 + 2] Cycloaddition of Phosphole Derivatives with Dienophiles 243
42.6.4.1.4.4 Variation 4: 2,5-Dihydrophospholes from Diallylphosphines via Alkene Metathesis 246
42.6.4.1.5 Method 5: Transformation of Cyclic Phosphines 247
42.6.4.1.5.1 Variation 1: Transformation of P-Substituents in Five- and Six-Membered Heterocycles 247
42.6.4.1.5.2 Variation 2: Lithiation and Electrophilic Substitution at a-C--H Bonds in Cyclic Phosphine Oxides and Borane Complexes 248
42.6.4.1.6 Methods 6: Miscellaneous Reactions 250
42.6.5 Product Subclass 5: Cyclic Phosphines with Seven-Membered and Larger Rings 251
42.6.5.1 Synthesis of Product Subclass 5 252
42.6.5.1.1 Method 1: P-Alkylation of Phosphines 252
42.6.5.1.2 Method 2: P-Alkylation of Dihalophosphines 253
42.6.5.1.3 Method 3: P-Alkylation of Tertiary Phosphines or Diphosphines and Reduction 254
42.6.5.1.4 Method 4: Hydrophosphination of Alkenes and Alkynes 257
42.6.5.1.5 Methods 5: Miscellaneous Reactions 259
42.7 Product Class 7: Dialkylphosphinous Acids and Derivatives 268
42.7.1 Product Subclass 1: Dialkylphosphinous Acid Halides 268
42.7.1.1 Synthesis of Product Subclass 1 268
42.7.1.1.1 Method 1: Synthesis from Phosphorous Halides by P--C Bond Formation 268
42.7.1.1.2 Method 2: Ligand Exchange in Dialkylphosphinous Acid Derivatives 269
42.7.1.2 Applications of Product Subclass 1 in Organic Synthesis 270
42.7.2 Product Subclass 2: Dialkylphosphinous Acids 271
42.7.2.1 Synthesis of Product Subclass 2 271
42.7.2.1.1 Method 1: Synthesis from H-Phosphonates by Substitution 271
42.7.2.1.2 Method 2: Hydrolysis of Dialkylphosphinous Acid Derivatives 273
42.7.2.2 Applications of Product Subclass 2 in Organic Synthesis 273
42.7.3 Product Subclass 3: Dialkylphosphinous Acid Esters 274
42.7.3.1 Synthesis of Product Subclass 3 274
42.7.3.1.1 Method 1: Alcoholysis of Dialkylphosphinous Acid Derivatives 274
42.7.3.1.2 Method 2: Synthesis from Phosphorous Acid Monoester Dihalides by P--C Bond Formation 275
42.7.3.2 Applications of Product Subclass 3 in Organic Synthesis 276
42.7.4 Product Subclass 4: Dialkylthiophosphinous Acids 277
42.7.4.1 Synthesis of Product Subclass 4 277
42.7.4.1.1 Method 1: Synthesis from Dialkylphosphinous Acid Derivatives 277
42.7.4.2 Applications of Product Subclass 4 in Organic Synthesis 277
42.7.5 Product Subclass 5: Dialkylthiophosphinous Acid Esters 278
42.7.5.1 Synthesis of Product Subclass 5 278
42.7.5.1.1 Method 1: Synthesis from Dialkylphosphinous Acid Halides 278
42.7.6 Product Subclass 6: Dialkylselenophosphinous Acids 278
42.7.6.1 Synthesis of Product Subclass 6 279
42.7.6.1.1 Method 1: Synthesis from Dialkylphosphines 279
42.7.7 Product Subclass 7: Dialkylselenophosphinous Acid Esters 279
42.7.7.1 Synthesis of Product Subclass 7 279
42.7.7.1.1 Method 1: Synthesis from Dialkylphosphinous Acid Halides 279
42.7.8 Product Subclass 8: Dialkylphosphinous Acid Amides 280
42.7.8.1 Synthesis of Product Subclass 8 280
42.7.8.1.1 Method 1: Aminolysis of Dialkylphosphinous Acid Derivatives 280
42.7.8.1.2 Method 2: Synthesis from Phosphorous Acid Derivatives by P--C Bond Formation 281
42.7.8.2 Applications of Product Subclass 8 in Organic Synthesis 281
42.8 Product Class 8: Alkylphosphonous Acids and Derivatives 290
42.8.1 Product Subclass 1: Alkylphosphonous Acid Dihalides 290
42.8.1.1 Synthesis of Product Subclass 1 291
42.8.1.1.1 Method 1: Electrophilic Alkylation of Phosphorus Trihalides 291
42.8.1.1.2 Method 2: Nucleophilic Alkylation of Phosphorus Trihalides by Organometallic Reagents 291
42.8.1.1.3 Method 3: Ligand Exchange Using Alkylphosphines as Substrates 292
42.8.1.2 Applications of Product Subclass 1 in Organic Synthesis 293
42.8.2 Product Subclass 2: Alkylphosphonous Acid Monohalides 294
42.8.2.1 Synthesis of Product Subclass 2 294
42.8.2.1.1 Method 1: Partial Hydrolysis of Alkyl(dihalo)phosphines 294
42.8.3 Product Subclass 3: Alkylphosphonous Acid Monoester Monohalides 294
42.8.3.1 Synthesis of Product Subclass 3 294
42.8.3.1.1 Method 1: Ligand Exchange in Alkyl(dihalo)phosphines 294
42.8.4 Product Subclass 4: Alkylthiophosphonous Acid Monohalide Monoesters 295
42.8.4.1 Synthesis of Product Subclass 4 295
42.8.4.1.1 Method 1: Ligand Exchange of Alkyl(dihalo)phosphines 295
42.8.5 Product Subclass 5: Alkylphosphonous Acid Monoamide Monohalides 296
42.8.5.1 Synthesis of Product Subclass 5 296
42.8.5.1.1 Method 1: Partial Aminolysis of Alkyl(dihalo)phosphines 296
42.8.5.1.2 Method 2: Ligand Exchange in Alkyl(amino)phosphine Derivatives 297
42.8.6 Product Subclass 6: Alkylphosphonous Acids 298
42.8.6.1 Synthesis of Product Subclass 6 298
42.8.6.1.1 Method 1: Hydrolysis of Alkyl(halo)phosphines 298
42.8.6.1.2 Method 2: Hydrophosphination of Alkenes 299
42.8.6.2 Applications of Product Subclass 6 in Organic Synthesis 299
42.8.7 Product Subclass 7: Alkylphosphonous Acid Monoesters 300
42.8.7.1 Synthesis of Product Subclass 7 300
42.8.7.1.1 Method 1: Alcoholysis of Alkylphosphines 300
42.8.7.1.2 Method 2: Esterification of Monoalkylphosphinic Acids 301
42.8.7.1.3 Method 3: Hydrolysis of Dialkyl Phosphonites and Related Compounds 302
42.8.7.1.4 Method 4: Hydrophosphination of Alkenes 302
42.8.7.2 Applications of Product Subclass 7 in Organic Synthesis 303
42.8.8 Product Subclass 8: Alkylphosphonous Acid Diesters 303
42.8.8.1 Synthesis of Product Subclass 8 303
42.8.8.1.1 Method 1: Alcoholysis of Alkylphosphonites 303
42.8.8.1.2 Method 2: Synthesis from Halophosphonites 304
42.8.8.2 Applications of Product Subclass 8 in Organic Synthesis 305
42.8.9 Product Subclass 9: Alkylthiophosphonous Acid S-Monoesters 305
42.8.9.1 Synthesis of Product Subclass 9 305
42.8.9.1.1 Method 1: Hydrolysis of Alkyl(alkylsulfanyl)(halo)phosphines 305
42.8.10 Product Subclass 10: Alkylphosphonous Acid Monoamides 306
42.8.10.1 Synthesis of Product Subclass 10 306
42.8.10.1.1 Method 1: Hydrolysis of Alkyl(diamino)phosphines 306
42.8.11 Product Subclass 11: Alkylthiophosphonous Acid O-Monoesters 306
42.8.11.1 Synthesis of Product Subclass 11 307
42.8.11.1.1 Method 1: Synthesis from Alkyl(alkoxy)(halo)phosphines 307
42.8.12 Product Subclass 12: Alkylthiophosphonous Acid Diesters 307
42.8.12.1 Synthesis of Product Subclass 12 307
42.8.12.1.1 Method 1: Alcoholysis of Alkyl(alkylsulfanyl)(halo)phosphines 307
42.8.13 Product Subclass 13: Alkylphosphonous Acid Monoester Monoamides 308
42.8.13.1 Synthesis of Product Subclass 13 308
42.8.13.1.1 Method 1: Alcoholysis of Alkylphosphine Derivatives 308
42.8.13.1.2 Method 2: Aminolysis of Alkylphosphonous Acid Derivatives 309
42.8.13.2 Applications of Product Subclass 13 in Organic Synthesis 309
42.8.14 Product Subclass 14: Alkyldithiophosphonous Acid Diesters 310
42.8.14.1 Synthesis of Product Subclass 14 310
42.8.14.1.1 Method 1: Synthesis from Primary Alkylphosphines and Disulfides 310
42.8.14.1.2 Method 2: Thioalcoholysis of Alkyl(dihalo)phosphines 310
42.8.15 Product Subclass 15: Alkylthiophosphonous Acid Monoester Monoamides 311
42.8.15.1 Synthesis of Product Subclass 15 311
42.8.15.1.1 Method 1: Thioalcoholysis of Alkyl(diamino)phosphines 311
42.8.16 Product Subclass 16: Alkyldiselenophosphonous Acid Diesters 312
42.8.16.1 Synthesis of Product Subclass 16 312
42.8.16.1.1 Method 1: Selenoalcoholysis of Alkyl(dihalo)phosphines 312
42.8.17 Product Subclass 17: Alkylphosphonous Acid Diamides 312
42.8.17.1 Synthesis of Product Subclass 17 312
42.8.17.1.1 Method 1: Aminolysis of Substituted Alkylphosphines 312
42.8.17.1.2 Method 2: Synthesis from Diamino(halo)phosphines 313
42.8.17.2 Applications of Product Subclass 17 in Organic Synthesis 313
42.9 Product Class 9: Phosphorous Acid and Derivatives 322
42.9.1 Product Subclass 1: Phosphorous Acid Monoester Dihalides 322
42.9.1.1 Synthesis of Product Subclass 1 322
42.9.1.1.1 Method 1: Alcoholysis of Phosphorus Trihalides 322
42.9.1.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives 323
42.9.1.2 Applications of Product Subclass 1 in Organic Synthesis 323
42.9.2 Product Subclass 2: Phosphorothious Acid S-Monoester Dihalides 323
42.9.2.1 Synthesis of Product Subclass 2 324
42.9.2.1.1 Method 1: Thioalcoholysis of Phosphorus Trihalides 324
42.9.2.2 Applications of Product Subclass 2 in Organic Synthesis 324
42.9.3 Product Subclass 3: Phosphorous Acid Monoamide Dihalides 324
42.9.3.1 Synthesis of Product Subclass 3 324
42.9.3.1.1 Method 1: Aminolysis of Phosphorus Trihalides 324
42.9.3.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives 325
42.9.3.2 Applications of Product Subclass 3 in Organic Synthesis 326
42.9.4 Product Subclass 4: Phosphorous Acid Monoester Monohalides 326
42.9.5 Product Subclass 5: Phosphorous Acid Diester Monohalides 326
42.9.5.1 Synthesis of Product Subclass 5 327
42.9.5.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives 327
42.9.5.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives 327
42.9.5.3 Applications of Product Subclass 5 in Organic Synthesis 328
42.9.6 Product Subclass 6: Phosphorothious Acid Diester Monohalides 329
42.9.6.1 Synthesis of Product Subclass 6 329
42.9.6.1.1 Method 1: Amine--Halogen Exchange in Phosphorothious Acid Diester Monoamides 329
42.9.7 Product Subclass 7: Phosphorous Acid Monoester Monoamide Monohalides 329
42.9.7.1 Synthesis of Product Subclass 7 330
42.9.7.1.1 Method 1: Alcoholysis of Phosphorous Acid Monoamide Dihalides 330
42.9.7.1.2 Method 2: Aminolysis of Phosphorous Acid Monoester Dihalides 330
42.9.7.1.3 Method 3: Consecutive Alcoholysis and Aminolysis of Phosphorus Trihalides 330
42.9.7.1.4 Method 4: Ligand-Exchange Reactions of Phosphorous Acid Derivatives 331
42.9.7.2 Applications of Product Subclass 7 in Organic Synthesis 331
42.9.8 Product Subclass 8: Phosphorodithious Acid Diester Monohalides 332
42.9.8.1 Synthesis of Product Subclass 8 332
42.9.8.1.1 Method 1: Thioalcoholysis of Phosphorus Trihalides 332
42.9.8.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives 332
42.9.9 Product Subclass 9: Phosphorothious Acid Monoester Monoamide Monohalides 333
42.9.9.1 Synthesis of Product Subclass 9 333
42.9.9.1.1 Method 1: Amine--Halogen Exchange in Phosphorothious Acid Diester Monoamides 333
42.9.10 Product Subclass 10: Phosphorous Acid Diamide Monohalides 334
42.9.10.1 Synthesis of Product Subclass 10 334
42.9.10.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives 334
42.9.10.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives 335
42.9.10.2 Applications of Product Subclass 10 in Organic Synthesis 335
42.9.11 Product Subclass 11: Phosphorous Acid Monoesters 335
42.9.11.1 Synthesis of Product Subclass 11 336
42.9.11.1.1 Method 1: Hydrolysis of Phosphorous Acid Esters 336
42.9.11.1.2 Method 2: Synthesis from Other Phosphorous Acid Derivatives 336
42.9.11.1.3 Method 3: Esterification of Phosphorous Acid 337
42.9.11.2 Applications of Product Subclass 11 in Organic Synthesis 338
42.9.12 Product Subclass 12: Phosphorous Acid Diesters (Secondary Phosphites) 338
42.9.12.1 Synthesis of Product Subclass 12 338
42.9.12.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives 338
42.9.12.1.2 Method 2: Alcoholysis of Phosphorous Acid Derivatives 339
42.9.12.1.3 Method 3: Other Syntheses from Phosphorous Acid Derivatives 340
42.9.12.1.4 Method 4: Esterification of Phosphorous Acid Derivatives 340
42.9.12.2 Applications of Product Subclass 12 in Organic Synthesis 341
42.9.13 Product Subclass 13: Phosphorous Acid Triesters (Tertiary Phosphites) 342
42.9.13.1 Synthesis of Product Subclass 13 342
42.9.13.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives 342
42.9.13.1.2 Method 2: Transesterification of Phosphorous Acid Triesters 344
42.9.13.2 Applications of Product Subclass 13 in Organic Synthesis 344
42.9.14 Product Subclass 14: Phosphorothious Acid O-Monoesters 345
42.9.14.1 Synthesis of Product Subclass 14 345
42.9.14.1.1 Method 1: Sulfanylation of Phosphorous Acid Diesters 345
42.9.15 Product Subclass 15: Phosphorothious Acid O,O-Diesters 346
42.9.15.1 Synthesis of Product Subclass 15 346
42.9.15.1.1 Method 1: Sulfanylation of Phosphorous Acid Derivatives 346
42.9.15.2 Applications of Product Subclass 15 in Organic Synthesis 347
42.9.16 Product Subclass 16: Phosphorothious Acid Triesters 347
42.9.16.1 Synthesis of Product Subclass 16 347
42.9.16.1.1 Method 1: Alcoholysis of Phosphorothious Acid Derivatives 347
42.9.16.1.2 Method 2: Thioalcoholysis of Phosphorous Acid Derivatives 348
42.9.17 Product Subclass 17: Phosphorodithious Acid S,S-Diesters 348
42.9.18 Product Subclass 18: Phosphorodithious Acid O-Monoesters 348
42.9.19 Product Subclass 19: Phosphorodithious Acid Triesters 349
42.9.19.1 Synthesis of Product Subclass 19 349
42.9.19.1.1 Method 1: Thioalcoholysis of Phosphorous Acid Derivatives 349
42.9.20 Product Subclass 20: Phosphoroselenous Acid O,O-Diesters 350
42.9.20.1 Synthesis of Product Subclass 20 350
42.9.20.1.1 Method 1: Selanylation of Phosphorous Acid Diester Monohalides 350
42.9.21 Product Subclass 21: Phosphorous Acid Monoester Monoamides 350
42.9.21.1 Synthesis of Product Subclass 21 350
42.9.21.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives 350
42.9.22 Product Subclass 22: Phosphorous Acid Diester Monoamides 351
42.9.22.1 Synthesis of Product Subclass 22 351
42.9.22.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives 351
42.9.22.1.2 Method 2: Aminolysis of Phosphorous Acid Derivatives 353
42.9.22.2 Applications of Product Subclass 22 in Organic Synthesis 353
42.9.23 Product Subclass 23: Phosphorothious Acid Diester Monoamides 354
42.9.23.1 Synthesis of Product Subclass 23 354
42.9.23.1.1 Method 1: Thioalcoholysis of Phosphorous Acid Derivatives 354
42.9.24 Product Subclass 24: Phosphorous Acid Diamides 355
42.9.24.1 Synthesis of Product Subclass 24 355
42.9.24.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives 355
42.9.25 Product Subclass 25: Phosphorous Acid Monoester Diamides 356
42.9.25.1 Synthesis of Product Subclass 25 356
42.9.25.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives 356
42.9.25.1.2 Method 2: Aminolysis of Phosphorous Acid Derivatives 357
42.9.25.2 Applications of Product Subclass 25 in Organic Synthesis 358
42.9.26 Product Subclass 26: Phosphorotrithious Acid Triesters 358
42.9.26.1 Synthesis of Product Subclass 26 358
42.9.26.1.1 Method 1: Thioalcoholysis of Phosphorous Acid Derivatives 358
42.9.27 Product Subclass 27: Phosphorodithious Acid Diester Monoamides 359
42.9.27.1 Synthesis of Product Subclass 27 359
42.9.27.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives 359
42.9.28 Product Subclass 28: Phosphorothious Acid Monoester Diamides 359
42.9.28.1 Synthesis of Product Subclass 28 360
42.9.28.1.1 Method 1: Thioalcoholysis of Phosphorous Acid Derivatives 360
42.9.29 Product Subclass 29: Phosphorotriselenous Acid Triesters 360
42.9.29.1 Synthesis of Product Subclass 29 360
42.9.29.1.1 Method 1: Reaction of a Diselenide with Elemental Phosphorus 360
42.9.30 Product Subclass 30: Phosphorous Acid Triamides 360
42.9.30.1 Synthesis of Product Subclass 30 361
42.9.30.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives 361
42.9.30.2 Applications of Product Subclass 30 in Organic Synthesis 362
42.10 Applications of Tricoordinated Phosphorus Compounds in Homogeneous Catalysis 394
42.10.1 General Catalytic Methods 394
42.10.1.1 Formation of C--C Bonds 394
42.10.1.1.1 Method 1: Palladium-Promoted Cross-Coupling Reactions 394
42.10.1.1.2 Method 2: Catalysis with Phosphonium Salts as Ligand Precursors 399
42.10.1.2 Formation of C--N Bonds 400
42.10.1.2.1 Method 1: Amination of Aryl and Hetaryl Halides or Trifluoromethanesulfonates 400
42.10.1.2.2 Method 2: Amination of Alk-1-enyl Halides or Trifluoromethanesulfonates 407
42.10.1.2.3 Method 3: Intramolecular Amination Reactions 407
42.10.1.3 Formation of C--O Bonds 408
42.10.1.3.1 Method 1: Alkyl Aryl Ether Synthesis 408
42.10.1.3.2 Method 2: Diaryl Ether Synthesis 409
42.10.1.4 Formation of C--P Bonds 410
42.10.1.4.1 Method 1: Formation of Alkylphosphorus Compounds 410
42.10.1.4.2 Method 2: Formation of Alkenylphosphorus Compounds 411
42.10.1.4.2.1 Variation 1: Hydrophosphination of Alkynes 411
42.10.1.4.2.2 Variation 2: Coupling Reactions 413
42.10.1.4.3 Method 3: Formation of Alkynylphosphorus Compounds 415
42.10.1.4.4 Method 4: Formation of Arylphosphorus Compounds 415
42.10.1.5 Formation of C--S Bonds 416
42.10.1.5.1 Method 1: Formation of an Aryl--Sulfur Bond 417
42.10.1.5.2 Method 2: Formation of an Alkenyl--Sulfur Bond 417
42.10.1.5.3 Method 3: Formation of an Alkynyl--Sulfur Bond 418
42.10.1.6 Formation of C--Sn Bonds 419
42.10.1.7 Synthesis with Catalyst Recycling 420
42.10.1.7.1 Method 1: Catalysis with Fluorinated Phosphines 420
42.10.1.7.2 Method 2: Catalysis with Water-Soluble Phosphines 421
42.10.1.7.2.1 Variation 1: Catalysis with Sulfonated and Carboxylated Phosphines 422
42.10.1.7.2.2 Variation 2: Catalysis with Phosphines Bearing Ammonium Groups 423
42.10.1.7.2.3 Variation 3: Catalysis with Carbohydrate-Derived Phosphines 424
42.10.1.7.2.4 Variation 4: Catalysis with Polyether Phosphines 424
42.10.1.7.3 Method 3: Catalysis with Polymer-Supported Phosphines 425
42.10.1.7.3.1 Variation 1: Metal-Promoted Catalysis with Polymer-Supported Phosphines 425
42.10.1.7.3.2 Variation 2: Catalysis with Polymer-Supported Phosphine Reagents 427
42.10.2 Enantioselective Catalytic Methods 438
42.10.2.1 Approaches to Enantioselective Catalysts 438
42.10.2.1.1 Method 1: Approaches to Chiral Cyclic Phosphines 444
42.10.2.1.1.1 Variation 1: Phospholane-Based Chiral Ligands 444
42.10.2.1.1.2 Variation 2: Phosphetane-Based Chiral Ligands 445
42.10.2.1.1.3 Variation 3: Phosphepin-Based Chiral Ligands 446
42.10.2.1.2 Method 2: Approaches to Atropisomeric Biaryl Bisphosphines 446
42.10.2.1.3 Method 3: Approaches to Ferrocenylphosphines with Planar Chirality 449
42.10.2.1.4 Method 4: Approaches to Hybrid Phosphorus--Nitrogen Ligands 452
42.10.2.1.4.1 Variation 1: Phosphino-4,5-dihydrooxazole Ligands 452
42.10.2.1.4.2 Variation 2: Phosphinite--4,5-Dihydrooxazole Ligands 455
42.10.2.1.4.3 Variation 3: Phosphino-4,5-dihydro-1H-imidazole Ligands 455
42.10.2.1.4.4 Variation 4: Phosphinopyridine and Phosphinoquinoline Ligands 455
42.10.2.1.4.5 Variation 5: Pyridylphosphinite and Quinolylphosphinite Ligands 456
42.10.2.1.4.6 Variation 6: Trost Ligands 456
42.10.2.1.5 Method 5: Approaches to Ligands Bearing P--O and P--N Bonds 457
42.10.2.1.5.1 Variation 1: Phosphinite [P(C,C,O)] Ligands 457
42.10.2.1.5.2 Variation 2: Phosphonite [P(C,O,O)] Ligands 457
42.10.2.1.5.3 Variation 3: Phosphite [P(O,O,O)] Ligands 457
42.10.2.1.5.4 Variation 4: Phosphoramidite [P(O,O,N)] Ligands 457
42.10.2.2 Enantioselective C--C Bond-Forming Reactions 458
42.10.2.2.1 Method 1: Metal-Catalyzed Allylic Alkylation (Tsuji--Trost Reaction) 458
42.10.2.2.1.1 Variation 1: Using 1,3-Symmetrically Substituted Allylic Ligands 458
42.10.2.2.1.2 Variation 2: Using Monosubstituted Allylic Ligands 460
42.10.2.2.1.3 Variation 3: Using 1,3-Dissymmetrically Disubstituted Allylic Substrates 462
42.10.2.2.2 Method 2: Palladium-Catalyzed Arylation of Alkenes (Heck Reaction) 465
42.10.2.2.2.1 Variation 1: Selection of Enantiotopic C==C Bonds of an Achiral Substrate 466
42.10.2.2.2.2 Variation 2: Selection of Enantiotopic Faces of an Achiral Alkenic Substrate 467
42.10.2.2.2.3 Variation 3: Selection of Enantiotopic Sites of an Achiral Alkenic Substrate 470
42.10.2.2.3 Method 3: Metal-Catalyzed Coupling Reactions 471
42.10.2.2.4 Method 4: Conjugate Addition Reactions 474
42.10.2.2.4.1 Variation 1: Metal-Catalyzed 1,4-Addition of Organometallic Reagents to Activated Alkenes 474
42.10.2.2.4.2 Variation 2: Copper-Catalyzed Asymmetric 1,4-Addition of Organozinc Reagents 474
42.10.2.2.4.3 Variation 3: Conjugate Addition to Cyclohexa-2,5-dienones 475
42.10.2.2.4.4 Variation 4: Copper-Catalyzed Asymmetric 1,4-Addition of Grignard Reagents 476
42.10.2.2.4.5 Variation 5: Rhodium-Catalyzed Asymmetric 1,4-Addition of Organoboron Reagents 476
42.10.2.2.5 Methods 5: Miscellaneous Methods 478
42.10.2.2.5.1 Variation 1: Metal-Catalyzed Addition of Organometallic Reagents to Unactivated Alkenes 478
42.10.2.2.5.2 Variation 2: Metal-Catalyzed Addition of Organometallic Reagents to Carbonyl Compounds 479
42.10.2.3 Enantioselective C--H Bond-Forming Reactions 480
42.10.2.3.1 Method 1: Rhodium-Promoted Hydrogenation of Alkenes 480
42.10.2.3.2 Method 2: Iridium-Promoted Hydrogenation of Nonfunctionalized Alkenes 485
42.10.2.3.3 Method 3: Iridium-Promoted Hydrogenation of Imines 488
42.10.2.3.4 Method 4: Ruthenium-Promoted Hydrogenation of Ketones 491
42.10.2.3.5 Method 5: Rhodium-Promoted Hydroformylation of Alkenes 498
42.10.2.3.6 Method 6: Rhodium-Promoted Hydroboration of Alkenes 501
42.11 Applications of Tricoordinated Phosphorus Compounds in Organocatalysis 516
42.11.1 Method 1: Morita--Baylis--Hillman Reactions 516
42.11.1.1 Variation 1: Tandem Phosphorylsilylation/Ireland--Claisen Rearrangement 519
42.11.1.2 Variation 2: Intramolecular Morita--Baylis--Hillman Allylic Alkylation 520
42.11.1.3 Variation 3: a-Arylation of Enones with Hypervalent Bismuth Reagents 521
42.11.1.4 Variation 4: Phosphine-Mediated Reductive Condensation of Acyloxybutynoates 521
42.11.1.5 Variation 5: Regioselective Allylic Displacement 522
42.11.1.6 Variation 6: The Morita--Baylis--Hillman Reaction Using Air-Stable Phosphine Reagents 523
42.11.1.7 Variation 7: Asymmetric Morita--Baylis--Hillman Reactions 523
42.11.1.8 Variation 8: The Aza-Morita--Baylis--Hillman Reaction 524
42.11.2 Method 2: Michael Addition Reactions 526
42.11.3 Method 3: Nucleophilic Addition Reactions at Nonactivated Positions 528
42.11.3.1 Variation 1: Chiral Nucleophilic Addition Reactions 531
42.11.3.2 Variation 2: Nucleophilic Interception at the a-Position 532
42.11.3.3 Variation 3: Tandem a- or .-Addition and Michael Addition Reactions 533
42.11.4 Method 4: [3 + 2]-Cycloaddition Reactions 534
42.11.5 Method 5: [4 + 2]-Cycloaddition Reactions 539
42.11.6 Method 6: Acylation and Kinetic Resolution of Alcohols 542
42.11.7 Method 7: Isomerization of Activated Alkynes to Dienes 544
42.12 Product Class 12: Alkylphosphonium Salts 550
42.12.1 Product Subclass 1: Non-Heteroatom-Substituted Alkylphosphonium Salts 550
42.12.1.1 Synthesis of Product Subclass 1 550
42.12.1.1.1 Method 1: Alkylation of Phosphines 550
42.12.1.1.1.1 Variation 1: Alkylation of Tertiary Phosphines 550
42.12.1.1.1.2 Variation 2: Alkylation of Tertiary Phosphines Using Alcohols or Derivatives 551
42.12.1.1.1.3 Variation 3: Successive Alkylation of Phosphines, Phosphides, or Polyphosphines 552
42.12.1.1.1.4 Variation 4: Nucleophilic Addition of Phosphines or Derivatives to Alkenes or Alkynes 552
42.12.1.1.2 Method 2: Modification of Phosphonium Salts 554
42.12.1.1.2.1 Variation 1: Diels--Alder Reaction of Triphenyl(vinyl)phosphonium Salts with 1,4-Dienes 554
42.12.1.1.2.2 Variation 2: Modification of Phosphonium Salts by Reaction of Ylides 554
42.12.1.1.3 Method 3: Reaction of Phosphaalkenes 555
42.12.2 Product Subclass 2: Hydroxyphosphonium Salts 556
42.12.2.1 Synthesis of Product Subclass 2 556
42.12.2.1.1 Method 1: Synthesis of a-Hydroxyphosphonium Salts and Derivatives 556
42.12.2.1.1.1 Variation 1: Addition of Phosphines to Aldehydes or Ketones 556
42.12.2.1.1.2 Variation 2: Alkylation of (a-Hydroxyalkyl)phosphines or Derivatives 558
42.12.2.1.1.3 Variation 3: Reaction of Phosphines with Acetals, Ketals, or Hemiacetals 560
42.12.2.1.1.4 Variation 4: Reaction of Phosphines with Enol Ethers 560
42.12.2.1.2 Method 2: Synthesis of ß-Hydroxyphosphonium Salts and Derivatives 561
42.12.2.1.2.1 Variation 1: Alkylation of Phosphines with ß-Hydroxyalkyl Halides or Derivatives 561
42.12.2.1.2.2 Variation 2: Alkylation of (ß-Hydroxyalkyl)phosphines or Derivatives 564
42.12.2.1.2.3 Variation 3: Reaction of Phosphines with Epoxides 567
42.12.2.1.2.4 Variation 4: Reaction of Ylides with Ketones or Aldehydes 569
42.12.2.1.2.5 Variation 5: Transformation of ß-Functionalized Phosphonium Salts 571
42.12.2.1.3 Method 3: Synthesis of .-Hydroxyphosphonium Salts and Derivatives 573
42.12.2.1.3.1 Variation 1: Alkylation of Phosphines with .-Hydroxyalkyl Halides or Derivatives 573
42.12.2.1.3.2 Variation 2: Alkylation of .-Hydroxyphosphines and Derivatives with Alkyl Halides 575
42.12.2.1.3.3 Variation 3: Reaction of Ylides with Epoxides and 3-Oxaalkyl Halides 576
42.12.2.1.3.4 Variation 4: Transformation of .-Functionalized Phosphonium Salts 577
42.12.3 Product Subclass 3: Sulfanyl- and Selanylphosphonium Salts and Derivatives 578
42.12.3.1 Synthesis of Product Subclass 3 578
42.12.3.1.1 Method 1: Synthesis of a-Sulfanyl and a-Selanylphosphonium Salts and Derivatives 578
42.12.3.1.1.1 Variation 1: Alkylation of Phosphines with Sulfur- or Selenium-Substituted Alkyl Halides 578
42.12.3.1.1.2 Variation 2: Alkylation of Phosphines with Bis(sulfanyl)- or Bis(selanyl) Alkyl Halides, or Cationic Derivatives 580
42.12.3.1.1.3 Variation 3: Transformation of Phosphonium Salts with Anionic Sulfur Nucleophiles 582
42.12.3.1.1.4 Variation 4: Reaction of Ylides with Sulfur- or Selenium-Containing Electrophiles 583
42.12.3.1.2 Method 2: Synthesis of ß-Sulfanyl- and ß-Selanylphosphonium Salts and Derivatives 584
42.12.3.1.2.1 Variation 1: Alkylation of Phosphines with Sulfur- or Selenium-Containing Alkyl Halides or Sulfonates 585
42.12.3.1.2.2 Variation 2: Reaction of Phosphines with 1,1,2-Trimethyldisulfanium or 1-Methyl-1,2-diphenyldisulfanium Salts 586
42.12.3.1.2.3 Variation 3: Reaction of Vinylphosphonium Salts with Sulfur Dioxide, Thiols, or Associated Anions 587
42.12.3.1.2.4 Variation 4: Reaction of Ylides with Miscellaneous Electrophiles 589
42.12.3.1.3 Method 3: Synthesis of .-Sulfanyl- and .-Selanylphosphonium Salts and Derivatives 590
42.12.3.1.3.1 Variation 1: Alkylation of Phosphines with Sulfur- or Selenium-Substituted Alkyl Halides or Related Compounds 590
42.12.3.1.3.2 Variation 2: Transformation of Phosphonium Salts 591
42.12.4 Product Subclass 4: Carbonylphosphonium Salts and Derivatives 592
42.12.4.1 Synthesis of Product Subclass 4 592
42.12.4.1.1 Method 1: Synthesis of P-Carbonylphosphonium Salts and Derivatives 592
42.12.4.1.1.1 Variation 1: Reaction of Phosphines with Various Carbonyl Electrophiles 593
42.12.4.1.1.2 Variation 2: Alkylation of P-Carbonylphosphines with Alkyl Halides or Sulfonates 595
42.12.4.1.2 Method 2: Synthesis of a-Carbonylphosphonium Salts and Derivatives 597
42.12.4.1.2.1 Variation 1: Alkylation of Phosphines with a-(Halomethyl)carbonyl Species 597
42.12.4.1.2.2 Variation 2: Reaction of Ylides with Carbonylated Electrophiles 600
42.12.4.1.2.3 Variation 3: Reaction of Stabilized Ylides with Other Electrophiles 603
42.12.4.1.2.4 Variations 4: Miscellaneous Reactions 604
42.12.4.1.3 Method 3: Synthesis of ß-Carbonyl-Substituted Phosphonium Salts and Derivatives 605
42.12.4.1.3.1 Variation 1: Alkylation of Phosphines with ß-Carbonyl-Substituted Alkyl Halides 606
42.12.4.1.3.2 Variation 2: Reaction of Phosphines with a,ß-Unsaturated Carbonyl Species 608
42.12.4.1.3.3 Variation 3: Alkylation of ß-Carbonylphosphines with Alkyl Halides 612
42.12.5 Product Subclass 5: Polyphosphonium Salts 612
42.12.5.1 Synthesis of Product Subclass 5 612
42.12.5.1.1 Method 1: Synthesis of Multiphosphonium Salts 613
42.12.5.1.1.1 Variation 1: Reaction with Multihalides 613
42.12.5.1.1.2 Variation 2: Reaction of Unsaturated Precursors 613
42.12.5.1.1.3 Variation 3: Recursive Synthesis from a Phosphine 614
42.12.5.1.2 Method 2: Synthesis of Polymeric Phosphonium Salts 614
42.12.5.1.2.1 Variation 1: Reaction of Phosphonium Monomers 614
42.12.5.1.2.2 Variation 2: Functionalization of Polymeric Backbones 616
42.12.6 Product Subclass 6: Cyclic Phosphonium Salts 617
42.12.6.1 Synthesis of Product Subclass 6 617
42.12.6.1.1 Method 1: Cyclization onto Phosphorus 617
42.12.6.1.1.1 Variation 1: Reaction of Secondary Phosphines or Derivatives with 1,n-Dielectrophiles 617
42.12.6.1.1.2 Variation 2: Intramolecular Cyclization of Tertiary Phosphines 618
42.12.6.1.1.3 Variation 3: Intermolecular Cyclization of Tertiary Phosphines 619
42.12.6.1.1.4 Variation 4: Reaction of Halophosphines 621
42.12.6.1.1.5 Variation 5: Reaction of Methylenephosphonium Ions 622
42.12.6.1.2 Method 2: Cyclization between Two Phosphorus Substituents 623
42.12.7 Product Subclass 7: Heterophosphonium Salts 624
42.12.7.1 Synthesis of Product Subclass 7 624
42.12.7.1.1 Method 1: Synthesis from Tricoordinate Phosphorus Compounds 624
42.12.7.1.1.1 Variation 1: Alkylation of Tricoordinate Reagents 624
42.12.7.1.1.2 Variation 2: Reaction of Phosphines with Heteroatomic Electrophiles 627
42.12.7.1.2 Method 2: Synthesis from Tetracoordinate Phosphorus Compounds 628
42.12.7.1.2.1 Variation 1: Modification of Heterophosphonium Salts 628
42.12.7.1.2.2 Variation 2: Reaction of Electrophiles with Tetracoordinate Phosphorus Derivatives 629
42.12.7.1.2.3 Variation 3: Reaction of Secondary Phosphine--Borane Complexes 629
42.13 Product Class 13: Trialkylphosphine Oxides, Sulfides, Selenides, Tellurides, and Imides 642
42.13.1 Product Subclass 1: Trialkylphosphine Oxides 642
42.13.1.1 Synthesis of Product Subclass 1 642
42.13.1.1.1 Method 1: Oxidation of Trialkylphosphines 642
42.13.1.1.1.1 Variation 1: Oxidation with Hydrogen Peroxide 642
42.13.1.1.1.2 Variation 2: Oxidation with Sulfur(VI) Oxides 643
42.13.1.1.1.3 Variation 3: Oxidation by Nitrous Oxide 644
42.13.1.1.1.4 Variation 4: Oxidation with an Iodosylaryl Sulfone 644
42.13.1.1.2 Method 2: Oxidation of Phosphonium Salts 645
42.13.1.1.3 Method 3: Addition of Dialkylphosphine Oxides to Alkenes 646
42.13.1.1.4 Method 4: Addition of Dialkylphosphine Oxides to Ketones or Aldehydes 647
42.13.1.1.5 Method 5: Reactions of Dialkylphosphine Oxides with Alkyl Halides 649
42.13.1.1.5.1 Variation 1: Base-Induced Ionization 649
42.13.1.1.5.2 Variation 2: Lewis Acid Catalysis 650
42.13.1.1.5.3 Variation 3: Reduction with Sodium Bis(2-methoxyethoxy)aluminum Hydride 651
42.13.1.1.6 Method 6: Additions of Dialkyl(chloro)phosphines to Enones 652
42.13.1.1.7 Method 7: Reactions of Chlorophosphine Oxides with Grignard Reagents 653
42.13.1.1.8 Method 8: Reactions of Dialkylphosphinites with Alkyl Halides 654
42.13.1.1.9 Method 9: Isomerization of Dialkylphosphinites 656
42.13.1.1.10 Method 10: Cycloaddition of Alkyl(dichloro)phosphines with Dienes 657
42.13.1.1.11 Method 11: Addition of Dialkylphosphine Oxides to Imines 659
42.13.1.1.12 Method 12: Hydrogenation of Tertiary Arylphosphine Oxides 659
42.13.1.1.13 Method 13: Conversion of Trialkylphosphine Ylides into Trialkylphosphine Oxides 661
42.13.1.1.14 Method 14: Oxygenation of Trialkylphosphine Imides 662
42.13.1.1.14.1 Variation 1: By Reaction with a Ketone 662
42.13.1.1.14.2 Variation 2: By Reaction with Methanol 662
42.13.1.1.14.3 Variation 3: By Treatment with an Oxidizing Agent 663
42.13.1.1.15 Method 15: Oxygenation of Trialkylphosphine Sulfides 663
42.13.1.1.15.1 Variation 1: Treatment with Phosgene 663
42.13.1.1.15.2 Variation 2: Treatment with Dimethyldioxirane 664
42.13.1.1.15.3 Variation 3: Treatment with Trifluoroacetic Anhydride 664
42.13.1.1.15.4 Variation 4: Treatment with 7-Oxabicyclo[4.1.0]heptane and Trifluoroacetic Acid 664
42.13.1.1.16 Method 16: Oxygenation of a Trialkylphosphine Selenide 664
42.13.2 Product Subclass 2: Trialkylphosphine Sulfides 665
42.13.2.1 Synthesis of Product Subclass 2 665
42.13.2.1.1 Method 1: Addition of Dialkylphosphine Sulfides to Alkenes 665
42.13.2.1.1.1 Variation 1: Base-Promoted Addition 665
42.13.2.1.1.2 Variation 2: Free-Radical-Initiated Addition 666
42.13.2.1.2 Method 2: Addition of Dialkylphosphine Sulfides to Aldehydes or Ketones 666
42.13.2.1.3 Method 3: Sulfurization of Trialkylphosphines with Elemental Sulfur 668
42.13.2.1.4 Method 4: Reaction of Dialkyl(vinyl)phosphine Sulfides with Nucleophiles 668
42.13.2.1.5 Method 5: Reaction of Triethylphosphine with a (Phosphonio)(phos-phoranylidene)methanethiolate 669
42.13.2.1.6 Method 6: Addition of a 1,3-Diene to an Alkyl(chloro)(methyl-sulfanyl)phosphine 669
42.13.2.1.7 Method 7: Sulfurization of Trialkylphosphine Oxides 670
42.13.3 Product Subclass 3: Trialkylphosphine Selenides 670
42.13.3.1 Synthesis of Product Subclass 3 670
42.13.3.1.1 Method 1: Addition of a Dialkylphosphine Selenide to an Aldehyde 670
42.13.3.1.2 Method 2: Addition of Potassium Selenocyanate to Trialkylphosphines 671
42.13.3.1.3 Method 3: Addition of Elemental Selenium to Trialkylphosphines 672
42.13.3.1.4 Method 4: Catalytic Reaction of Diphenyl Diselenide and Tributylphosphine under Microwave Irradiation 672
42.13.3.1.5 Method 5: Reaction of a 1,2,3-Selenadiazole with a Trialkylphosphine 673
42.13.4 Product Subclass 4: Trialkylphosphine Tellurides 673
42.13.4.1 Synthesis of Product Subclass 4 673
42.13.4.1.1 Method 1: Addition of Elemental Tellurium to Trialkylphosphines 673
42.13.5 Product Subclass 5: Trialkylphosphine Imides [Trialkyl(imino)phosphoranes] 674
42.13.5.1 Synthesis of Product Subclass 5 674
42.13.5.1.1 Method 1: Reaction of an Azide with a Trialkylphosphine (The Staudinger Reaction) 674
42.13.5.1.2 Method 2: Addition of Base to Aminophosphonium Salts 675
42.13.5.1.3 Method 3: Addition of an Iodonium Ylide to Tributylphosphine 675
42.14 Product Class 14: Dialkylphosphinic Acids and Derivatives 680
42.14.1 Product Subclass 1: Dialkyltrihalophosphoranes and Other Heteroatom-Containing Analogues 681
42.14.1.1 Synthesis of Product Subclass 1 681
42.14.1.1.1 Method 1: Halogenation of Dialkylhalophosphines 682
42.14.1.1.2 Method 2: Electrochemical Fluorination of Secondary Phosphines 683
42.14.2 Product Subclass 2: Dialkylphosphinic Halides 683
42.14.2.1 Synthesis of Product Subclass 2 683
42.14.2.1.1 Method 1: Halogenation of Tri- and Tetracoordinated Phosphorus-Containing Precursors 683
42.14.2.1.1.1 Variation 1: Halogenation of Dialkylphosphinic Acids and Derivatives 683
42.14.2.1.1.2 Variation 2: Halogenation of Dialkylphosphine Oxides 684
42.14.2.1.1.3 Variation 3: Halogenation of Dialkylphosphines and Dialkylphosphinites 685
42.14.2.1.2 Method 2: Oxidation of Dialkylhalophosphines 685
42.14.2.1.3 Method 3: Synthesis from Dialkyltrihalophosphoranes 686
42.14.3 Product Subclass 3: Dialkylphosphinic Acids 687
42.14.3.1 Synthesis of Product Subclass 3 687
42.14.3.1.1 Method 1: Oxidation of Secondary Dialkylphosphines 687
42.14.3.1.2 Method 2: Dealkylation of Alkyl Dialkylphosphinates 687
42.14.3.1.3 Method 3: Alkylation Reactions of Tri- and Tetracoordinated Phosphorus-Containing Precursors 688
42.14.3.1.3.1 Variation 1: Alkylation of Hypophosphorous Acid Salts 688
42.14.3.1.3.2 Variation 2: Alkylation of Bis(trimethylsilyl) Phosphonite 689
42.14.3.1.4 Method 4: Hydrolysis of Tetra- and Pentacoordinated Phosphorus-Containing Precursors 689
42.14.3.1.4.1 Variation 1: Hydrolysis of Dialkylphosphinic Halides 689
42.14.3.1.4.2 Variation 2: Hydrolysis of P,P-Dialkylphosphinic Amides 690
42.14.3.1.4.3 Variation 3: Hydrolysis of Dialkyltrihalophosphoranes 691
42.14.3.1.5 Method 5: Oxidative Cleavage of Tetraalkyldiphosphine Disulfides 691
42.14.3.1.6 Method 6: Reaction of Alkylphosphinic Acids with Alkenes 692
42.14.4 Product Subclass 4: Alkyl/Aryl Dialkylphosphinates 692
42.14.4.1 Synthesis of Product Subclass 4 692
42.14.4.1.1 Method 1: Oxidation of Alkyl/Aryl Dialkylphosphinites 692
42.14.4.1.2 Method 2: Arbuzov Reaction of Dialkyl Alkylphosphonites 693
42.14.4.1.3 Method 3: Reaction of Dialkylphosphinic Halides with Alcohols or Phenols 694
42.14.4.1.4 Method 4: Alkylation of Alkyl Alkylphosphinates 694
42.14.4.1.5 Method 5: Esterification of Dialkylphosphinic Acids and Transesterification of Alkyl Dialkylphosphinates 696
42.14.5 Product Subclass 5: S-Alkyl/Aryl Dialkylphosphinothioates 697
42.14.5.1 Synthesis of Product Subclass 5 697
42.14.5.1.1 Method 1: S-Alkylation of Dialkylphosphinothioic O-Acids 697
42.14.5.1.2 Method 2: Reaction of Dialkylphosphinic Halides with Thiols 698
42.14.5.1.3 Method 3: Reaction of Secondary Phosphine Oxides or Dialkylhalophosphine Derivatives with Disulfides or Thiocarbonyl Derivatives 698
42.14.6 Product Subclass 6: P,P-Dialkylphosphinic Amides 699
42.14.6.1 Synthesis of Product Subclass 6 699
42.14.6.1.1 Method 1: Reaction of Dialkylphosphinic Halides with Amine Derivatives 699
42.14.6.1.2 Method 2: Oxidation of Aminophosphines 700
42.14.6.1.3 Method 3: Reaction of Dialkylhalophosphines with Hydroxylamine Derivatives 701
42.14.7 Product Subclass 7: Dialkylphosphinothioic Halides 701
42.14.7.1 Synthesis of Product Subclass 7 701
42.14.7.1.1 Method 1: Halogenation of Pentavalent Phosphinothioic Precursors 701
42.14.7.1.1.1 Variation 1: Halogenation of Dialkylphosphinothioic Acids 701
42.14.7.1.1.2 Variation 2: Halogenation of Tetraalkyldiphosphine Disulfides 702
42.14.7.1.1.3 Variation 3: Halogenation of Se-Alkyl Dialkylphosphinoselenothioates 702
42.14.7.1.2 Method 2: Addition of Sulfur to Dialkylhalophosphines 703
42.14.7.1.3 Method 3: Reaction of Phosphonothioic Dihalides with Organometallic Reagents 703
42.14.7.1.4 Method 4: Halogenation of Dialkylphosphinothioic Amides and S-Amino Derivatives of Dialkylphosphinodithioic Acids 704
42.14.8 Product Subclass 8: Dialkylphosphinothioic O-Acids and Their Sulfur and Selenium Analogues 705
42.14.8.1 Synthesis of Product Subclass 8 705
42.14.8.1.1 Method 1: Hydrolysis of Dialkylphosphinothioic Halides 705
42.14.8.1.2 Method 2: Preparation of Dialkylphosphinodithioic Acids 705
42.14.8.1.3 Method 3: Preparation of Dialkylphosphinoselenothioic Se-Acids 706
42.14.9 Product Subclass 9: O-Alkyl/Aryl Dialkylphosphinothioates 706
42.14.9.1 Synthesis of Product Subclass 9 706
42.14.9.1.1 Method 1: Reaction of Dialkylphosphinothioic Halides with Alcohols or Phenols 706
42.14.9.1.2 Method 2: Sulfuration of Alkyl Dialkylphosphinites 707
42.14.9.1.3 Method 3: Alkylation of O-Alkyl Alkylphosphinothioates 708
42.14.9.1.4 Method 4: Reaction of Tetraalkyldiphosphine Disulfides or Phosphine Sulfides 708
42.14.10 Product Subclass 10: Alkyl/Aryl Dialkylphosphinodithioates and Se-Alkyl/Aryl Dialkylphosphinoselenothioates 709
42.14.10.1 Synthesis of Product Subclass 10 709
42.14.10.1.1 Method 1: Alkylation of Dialkylphosphinodithioic Acids or Their Salts 709
42.14.10.1.2 Method 2: Arbuzov-Type Alkylation of Alkylphosphonotrithioates 709
42.14.10.1.3 Method 3: Reaction of Tetraalkyldiphosphine Disulfides with Disulfides and Diselenides 710
42.14.11 Product Subclass 11: P,P-Dialkylphosphinothioic Amides 711
42.14.11.1 Synthesis of Product Subclass 11 711
42.14.11.1.1 Method 1: Reaction of Dialkylphosphinothioic Halides with Amines 711
42.14.11.1.2 Method 2: Sulfuration of Aminophosphines 712
42.14.12 Product Subclass 12: Dialkylphosphinoselenoic Halides 712
42.14.12.1 Synthesis of Product Subclass 12 712
42.14.12.1.1 Method 1: Addition of Selenium to Dialkylhalophosphines 712
42.14.13 Product Subclass 13: Dialkylphosphinoselenoic O-Acids and Dialkylphosphinodiselenoic Acids 713
42.14.13.1 Synthesis of Product Subclass 13 713
42.14.13.1.1 Method 1: Hydrolysis of Dialkylphosphinoselenoic Halides 713
42.14.13.1.2 Method 2: Acidification of Sodium Dialkylphosphinodiselenoates 714
42.14.14 Product Subclass 14: O-Alkyl/Aryl Dialkylphosphinoselenoates 714
42.14.14.1 Synthesis of Product Subclass 14 714
42.14.14.1.1 Method 1: Addition of Selenium to Dialkylphosphinites 714
42.14.14.1.2 Method 2: Reaction of Dialkylphosphinoselenoic Halides with Alcohols 715
42.14.15 Product Subclass 15: S-Alkyl/Aryl Dialkylphosphinoselenothioates 715
42.14.15.1 Synthesis of Product Subclass 15 715
42.14.15.1.1 Method 1: Addition of Selenium to Dialkylphosphinothioites 715
42.14.16 Product Subclass 16: P,P-Dialkylphosphinoselenoic Amides 716
42.14.16.1 Synthesis of Product Subclass 16 716
42.14.16.1.1 Method 1: Addition of Selenium to Aminophosphines 716
42.14.16.1.2 Method 2: Reaction of Dialkylphosphinoselenoic Halides with Amines 716
42.14.17 Product Subclass 17: Anhydrides of Dialkylphosphinic Acids and Their Sulfur and Selenium Analogues 717
42.14.17.1 Synthesis of Product Subclass 17 717
42.14.17.1.1 Method 1: Oxidation of Dialkylphosphine Disulfides 717
42.14.17.1.2 Method 2: Condensation of Dialkylphosphinic Acid Esters with Dialkylphosphinic Halides and Their Sulfur Analogues 718
42.14.17.1.3 Method 3: Self-Condensation of Dialkylphosphinic Halides and Their Sulfur Analogues 718
42.14.17.1.4 Method 4: Oxidation or Sulfuration of Dialkylphosphinous Anhydrides 720
42.15 Product Class 15: Alkylphosphonic Acids and Derivatives 726
42.15.1 Product Subclass 1: Alkylphosphonic Dihalides and Their Sulfur and Selenium Derivatives 727
42.15.1.1 Synthesis of Product Subclass 1 727
42.15.1.1.1 Method 1: Alkylphosphonic Dihalides from Alkylphosphonic Acids and Their Derivatives 727
42.15.1.1.1.1 Variation 1: Reaction of Phosphonic Acids with Halogenating Reagents 727
42.15.1.1.1.2 Variation 2: Reaction of Phosphonic Acid Diesters with Halogenating Reagents 728
42.15.1.1.2 Method 2: Alkylphosphonic Dihalides from Alkyltetrahalophosphoranes 729
42.15.1.1.3 Method 3: Hydrolytic (or Other) Decompositions of Aluminum Halide Complexes of Alkyltetrahalophosphoranes 729
42.15.1.1.4 Method 4: Oxidation of Alkyldihalophosphines 730
42.15.1.1.5 Method 5: Alkylphosphonic Dihalides from Phosphorus Trihalides 731
42.15.1.1.5.1 Variation 1: Reaction of Phosphorus Trihalides with Aliphatic Hydrocarbons 731
42.15.1.1.5.2 Variation 2: Other Protocols Based on the Use of Phosphorus Trichloride 731
42.15.1.1.6 Method 6: Alkylphosphonic Dihalides by Miscellaneous Procedures 731
42.15.1.1.7 Method 7: Synthesis of Alkylphosphonothioic Dihalides 732
42.15.1.1.7.1 Variation 1: Sulfuration of Alkylphosphonic Dihalides 732
42.15.1.1.7.2 Variation 2: Sulfuration of Alkyldihalophosphines 732
42.15.1.1.7.3 Variation 3: Other Protocols 732
42.15.1.1.8 Method 8: Synthesis of Alkylphosphonoselenoic Dihalides 733
42.15.1.1.8.1 Variation 1: Addition of Selenium to Alkyldihalophosphines 733
42.15.2 Product Subclass 2: Alkylphosphonic Acids and Their Sulfur and Selenium Analogues 733
42.15.2.1 Synthesis of Product Subclass 2 733
42.15.2.1.1 Method 1: Hydrolysis of Alkyltetrachlorophosphoranes 733
42.15.2.1.2 Method 2: Hydrolysis of Alkylphosphonic Dihalides 734
42.15.2.1.3 Method 3: Alkylphosphonic Acids from Alkylphosphonic Acid Esters 734
42.15.2.1.3.1 Variation 1: Hydrolysis of Alkylphosphonic Acid Esters 734
42.15.2.1.3.2 Variation 2: Dealkylation of Dialkyl Alkylphosphonates 735
42.15.2.1.4 Method 4: Hydrolysis of Alkylphosphonic Acid Amides 736
42.15.2.1.5 Method 5: Disproportionation of Alkylphosphonous Acids 737
42.15.2.1.6 Method 6: In Situ Oxidation of Alkylphosphonous Acids 737
42.15.2.1.7 Method 7: Oxidation of Primary Alkylphosphines 738
42.15.2.1.8 Method 8: Addition of Phosphorous Acid to Alkenes, Carbonyl Compounds, Imines, and Nitriles 738
42.15.2.1.9 Method 9: Reaction of Phosphorus Trichloride with Carbonyl Compounds or Carboxylic Acid Derivatives Followed by Hydrolysis 739
42.15.2.1.10 Method 10: Hydrolysis of 1-Aryl-1-[(4-tolylsulfinyl)amino]methylbis(di-ethylamino)phosphine--Boranes 740
42.15.2.1.11 Method 11: Synthesis of Alkylphosphonothioic Acids 741
42.15.3 Product Subclass 3: Alkyl/Aryl Alkylphosphonohalidates 741
42.15.3.1 Synthesis of Product Subclass 3 741
42.15.3.1.1 Method 1: Reaction of Dialkyl Alkylphosphonates with Halogenating Agents 741
42.15.3.1.2 Method 2: Reaction of Aluminum Halide Complexes of Alkyltetrachlorophosphoranes with Alcohols 742
42.15.3.1.3 Method 3: Reaction of Dialkyl Chlorophosphites with Alkyl Halides 742
42.15.3.1.4 Method 4: Reaction of Alkylphosphonic Dihalides with Alcohols or Phenols 743
42.15.3.1.5 Method 5: Halogenation of Alkylphosphinates 743
42.15.4 Product Subclass 4: S-Alkyl/Aryl Alkylphosphonohalidothioates and Sulfur Derivatives 743
42.15.4.1 Synthesis of Product Subclass 4 743
42.15.4.1.1 Method 1: Reaction of Alkylphosphonic Dihalides with Thiols 743
42.15.4.1.2 Method 2: Reaction of Alkyldichlorophosphines with Sulfenyl Chlorides 744
42.15.4.1.3 Method 3: Chlorination of O,O-Dialkyl Alkylphosphonothioates 744
42.15.4.1.4 Method 4: Reaction of Alkylphosphonothioic Dihalides with Alkane-/Arenethiols 744
42.15.5 Product Subclass 5: P-Alkylphosphonamidic Halides and Their Sulfur and Selenium Derivatives 745
42.15.5.1 Synthesis of Product Subclass 5 745
42.15.5.1.1 Method 1: Reaction of Alkylphosphonic Dihalides with Amines 745
42.15.5.1.2 Method 2: Exchange Reactions of Alkylphosphonic Diamides 746
42.15.5.1.3 Method 3: Rearrangement of Allyl Dialkylphosphoramidochloridites 746
42.15.5.1.4 Method 4: Oxidative Conversion of Aminochlorophosphines 747
42.15.5.1.5 Method 5: Ring Opening of 1-Functionalized Aziridines with Alkylphosphonic Dihalides 748
42.15.5.1.6 Method 6: Reaction of Alkylphosphonothioic Dihalides with Amines 749
42.15.5.1.7 Method 7: Addition of Sulfur to Alkyl(dialkylamino)halophosphines 749
42.15.5.1.8 Method 8: Reaction of Aminesulfenamides with Alkylphosphonic Dichlorides 750
42.15.5.1.9 Method 9: Reaction of Alkylphosphonoselenoic Dihalides with Amines 750
42.15.5.1.10 Method 10: Addition of Selenium to Alkyl(chloro)(dialkylamino)phosphines 751
42.15.6 Product Subclass 6: Alkyl/Aryl Hydrogen Alkylphosphonates and Their O-Alkyl/Aryl Sulfur and Selenium Derivatives 751
42.15.6.1 Synthesis of Product Subclass 6 751
42.15.6.1.1 Method 1: Synthesis from Alkylphosphonic Dichlorides 751
42.15.6.1.2 Method 2: Hydrolysis of Alkyl/Aryl Alkylphosphonochloridates 754
42.15.6.1.3 Method 3: Hydrolysis of Diesters of Alkylphosphonic Acids 755
42.15.6.1.4 Method 4: Esterification of Alkylphosphonic Acids 756
42.15.6.1.5 Method 5: Dealkylation of Dialkyl Alkylphosphonates 757
42.15.6.1.5.1 Variation 1: Dealkylation of Dialkyl Phosphonates with Sodium Iodide 758
42.15.6.1.5.2 Variation 2: Dealkylation of Dialkyl Phosphonates with Sodium Azide 758
42.15.6.1.5.3 Variation 3: Selective Monodebenzylation of Dibenzyl Phosphonates with Tertiary Amines 759
42.15.6.1.5.4 Variation 4: Dealkylation of Dialkyl Methylphosphonates with Diphenylguanidine 760
42.15.6.1.5.5 Variation 5: Silylation--Desilylation Procedure 761
42.15.6.1.6 Method 6: Alkyl/Aryl Hydrogen Alkylphosphonates by Miscellaneous Methods 761
42.15.6.1.7 Method 7: Hydrolysis of Dialkyl/Diaryl Alkylphosphonothioates 764
42.15.6.1.8 Method 8: Synthesis of O-Alkyl Hydrogen Alkylphosphonothioates from Alkylphosphonothioic Dichlorides 766
42.15.6.1.9 Method 9: Hydrolysis of O-Alkyl Alkylphosphonochloridothioates 766
42.15.6.1.10 Method 10: Synthesis of O-Alkyl Hydrogen Alkylphosphonothioates from O-Alkyl Alkylphosphonochloridates 767
42.15.6.1.11 Method 11: Addition of Sulfur to Alkyl Alkylphosphinates 768
42.15.6.1.12 Method 12: Horner--Wadsworth--Emmons Reaction of Phosphonamidates and Thiophosphonamidates 768
42.15.6.1.13 Method 13: Oxathiaphospholane Approach for the Synthesis of Nucleoside Methylphosphonothioic Acids 770
42.15.6.1.14 Method 14: Alcoholysis of Monothiophosphonic Anhydrides 771
42.15.6.1.15 Method 15: Synthesis of O-Alkyl Hydrogen Alkylphosphonoselenoates 772
42.15.7 Product Subclass 7: S-Alkyl/Aryl Hydrogen Alkylphosphonothioates and Their Sulfur and Selenium Derivatives 772
42.15.7.1 Synthesis of Product Subclass 7 772
42.15.7.1.1 Method 1: Coupling Reaction of Alkylphosphonic Acids with Thiols 772
42.15.7.1.2 Method 2: Alkylation of Alkylphosphonothioic Acid Anions with Alkyl Halides 773
42.15.8 Product Subclass 8: P-Alkylphosphonamidic Acids and Their Sulfur and Selenium Derivatives 773
42.15.8.1 Synthesis of Product Subclass 8 773
42.15.8.1.1 Method 1: Reaction of Alkyl/Aryl Alkylphosphonohalidates with Tertiary Amines 773
42.15.8.1.2 Method 2: Synthesis of P-Ethylphosphonamidothioic Acids 774
42.15.9 Product Subclass 9: O,O-Dialkyl/Diaryl Alkylphosphonates and Their Sulfur and Selenium Derivatives 775
42.15.9.1 Synthesis of Product Subclass 9 775
42.15.9.1.1 Method 1: Reaction of Alkylphosphonic Dihalides with Alcohols 775
42.15.9.1.2 Method 2: Reaction of Alkyl/Aryl Alkylphosphonohalidates with Alcohols 775
42.15.9.1.3 Method 3: Reaction of Phosphites with a-Halo Ketones 775
42.15.9.1.4 Method 4: Michaelis--Becker Reaction 775
42.15.9.1.5 Method 5: Michaelis--Arbuzov Reaction 777
42.15.9.1.6 Method 6: Addition of Tricoordinated Organophosphorus Derivatives to Unsaturated Systems 777
42.15.9.1.6.1 Variation 1: Addition of Dialkyl Phosphites to Alkenes, Allenes, and Alkynes 777
42.15.9.1.6.2 Variation 2: Addition of Dialkyl Phosphites to Carbonyl Groups 778
42.15.9.1.6.3 Variation 3: Addition of Dialkyl Phosphite Anions to Imines 780
42.15.9.1.7 Method 7: Transesterification Reactions 783
42.15.9.1.8 Method 8: Reaction of Alkyl/Aryl Hydrogen Phosphonates with Alcohols 784
42.15.9.1.9 Method 9: Reaction of O-Alkyl/Aryl Alkylphosphonohalidothioates with Alcohols 785
42.15.9.1.10 Method 10: Reaction of Alkylphosphonothioic Dihalides with Alcoholates 786
42.15.9.1.11 Method 11: Sulfurization of Tricoordinated Alkylphosphonous Acid Diesters 787
42.15.9.1.12 Method 12: Miscellaneous Protocols Leading to O,O-Dialkyl/Diaryl Alkylphosphonothioates 788
42.15.9.1.13 Method 13: Selenation of O,O-Dialkyl/Diaryl Alkylphosphonites 789
42.15.10 Product Subclass 10: O,S-Dialkyl/Diaryl Alkylphosphonothioates and Their Sulfur and Selenium Derivatives 790
42.15.10.1 Synthesis of Product Subclass 10 790
42.15.10.1.1 Method 1: Reaction of Alkyl/Aryl Alkylphosphonohalidates with Alkali Metal Thiolates 790
42.15.10.1.2 Method 2: Reaction of Dithiocarboxylic Acids with Dialkyl Chlorophosphites 790
42.15.10.1.3 Method 3: Reaction of Alkyl/Aryl Alkylphosphonohalidodithioates with Alcohols 790
42.15.10.1.4 Method 4: Reaction of Alkylphosphonic Dihalides with Alcohols and Thiols, or Sulfanyl Alcohols 790
42.15.10.1.5 Method 5: Alkylation of O-Alkyl/Aryl Alkylphosphonothioate Anions 792
42.15.10.1.6 Methods 6: Miscellaneous Procedures 793
42.15.11 Product Subclass 11: S,S-Dialkyl/Diaryl Alkylphosphonodithioates and Their Sulfur and Selenium Derivatives 793
42.15.11.1 Synthesis of Product Subclass 11 793
42.15.11.1.1 Method 1: Arbuzov Reaction of Trialkyl Trithiophosphites with Alkyl Halides 793
42.15.11.1.2 Method 2: Preparation of Di- and Trithioesters from Alkylphosphonothioic and Alkylphosphonic Dichlorides 794
42.15.11.1.3 Method 3: Addition of Phosphonodithioyl and Phosphonotrithioyl Radicals to Alkenes 795
42.15.12 Product Subclass 12: O- and S-Alkyl/Aryl P-Alkylphosphonamidates and Their Sulfur and Selenium Derivatives 796
42.15.12.1 Synthesis of Product Subclass 12 796
42.15.12.1.1 Method 1: Reaction of Alkyl/Aryl Alkylphosphonohalidates with Amines 796
42.15.12.1.2 Method 2: Reaction of Alkylphosphonic Dichlorides with Amino Alcohols or with an Alcohol and an Amine 798
42.15.12.1.3 Method 3: Reaction of P-Alkylphosphonamidic Halides with Alcohols 799
42.15.12.1.4 Method 4: Reaction of Dialkyl Amidophosphites with Alkyl Halides 800
42.15.12.1.5 Method 5: Oxidation of Alkylphosphonamidous Acid Esters 801
42.15.12.1.6 Method 6: Aminolysis of Dialkyl Alkylphosphonates 802
42.15.12.1.7 Method 7: Perkov-Type Reaction 802
42.15.12.1.8 Method 8: Reaction of Alkylphosphonothioic Dihalides with Amino Alcohols 802
42.15.12.1.9 Method 9: Reaction of O-Alkyl/Aryl Alkylphosphonohalidothioates with Amines 803
42.15.12.1.10 Method 10: Sulfuration or Selenation of Alkylphosphonamidites 804
42.15.13 Product Subclass 13: P-Alkylphosphonic Diamides and Their Sulfur and Selenium Derivatives 804
42.15.13.1 Synthesis of Product Subclass 13 804
42.15.13.1.1 Method 1: Reaction of Alkylphosphonic Dihalides with Amines 804
42.15.13.1.2 Method 2: Reaction of O-Alkyl Phosphorous Diamides with Alkyl Halides 805
42.15.13.1.3 Method 3: Reaction of N,N,N',N'-Tetraalkylphosphorodiamidic Chlorides with Organometallic Reagents 805
42.15.13.1.4 Method 4: Transamination of P-Alkylphosphonic Diamides 806
42.15.13.1.5 Method 5: Oxidation of P-Alkylphosphonous Diamides 806
42.15.13.1.6 Method 6: Sulfurization of Bis(dialkylamino)phosphines 807
42.15.13.1.7 Method 7: Reaction of Alkyl Phosphorodiamidothioites with Alkyl Halides 807
42.15.13.1.8 Method 8: Selenation of Bis(dialkylamino)phosphines 808
42.15.14 Product Subclass 14: Anhydrides of Alkylphosphonic Acids and Their Derivatives 808
42.15.14.1 Synthesis of Product Subclass 14 808
42.15.14.1.1 Method 1: Reaction of Dialkyl Alkylphosphonates with Halides of Oxoacids of Phosphorus 808
42.15.14.1.2 Method 2: Reaction of Alkylphosphonic Acids and Their Sulfur Analogues with Carbodiimides 809
42.15.14.1.2.1 Variation 1: Reaction of Alkylphosphonic Acids with Carbodiimides 809
42.15.14.1.2.2 Variation 2: Reaction of O-Alkyl/Aryl Alkylphosphonothioic Acids with Carbodiimides 809
42.15.14.1.3 Method 3: Reactions of Alkyl/Aryl Alkylphosphonohalidates and N,N,P-Trialkylphosphonamidic Halides 810
42.15.14.1.3.1 Variation 1: Reactions of Alkyl/Aryl Alkylphosphonohalidates with Nucleophiles 810
42.15.14.1.3.2 Variation 2: Reactions of N,N,P-Trialkylphosphonamidic Halides with Nucleophiles 810
42.15.14.1.4 Method 4: Synthesis of Oligomers of Alkylphosphonic and Alkylphosphonothioic Anhydrides 811
42.15.14.1.5 Methods 5: Miscellaneous Procedures 813
42.16 Product Class 16: Phosphoric Acid and Derivatives 826
42.16.1 Product Subclass 1: P==O Phosphates 827
42.16.1.1 Synthesis of Product Subclass 1 827
42.16.1.1.1 Mixed Anhydrides of Phosphoric Acid and Esters of Phosphoric Acid with Non-Phosphorus-Containing Acids 827
42.16.1.1.1.1 Method 1: Reaction of Phosphates with Anhydrides of Carboxylic Acids 827
42.16.1.1.1.2 Method 2: Reaction of Phosphate Esters with Anhydrides of Strong Carboxylic Acids 828
42.16.1.1.1.3 Method 3: Reaction of Phosphates or Phosphate Esters with Amino Acids in the Presence of Diisopropylcarbodiimide or Dicyclohexylcarbodiimide 828
42.16.1.1.2 Alkyl Dihydrogen Phosphates 829
42.16.1.1.2.1 Method 1: Phosphorylation of Alcohols with Phosphoryl Chloride 829
42.16.1.1.2.1.1 Variation 1: Phosphorylation of Unprotected Nucleosides 829
42.16.1.1.2.1.2 Variation 2: Phosphorylation of Other Alcohols 830
42.16.1.1.2.2 Method 2: Catalytic Condensation of Phosphoric Acid with Alcohols 831
42.16.1.1.2.3 Method 3: Phosphoramidites as Phosphorylating Agents 831
42.16.1.1.2.3.1 Variation 1: 5'-Phosphorylation of Solid-Supported Oligonucleotides by tert-Butyl 2-Cyanoethyl Diisopropylphosphoramidite 832
42.16.1.1.2.3.2 Variation 2: Solid-Phase Phosphoramidites for Selective Monophosphorylation of Carbohydrates and Nucleosides 833
42.16.1.1.2.4 Method 4: Disodium 2-({2-[Bis(4-methoxyphenyl)(phenyl)methoxy]eth-yl}sulfonyl)ethyl Phosphate as a Phosphorylating Agent for Primary and Secondary Alcohol Functions in Nucleosides 835
42.16.1.1.3 S-Alkyl Dihydrogen Phosphorothioates 836
42.16.1.1.3.1 Method 1: Selective Dealkylation 836
42.16.1.1.3.2 Method 2: S-Alkylation of Phosphorothioic Acid 837
42.16.1.1.4 Alkyl Trihydrogen Diphosphates 838
42.16.1.1.4.1 Method 1: Phosphorylation by Tris(tetrabutylammonium) Hydrogen Pyrophosphate 838
42.16.1.1.4.1.1 Variation 1: Phosphorylation of Homoallylic 4-Toluenesulfonates or Allylic Halides 838
42.16.1.1.4.1.2 Variation 2: Phosphorylation of 5'-Tosyl Nucleosides 839
42.16.1.1.4.2 Method 2: Phosphorylation of Activated 5'-Nucleoside Monophosphates 840
42.16.1.1.4.2.1 Variation 1: Activation by Imidazolides 840
42.16.1.1.4.2.2 Variation 2: Activation by Conversion into Phosphorodichloridates 842
42.16.1.1.5 S-Alkyl Trihydrogen Thiodiphosphates 842
42.16.1.1.5.1 Method 1: Thiophosphorylation of 4-Toluenesulfonates or Bromides 843
42.16.1.1.6 Alkyl Tetrahydrogen Triphosphates 844
42.16.1.1.6.1 Method 1: The Ludwig One-Pot, Three-Step Procedure 844
42.16.1.1.6.2 Method 2: The Ludwig--Eckstein Procedure 845
42.16.1.1.6.3 Method 3: Enzymatic Approaches 846
42.16.1.1.6.4 Method 4: Synthesis via a Reactive Pyrrolidinium Phosphoramidate Zwitterion Intermediate 848
42.16.1.1.6.5 Method 5: Solid-Phase Synthesis of Nucleoside ß-Triphosphates 849
42.16.1.1.7 Anhydrides of Phosphoric Acid: Nucleoside Triphosphate Analogues 851
42.16.1.1.7.1 Method 1: Synthesis of ß,.-Methylene Nucleoside Triphosphate Analogues through Activation by Trihaloacetic Anhydrides and 1-Methylimidazole 851
42.16.1.1.7.2 Method 2: Synthesis of ß,.-Methylene Deoxynucleoside Triphosphate Analogues via Morpholidates 853
42.16.1.1.7.3 Method 3: Synthesis of a,ß-Methylene Deoxynucleoside Triphosphate Analogues by Enzymatic Phosphorylation of the Corresponding a,ß-Methylene Deoxynucleoside Diphosphate Analogues 854
42.16.1.1.8 Alkyl/Aryl Phosphorohalidates 856
42.16.1.1.8.1 Method 1: Phosphorylation with Phosphoryl Chloride 856
42.16.1.1.8.2 Method 2: Synthesis of Alkyl/Aryl Phosphorodifluoridates 856
42.16.1.1.8.2.1 Variation 1: Fluorination of Alkyl or Aryl Phosphorodichloridates 856
42.16.1.1.8.2.2 Variation 2: Fluorination of P--N Imidazole Derivatives 857
42.16.1.1.9 S-Alkyl/S-Aryl Phosphorodihalidothioates 858
42.16.1.1.10 Dialkyl/Diaryl Hydrogen Phosphates 858
42.16.1.1.10.1 Method 1: Stepwise Esterification of Phosphoryl Chloride 859
42.16.1.1.10.2 Method 2: Selective Hydrolysis of Triesters of Phosphoric Acid 859
42.16.1.1.10.3 Method 3: Solid-Phase Synthesis of Dinucleoside and Nucleoside--Carbohydrate Phosphodiesters 860
42.16.1.1.11 O,S-Dialkyl/O,S-Diaryl Hydrogen Thiophosphates 861
42.16.1.1.11.1 Method 1: Alkylation of Sulfur in Phosphorothioate Derivatives 862
42.16.1.1.11.2 Method 2: Oxidation of O,S-Disubstituted Phosphonothiolates 863
42.16.1.1.11.3 Method 3: Selective Dealkylation of Triesters Bearing a P--S--C Bond System 864
42.16.1.1.12 S,S-Dialkyl/S,S-Diaryl Hydrogen Phosphorodithioates 865
42.16.1.1.12.1 Method 1: Reaction of Phosphorodichloridates with Alkane- or Arenethiols 865
42.16.1.1.12.2 Method 2: Reaction of Elemental Phosphorus with Benzenethiol 865
42.16.1.1.12.3 Method 3: Reaction of N-(Alkylsulfanyl)phthalimides with Phosphinates in the Presence of Hexamethyldisilazane 866
42.16.1.1.13 Dialkyl Dihydrogen Diphosphates 867
42.16.1.1.13.1 Method 1: Synthesis of Dialkyl Dihydrogen Diphosphates by Morpholidate Coupling 867
42.16.1.1.13.2 Method 2: Triphenylphosphine and Di-2-pyridyl Disulfide as Coupling Agents in One-Pot Syntheses of Symmetrical Dinucleoside 5',5''-Pyrophosphates 868
42.16.1.1.13.3 Method 3: Sugar Nucleoside Diphosphates via a Reactive Zwitterionic Phosphoramidate Intermediate 869
42.16.1.1.13.4 Method 4: Solid-Phase Synthesis of Symmetrical Nucleoside Phosphodiesters 870
42.16.1.1.14 Dialkyl/Diaryl Phophorohalidates 872
42.16.1.1.14.1 Method 1: Chlorination of Phosphites with 1,3,5-Trichloro-1,3,5-triazinane-2,4,6-trione or tert-Butyl(chloro)cyanamide 872
42.16.1.1.14.2 Method 2: Halogenation of Bis(fluoroalkyl) Phosphites 873
42.16.1.1.15 Trialkyl/Triaryl Phosphates 874
42.16.1.1.15.1 Method 1: Addition of Hydrogen Chloride to Vinyl Phosphates 874
42.16.1.1.15.2 Method 2: Phosphorylation 875
42.16.1.1.15.2.1 Variation 1: Phosphorylation with Diphenyl Phosphorochloridate 875
42.16.1.1.15.2.2 Variation 2: Phosphorylation with (2-Oxo-5,5-diphenyloxazolidin-3-yl)phosphonates 876
42.16.1.1.15.2.3 Variation 3: Phosphorylation Catalyzed by a Low-Molecular-Weight Peptide-Based Catalyst 879
42.16.1.1.15.3 Method 3: Phosphite Oxidation in the Presence of Alcohols 880
42.16.1.1.15.4 Method 4: Phosphate Esterification Promoted by Silver(I) Oxide 880
42.16.1.1.16 O,O,S-Trialkyl/O,O,S-Triaryl Phosphorothioates 881
42.16.1.1.16.1 Method 1: Synthesis of Phosphorothioates Containing an a,ß-Unsaturated Carbonyl Moiety 881
42.16.1.1.16.2 Method 2: Redox Reaction of a Phosphite with Tellurium Tetrachloride 883
42.16.1.1.16.3 Method 3: Solvent-Free S-Alkylation of Phosphites 883
42.16.1.1.17 O,O,Se-Trialkyl/O,O,Se-Triaryl Phosphoroselenoates 884
42.16.1.1.17.1 Method 1: Reaction of Potassium O,O-Dialkyl Phosphoroselenoates with Alkenyl(phenyl)iodonium Salts 884
42.16.1.1.17.2 Method 2: Selenophosphorylation of Silyl Enol Ethers 885
42.16.1.1.18 Tetraalkyl/Tetraaryl Diphosphates 886
42.16.1.1.18.1 Method 1: N-[Chloro(dimethylamino)methylene]-N-methylmethan-aminium Chloride as the Condensing Reagent 886
42.16.1.1.18.2 Method 2: Synthesis from a Phosphorochloridate 887
42.16.1.1.19 O,O,O,O-Tetraalkyl/O,O,O,O-Tetraaryl Thiodiphosphates 888
42.16.1.1.19.1 Method 1: Reaction of Phosphites with Sulfur Dichloride 888
42.16.2 Product Subclass 2: P==S Phosphorothioates 889
42.16.2.1 Synthesis of Product Subclass 2 889
42.16.2.1.1 O-Alkyl Dihydrogen Phosphorothioates 889
42.16.2.1.1.1 Method 1: Thiophosphorylation with Thiophosphoryl Chloride 890
42.16.2.1.1.2 Method 2: Sulfurization of Monoalkyl H-Phosphonates 891
42.16.2.1.1.2.1 Variation 1: Sulfurization of Monoalkyl H-Phosphonates with Elemental Sulfur 891
42.16.2.1.1.2.2 Variation 2: Sulfurization of a Bis(trimethylsilyl) Phosphite Ester 891
42.16.2.1.1.3 Method 3: Sulfurization of Trialkyl Phosphites 892
42.16.2.1.2 O-Alkyl/O-Aryl Dihydrogen Phosphorodithioates 894
42.16.2.1.2.1 Method 1: Oxidation of O-Alkyl Hydrogen Phosphonodithioates 894
42.16.2.1.2.2 Method 2: Sulfurization of Alkyl Phosphonothioates 896
42.16.2.1.2.2.1 Variation 1: Sulfurization of Deoxynucleotide Analogues 896
42.16.2.1.2.2.2 Variation 2: Sulfurization of Peptide Analogues 898
42.16.2.1.2.3 Method 3: Synthesis from Sulfidodithiaphospholanes 900
42.16.2.1.2.3.1 Variation 1: Synthesis of Nucleoside 3'-O-Phosphorodithioates 900
42.16.2.1.2.3.2 Variation 2: Synthesis of Nucleoside 5'-O-Phosphorodithioates 901
42.16.2.1.3 O-Alkyl/O-Aryl Trihydrogen Thiodiphosphates 901
42.16.2.1.3.1 Method 1: Phosphorylation of an O-Alkyl Phosphorothioate 902
42.16.2.1.3.2 Method 2: Synthesis via Imidazolides 902
42.16.2.1.3.3 Method 3: Ring Opening of a 5'-(1-Thiocyclotriphosphate) with Ethane-1,2-diamine 903
42.16.2.1.4 O-Alkyl Tetrahydrogen Thiotriphosphates 905
42.16.2.1.4.1 Method 1: Phosphorylation with 2-Chloro-4H-1,3,2-benzodioxaphos-phinin-4-one and Subsequent Reaction with Pyrophosphate 905
42.16.2.1.4.2 Method 2: Thiophosphorylation and Subsequent Reaction with Pyrophosphate 906
42.16.2.1.4.2.1 Variation 1: Direct Thiophosphorylation of the Hydroxy Group 907
42.16.2.1.4.2.2 Variation 2: Thiophosphorylation of Tributylstannyl Ethers 908
42.16.2.1.4.2.3 Variation 3: Enzymatic Phosphorylation 908
42.16.2.1.5 O-Alkyl Tetrahydrogen 1,1-Dithiotriphosphates 909
42.16.2.1.5.1 Method 1: Ring Opening of a 5'-(1-Sulfidocyclotriphosphate) with Lithium Sulfide 909
42.16.2.1.5.2 Method 2: Synthesis via 2-Sulfido-1,3,2-Dithiaphospholanes 910
42.16.2.1.6 Anhydrides of Phosphoric Acid: Nucleoside Triphosphate Analogues 912
42.16.2.1.7 O-Alkyl Tetrahydrogen 1,2,3-Trithiotriphosphates 913
42.16.2.1.8 O-Alkyl/O-Aryl Phosphorofluoridothioates 915
42.16.2.1.8.1 Method 1: Sulfurization of Phosphorofluoridites 915
42.16.2.1.8.2 Method 2: Oxidation and Fluorination of Thio- and Dithiophosphonates 918
42.16.2.1.9 O-Alkyl Phosphorodifluoridothioates 918
42.16.2.1.9.1 Method 1: Sulfurization of a Difluoridophosphite 918
42.16.2.1.9.2 Method 2: Synthesis from a Bis(1H-imidazol-1-yl)phosphinothioate 919
42.16.2.1.10 O,O-Dialkyl/O,O-Diaryl Hydrogen Phosphorothioates 920
42.16.2.1.10.1 Method 1: Stereocontrolled Synthesis via 2-Sulfido-1,3,2-oxathia-phospholanes 921
42.16.2.1.10.2 Method 2: Stereocontrolled Synthesis via Cyclic N-Acylphosphoramidites 923
42.16.2.1.10.3 Method 3: Stereocontrolled Synthesis via 3'-O-Oxazaphospholidines 924
42.16.2.1.10.4 Method 4: Sulfurization of Phosphite Triester 927
42.16.2.1.10.4.1 Variation 1: Sulfurization with 3H-1,2-Benzodithiol-3-one 1,1-Dioxide (Beaucage's Reagent) 927
42.16.2.1.10.4.2 Variation 2: Sulfurization with Phenylacetyl Disulfide 929
42.16.2.1.10.4.3 Variation 3: Sulfurization with 1,1',1'',1'''-[Disulfanediylbis(carbono-thioylnitrilo)]tetraethane 929
42.16.2.1.10.4.4 Variation 4: Sulfurization with Lawesson's Reagent 929
42.16.2.1.10.5 Method 5: Direct Sulfurization of Dialkyl H-Phosphonates 930
42.16.2.1.10.6 Method 6: Polymerization Catalyzed by Uranyl Ion 931
42.16.2.1.11 O,O-Dialkyl/O,O-Diaryl Hydrogen Phosphorodithioates 932
42.16.2.1.11.1 Method 1: Sulfurization of Disubstituted Phosphonodithioates 932
42.16.2.1.11.1.1 Variation 1: From Phosphorochloridites 933
42.16.2.1.11.1.2 Variation 2: Solid-Phase Synthesis of O,O-Dialkyl Phosphorodithoates 933
42.16.2.1.11.2 Method 2: The Dithiaphospholane Method 935
42.16.2.1.11.2.1 Variation 1: From N,N-Diisopropyl-1,3,2-dithiaphospholan-2-amine 935
42.16.2.1.11.2.2 Variation 2: From 2-Chloro-1,3,2-dithiaphospholane 937
42.16.2.1.11.3 Method 3: Dithiophosphorylation of Alcohols and Hydrolysis of the Triester 938
42.16.2.1.11.4 Method 4: Reduction and Subsequent Sulfurization of O,O-Dialkyl Phosphorochloridothioates 940
42.16.2.1.11.5 Method 5: Solid-Phase Sulfurization of Phosphoramidothioites 940
42.16.2.1.12 O,O-Dialkyl/O,O-Diaryl Phosphorofluoridothioates 942
42.16.2.1.12.1 Method 1: Sulfurization of Phosphorofluoridites 942
42.16.2.1.12.2 Method 2: Fluorination of O,O-Dialkyl Phosphonothioates 943
42.16.2.1.12.3 Method 3: Desulfurization of Phosphorodithioates 944
42.16.2.1.13 O,O,O-Trialkyl/O,O,O-Triaryl Phosphorothioates 945
42.16.2.1.13.1 Method 1: Sulfurization of Trivalent Phosphorus Compounds 945
42.16.2.1.13.1.1 Variation 1: Sulfurization with Thiirane 946
42.16.2.1.13.1.2 Variation 2: Sulfurization with Dibenzoyl Tetrasulfide 946
42.16.2.1.13.1.3 Variation 3: Sulfurization with Bis[3-(triethoxysilyl)propyl] Tetrasulfide 946
42.16.2.1.13.2 Method 2: Methanolysis of Phosphoramidothioates 947
42.16.2.1.14 O,O,S-Trialkyl/O,O,S-Triaryl Phosphorodithioates 948
42.16.2.1.14.1 Method 1: Thiophosphorylation of Silyl Enol Ethers 948
42.16.2.1.14.2 Method 2: Alkylation of O,O-Dialkyl Phosphorodithioates 949
42.16.2.1.14.3 Method 3: S-Alkynylation of Potassium O,O-Dialkyl Phosphorodithioates 949
42.16.2.1.14.4 Method 4: Sulfurization of Phosphorochloridothioates 950
42.16.3 Product Subclass 3: P==Se Phosphates 950
42.16.3.1 Synthesis of Product Subclass 3 951
42.16.3.1.1 O,O-Dialkyl Phosphoroselenoates 951
42.16.3.1.1.1 Method 1: Synthesis via Phosphoramidites 951
42.16.3.1.1.2 Method 2: Synthesis via H-Phosphonates 953
42.16.3.1.1.2.1 Variation 1: Oxidation of O,O-Dialkyl Phosphonates with Potassium Selenocyanate 953
42.16.3.1.1.2.2 Variation 2: Oxidation of O,O-Dialkyl H-Phosphonates with Triphenylphosphine Selenide 954
42.16.3.1.1.2.3 Variation 3: Oxidation of O,O-Dialkyl H-Phosphonates with 3H-1,2-Benzothiaselenol-3-one 954
42.16.3.1.1.2.4 Variation 4: Oxidation of O,O-Dialkyl H-Phosphonates with 3-(Phthalimidoselanyl)propanenitrile 956
42.16.3.1.1.3 Method 3: Synthesis via 1,3,2-Oxathiaphospholane 2-Selenides 958
42.16.3.1.2 O,O,O-Trialkyl Phosphoroselenoates 960
42.16.3.1.2.1 Method 1: The Phosphoramidite Approach 960
42.17 Product Class 17: Phosphazenes 970
42.17.1 Product Subclass 1: Schwesinger Bases 970
42.17.1.1 Synthesis of Product Subclass 1 971
42.17.1.1.1 Method 1: Synthesis from Phosphonium Salts 971
42.17.1.2 Applications of Product Subclass 1 in Organic Synthesis 972
42.17.1.2.1 Method 1: Deprotonation Reactions 972
42.17.1.2.2 Method 2: Addition of O- and N-Nucleophiles to Alkynes 977
42.17.1.2.3 Method 3: Activation of Arene--Silicon Bonds 977
42.17.1.2.4 Method 4: Halogen--Zinc Exchange Reactions of Aryl Iodides 978
42.17.1.2.5 Method 5: Sigmatropic Rearrangement of Allylic Amines and Alcohols 979
42.17.1.2.6 Method 6: Synthesis of Diaryl Ethers and Sulfides 980
42.17.1.2.7 Method 7: Michael Addition 981
42.17.2 Product Subclass 2: Proazaphosphatrane Sulfides 981
42.17.2.1 Synthesis of Product Subclass 2 981
42.17.2.1.1 Method 1: Reaction of Proazaphosphatranes with Sulfur 981
42.17.2.2 Applications of Product Subclass 2 in Organic Synthesis 982
42.17.2.2.1 Method 1: Baylis--Hillman Reaction 982
42.17.3 Product Subclass 3: Proazaphosphatrane Oxides 982
42.17.3.1 Synthesis of Product Subclass 3 983
42.17.3.1.1 Method 1: Reaction of Proazaphosphatranes with Bis(trimethylsilyl) Peroxide 983
42.17.3.2 Applications of Product Subclass 3 in Organic Synthesis 983
42.17.3.2.1 Method 1: Silylation of Alcohols 983
42.17.3.2.2 Method 2: Transformation of Isocyanates into Carbodiimides 984
42.17.4 Product Subclass 4: Phosphoramides 984
42.17.4.1 Synthesis of Product Subclass 4 985
42.17.4.1.1 Method 1: Synthesis by Oxidation 985
42.17.4.1.2 Method 2: Synthesis by Nucleophilic Substitution 985
42.17.4.2 Applications of Product Subclass 4 in Organic Synthesis 986
42.17.4.2.1 Method 1: Asymmetric Aldol Reactions 986
42.17.4.2.2 Method 2: Enantioselective Allylation Reactions 987
42.17.4.2.3 Method 3: Asymmetric Diels--Alder Reaction 988
42.17.4.2.4 Method 4: Borane Reduction of Ketones 988
42.17.4.2.5 Method 5: Oxidation Reactions 988
42.17.4.2.6 Method 6: Reduction Reactions 989
42.17.4.2.7 Method 7: Conjugate Addition Reactions 990
42.17.5 Product Subclass 5: Linear and Cyclic Organophosphazenes 991
42.17.5.1 Synthesis of Product Subclass 5 991
42.17.5.1.1 Method 1: Reaction of Phosphorus Pentachloride with Ammonium Chloride or Tris(trimethylsilyl)amine 991
42.17.5.2 Applications of Product Subclass 5 in Organic Synthesis 993
42.17.5.2.1 Method 1: Synthesis of Poly(dichlorophosphazene) 993
42.18 Product Class 18: Pentacoordinated Phosphoranes 1000
42.18.1 Synthesis of Product Class 18 1001
42.18.1.1 Method 1: Nucleophilic Substitution on Pentacoordinated Phosphoranes 1001
42.18.1.1.1 Variation 1: Addition of Alcohols to Phosphoranes 1001
42.18.1.1.2 Variation 2: Addition of Amines to Halophosphoranes 1001
42.18.1.1.3 Variation 3: Reaction of Alkoxy- or Aminosilanes with Halophosphoranes 1002
42.18.1.1.4 Variation 4: Reaction of Unsaturated Compounds with Halophosphoranes 1002
42.18.1.2 Method 2: Addition to Tetracoordinated Phosphorus Compounds 1003
42.18.1.2.1 Variation 1: Addition of Carbonyl Compounds to Phosphorus Ylides 1003
42.18.1.2.2 Variation 2: Addition of 1,3-Dipoles to Phosphorus Ylides 1005
42.18.1.2.3 Variation 3: Addition to Phosphonium Salts 1006
42.18.1.2.4 Variation 4: Addition to Alkylated Iminophosphoranes 1009
42.18.1.3 Method 3: Oxidation of Tricoordinated Phosphorus Compounds 1010
42.18.1.3.1 Variation 1: Reaction with Dihalogens 1010
42.18.1.3.2 Variation 2: Reactions with Other Halogenating Reagents 1011
42.18.1.3.3 Variation 3: Reaction with Peroxides 1012
42.18.1.3.4 Variation 4: Reaction with a-Diketones 1012
42.18.1.3.5 Variation 5: Reaction with a,ß-Unsaturated Carbonyl Compounds 1014
42.18.1.4 Method 4: Condensation Reactions 1015
42.18.1.4.1 Variation 1: Dehydrative Condensation 1015
42.18.1.4.2 Variation 2: Reaction of Carbonyl Compounds with Tricoordinated Phosphorus 1017
42.18.1.5 Method 5: Insertion Reactions 1018
42.18.1.5.1 Variation 1: Insertion of Tricoordinated Phosphorus 1018
42.18.1.5.2 Variation 2: Insertion into the P--H Bond of Hydrophosphoranes 1019
42.19 Product Class 19: Hexacoordinated Phosphates 1024
42.19.1 Product Subclass 1: Anionic Hexacoordinated Phosphorus Derivatives with P--O Bonds Only 1025
42.19.1.1 Synthesis of Product Subclass 1 1025
42.19.1.1.1 Method 1: Direct Synthesis from Phosphorus Pentachloride 1025
42.19.1.1.2 Method 2: Stepwise Synthesis from Phosphorus(III) Compounds 1027
42.19.1.1.2.1 Variation 1: From Phosphites 1028
42.19.1.1.2.2 Variation 2: From Phosphorous Triamides 1029
42.19.2 Product Subclass 2: Anionic Hexacoordinated Phosphorus Derivatives with P--O and P--C Bonds 1033
42.19.2.1 Synthesis of Product Subclass 2 1033
42.19.2.1.1 Method 1: Stepwise Synthesis from Phosphorus(V) Adducts 1033
42.19.2.1.2 Method 2: Direct Oxidation of Phosphorus(III) Adducts 1035
Keyword Index 1040
Author Index 1096
Abbreviations 1168

Erscheint lt. Verlag	14.5.2014
Reihe/Serie	Science of Synthesis
Reihe/Serie	Science of Synthesis
Verlagsort	Stuttgart
Sprache	englisch
Themenwelt	Naturwissenschaften ► Chemie ► Organische Chemie
Themenwelt	Technik
Schlagworte	Chemie • Chemische Synthese • chemistry of organic compound • chemistry organic reaction • chemistry reference work • C HEMISTRY REFERENCE WORK • chemistry synthetic methods • compound functional group • compound organic synthesis • compounds • Mechanism • methods in organic synthesis • methods peptide synthesis • one saturated carbon-heteroatom bond • Organic Chemistry • organic chemistry functional groups • organic chemistry reactions • organic chemistry review • organic chemistry synthesis • ORGANIC CHEM ISTRY SYNTHESIS • organic method • organic reaction • organic reaction mechanism • ORGANI C REACTION MECHANISM • Organic Syntheses • organic synthesis • organic synthesis reference work • Organisch-chemische Synthese • Organische Chemie • organophosphorus • ORGANOPHOS PHORUS • organophosphorus chemistry • Peptide synthesis • phosphorus • Practical • practical organic chemistry • Reactions • reference work • Review • review organic synthesis • review synthetic methods • REVIEW SYNTHE TIC METHODS • Synthese • Synthetic chemistry • Synthetic Methods • Synthetic Organic Chemistry • synthetic transformation
ISBN-10	3-13-172211-8 / 3131722118
ISBN-13	978-3-13-172211-9 / 9783131722119

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