Science of Synthesis Knowledge Updates 2011 Vol. 1 (eBook)

Erick M. Carreira, Jozef Drabowicz, Kazuaki Ishihara, Jie Jack Li, Eric Jim Thomas (Herausgeber)

eBook Download: PDF

2014 | 1. Auflage
572 Seiten
Thieme (Verlag)
978-3-13-178711-8 (ISBN)

Infos

The Science of Synthesis Editorial Board,together with the volume editors and authors, is constantly reviewing the whole field of synthetic organic chemistry as presented in Science of Synthesis and evaluating significant developments in synthetic methodology. Four annual volumes updating content across all categories ensure that you always have access to state-of-the-art synthetic methodology.

Content of this volume: Dialkyl- and Diarylmagnesiums, 1H- and 2H-Indazoles, Quinolizinium Salts and Benzo Analogues, 1,2-Diselenins, 1,4-Diselenins, Pyrimidines, Acyclic Dialkyl Selenoxides and Derivatives.

Inhalt

Science of Synthesis: Knowledge Updates 2011/1 1
Title page 5
Imprint 7
Preface 8
Abstracts 10
Overview 14
Table of Contents 16
Volume 7: Compounds of Groups 13 and 2 (Al, Ga, In, Tl, Be ··· Ba) 34
7.6 Product Class 6: Magnesium Compounds 34
7.6.15 Product Subclass 15: Dialkyl- and Diarylmagnesiums 34
Synthesis of Product Subclass 15 34
7.6.15.1 Method 1: Disproportion of Grignard Reagents 34
7.6.15.1.1 Variation 1: Reaction of Magnesium Metal with 2-Chlorobutane 35
7.6.15.2 Method 2: Reaction of Grignard Reagents with Organolithium Reagents 35
7.6.15.2.1 Variation 1: Reaction of Activated Magnesium Halides with Organolithium Reagents 36
7.6.15.3 Method 3: Reaction of Diorganomercury(II) Compounds with Magnesium Metal 37
7.6.15.4 Method 4: Reaction of Alkenes and Activated Magnesium Hydride 37
7.6.15.5 Method 5: Reaction of 1,3-Dienes with Activated Magnesium Metal 38
Applications of Product Subclass 15 in Organic Synthesis 39
7.6.15.6 Method 6: Reactions of Organomagnesium Compounds 39
7.6.15.7 Method 7: Reactions Involving Diorganomagnesium Compounds Obtained from 1,3-Dienes 42
7.6.15.8 Method 8: Catalysts Derived from Diorganomagnesium Compounds 43
7.6.15.9 Method 9: Miscellaneous Reactions of Diorganomagnesium Compounds 44
Volume 12: Five-Membered Hetarenes with Two Nitrogen or Phosphorus Atoms 48
12.2 Product Class 2: 1H- and 2H-Indazoles 48
12.2.5 1H- and 2H-Indazoles 48
12.2.5.1 Synthesis by Ring-Closure Reactions 49
12.2.5.1.1 By Annulation to an Arene 49
12.2.5.1.1.1 By Formation of One N--N and One N--C Bond 49
12.2.5.1.1.1.1 Fragments N--Arene--C and N 49
12.2.5.1.1.1.1.1 Method 1: From 2-Alkylanilines by Diazotization or Nitrosation 49
12.2.5.1.1.1.1.2 Method 2: From 2-Acylnitroarenes 50
12.2.5.1.1.2 By Formation of Two N--C Bonds 51
12.2.5.1.1.2.1 Fragment Arene--C and N--N 51
12.2.5.1.1.2.1.1 Method 1: From 1-Acyl-2-haloarenes and Hydrazine 51
12.2.5.1.1.2.1.2 Method 2: From 1-Alkyl-2-haloarenes and Hydrazines 53
12.2.5.1.1.2.1.3 Method 3: From 2-Arylidenecyclohexanones and Hydrazines 54
12.2.5.1.1.2.1.4 Method 4: From 2-Acylcyclohexanones and Hydrazine 55
12.2.5.1.1.2.1.5 Method 5: From 2-Acylhydroxyarenes and Hydrazine 56
12.2.5.1.1.2.1.6 Method 6: From [2-(Halomethyl)aryl]zincs and Arenediazonium Salts 56
12.2.5.1.1.2.2 Fragments Arene and N--N--C 57
12.2.5.1.1.2.2.1 Method 1: From Benzyne and Diazo Compounds 57
12.2.5.1.1.2.2.1.1 Variation 1: Using Acyl Diazomethanes 58
12.2.5.1.1.2.2.1.2 Variation 2: Using (Trimethylsilyl)diazomethane 59
12.2.5.1.1.2.2.1.3 Variation 3: Using Sydnones 61
12.2.5.1.1.2.2.1.4 Variation 4: Using Azomethine Imides 61
12.2.5.1.1.2.2.2 Method 2: From Quinones and Arylhydrazones 62
12.2.5.1.1.2.2.3 Method 3: From Nitroarenes or Nitroalkenes and Hydrazones 63
12.2.5.1.1.3 By Formation of One N--C and One C--C Bond 63
12.2.5.1.1.3.1 Fragments N--N--Arene and C 63
12.2.5.1.1.3.1.1 Method 1: From Arylhydrazines and Acyl Derivatives 63
12.2.5.1.1.3.1.2 Method 2: From Arylhydrazones 65
12.2.5.1.1.3.1.3 Method 3: By Carbonylation 65
12.2.5.1.1.4 By Formation of One N--N Bond 65
12.2.5.1.1.4.1 Fragment N–Arene–C--N 65
12.2.5.1.1.4.1.1 Method 1: From 2-Acylamino- or 2-Acylazidoarenes 65
12.2.5.1.1.4.1.1.1 Variation 1: Using Oximes 65
12.2.5.1.1.4.1.1.2 Variation 2: From 2-Amino- and 2-Azidobenzamides 66
12.2.5.1.1.4.1.2 Method 2: From 1-Acyl-2-nitroarenes 67
12.2.5.1.1.4.1.2.1 Variation 1: From 2-Nitroiminoarenes 67
12.2.5.1.1.4.1.2.2 Variation 2: From 2-Nitrobenzamides 68
12.2.5.1.1.4.1.3 Method 3: From 1-(Aminomethyl)-2-nitroarenes 68
12.2.5.1.1.5 By Formation of One N--C Bond 70
12.2.5.1.1.5.1 Fragment N--N--Arene--C 70
12.2.5.1.1.5.1.1 Method 1: From (2-Alkynylphenyl)triazenes 70
12.2.5.1.1.5.1.2 Method 2: From Azoarenes 71
12.2.5.1.1.5.1.2.1 Variation 1: From 2-Diazenylbenzonitriles or (2-Ethynylphenyl)diazenes 71
12.2.5.1.1.5.1.2.2 Variation 2: From 2-Acyl-1-diazenylarenes or 2-(Phenyldiazenyl)benzhydrols 71
12.2.5.1.1.5.1.3 Method 3: From 2-Hydrazinobenzonitriles 72
12.2.5.1.1.5.2 Fragment N--N--C--Arene 72
12.2.5.1.1.5.2.1 Method 1: From (2-Halobenzyl)hydrazines and 2-Halobenzohydrazides 72
12.2.5.1.1.5.2.2 Method 2: From (2-Halobenzylidene)hydrazines 73
12.2.5.1.1.5.2.3 Method 3: From (2-Nitrobenzylidene)hydrazines 74
12.2.5.1.1.5.2.4 Method 4: From Benzophenone Hydrazones 75
12.2.5.1.1.6 By Formation of One C--C Bond 75
12.2.5.1.1.6.1 Fragment Arene--N--N--C 75
12.2.5.1.1.6.1.1 Method 1: From 2-Alkylidenehydrazinoarenes 75
12.2.5.1.2 By Annulation to the Heterocyclic Ring 76
12.2.5.1.2.1 By Formation of Two C--C Bonds 76
12.2.5.1.2.1.1 Fragments Pyrazole--C--C and C--C 76
12.2.5.1.2.1.1.1 Method 1: From 4-Styrylpyrazoles and Dienophiles 76
12.2.5.1.2.1.2 Fragments C--Pyrazole--C and C--C 76
12.2.5.1.2.1.2.1 Method 1: From Dihydropyrazol-3-ones and Dienophiles 76
12.2.5.1.2.1.2.2 Method 2: From Pyrazole-4,5-quinodimethane and Dienophiles 77
12.2.5.1.2.1.3 Fragments C--Pyrazole and C--C--C 78
12.2.5.1.2.1.3.1 Method 1: From 5-(Cyanomethyl)pyrazoles and a-Oxoketene Dithioacetals 78
12.2.5.1.2.2 By Formation of One C--C Bond 78
12.2.5.1.2.2.1 Fragment C--C--Pyrazole--C--C 78
12.2.5.1.2.2.1.1 Method 1: From 5-Phenyl-4-styryl-1H-pyrazoles or 1-(5-Phenyl-1H-pyrazol-4-yl)-2-phenylethanol 78
12.2.5.1.2.2.1.2 Method 2: From 3,4-Diethynyl-1H-pyrazoles 79
12.2.5.1.3 From Acyclic Reactants 79
12.2.5.1.3.1 Method 1: From Alkenylethynyl Carbenes 79
12.2.5.2 Synthesis By Ring Transformation 80
12.2.5.2.1 Formal Exchange of Ring Members with Retention of Ring Size 80
12.2.5.2.1.1 Method 1: Of a Five-Membered Heterocycle 80
12.2.5.2.2 Ring Contraction 82
12.2.5.2.2.1 Method 1: Of a Six-Membered Heterocycle 82
12.2.5.2.2.2 Method 2: Of a Seven-Membered Heterocycle 83
12.2.5.2.2.3 Method 3: Of a Seven-Membered Carbocycle 83
12.2.5.3 Aromatization 84
12.2.5.3.1 Method 1: Of a Six-Membered Carbocycle 84
12.2.5.4 Synthesis By Substituent Modification 85
12.2.5.4.1 Addition Reactions 85
12.2.5.4.1.1 Addition of Organic Groups 85
12.2.5.4.1.1.1 Method 1: Addition of Alkyl Groups 85
12.2.5.4.1.1.2 Method 2: Addition of a Ring System to the Heterocyclic Ring 85
12.2.5.4.1.2 Addition of Heteroatoms 86
12.2.5.4.1.2.1 Method 1: By Oxidation 86
12.2.5.4.1.2.2 Method 2: Reduction of the Heterocyclic Ring 87
12.2.5.4.2 Substitution of Existing Substituents 87
12.2.5.4.2.1 Of Hydrogen 87
12.2.5.4.2.1.1 Method 1: Metalation 87
12.2.5.4.2.1.1.1 Variation 1: Lithiation 87
12.2.5.4.2.1.1.2 Variation 2: Metalation by Transition Metals 88
12.2.5.4.2.1.2 Method 2: Halogenation 89
12.2.5.4.2.1.3 Method 3: Alkoxylation 90
12.2.5.4.2.1.4 Method 4: Alkylation 90
12.2.5.4.2.1.5 Method 5: Arylation 93
12.2.5.4.2.1.6 Method 6: Acylation 94
12.2.5.4.2.2 Of Heteroatoms 95
12.2.5.4.2.2.1 Method 1: Halogen–Metal Exchange 95
12.2.5.4.2.2.2 Method 2: Cross-Coupling Reactions of Haloindazoles 96
12.2.5.4.2.2.3 Method 3: Removal or Exchange of Silyl Groups 97
12.2.5.4.2.2.4 Method 4: Removal or Exchange of Alkoxy Groups 98
12.2.5.4.2.2.5 Method 5: Removal or Exchange of Amino or Nitro Groups 98
12.2.5.4.2.3 Of Carbon Functionalities 99
12.2.5.4.2.3.1 Method 1: Deacylation 99
12.2.5.4.2.3.2 Method 2: Decarboxylation 99
12.2.5.4.2.4 Modification of Substituents 100
12.2.5.4.2.4.1 Method 1: Modification of Carbonyl Groups 100
12.2.5.4.2.4.2 Method 2: Modification of Hydroxy Groups 100
12.2.5.4.2.4.3 Method 3: Modification of Nitro Groups 101
12.2.5.4.2.5 Rearrangement Reactions 101
12.2.5.4.2.5.1 Method 1: Rearrangement of 2H-Indazoles to 1H-Indazoles 101
12.2.5.4.2.5.2 Method 2: Rearrangement of Oxazino[3,2-b]indazoles by Nucleophilic Ring Opening 101
12.2.5.4.2.5.3 Method 3: Rearrangements of 3,4-Dihydropyrazino[1,2-b]indazol-2-ium 6-Oxides 102
Volume 15: Six-Membered Hetarenes with One Nitrogen or Phosphorus Atom 108
15.7 Product Class 7: Quinolizinium Salts and Benzo Analogues 108
15.7.5 Quinolizinium Salts and Benzo Analogues 108
15.7.5.1 Quinolizinium Salts 108
15.7.5.1.1 Synthesis by Ring-Closure Reactions 108
15.7.5.1.1.1 By Annulation to an Arene 108
15.7.5.1.1.1.1 By Formation of Two C--C Bonds 108
15.7.5.1.1.1.1.1 Method 1: Enyne–Allene Rearrangement of 1-[3-(2-Alkynylphenyl)prop-2-ynyl]pyridinium Derivatives 108
15.7.5.1.2 Aromatization 109
15.7.5.1.2.1 Method 1: Oxidation of 1,2-Dihydroquinolizinium Derivatives 109
15.7.5.1.3 Synthesis by Substituent Modification 112
15.7.5.1.3.1 Substitution of Existing Substituents 112
15.7.5.1.3.1.1 Of Heteroatoms 112
15.7.5.1.3.1.1.1 Method 1: Stille Coupling of Bromoquinolizinium Derivatives 112
15.7.5.1.3.1.1.2 Method 2: Suzuki–Miyaura Coupling of Bromoquinolizinium Derivatives 114
15.7.5.1.3.1.1.3 Method 3: Sonogashira Coupling of Bromoquinolizinium Derivatives 115
15.7.5.2 Benzo[b]quinolizinium Salts 117
15.7.5.2.1 Synthesis by Ring-Closure Reactions 117
15.7.5.2.1.1 By Annulation to an Arene 117
15.7.5.2.1.1.1 By Formation of One C--C Bond 117
15.7.5.2.1.1.1.1 Method 1: Cyclization of 1-Benzyl-2-(1-hydroxy-1-methoxymethyl)pyridinium Derivatives 117
15.7.5.2.2 Synthesis by Substituent Modification 118
15.7.5.2.2.1 Substitution of Existing Substituents 118
15.7.5.2.2.1.1 Of Heteroatoms 118
15.7.5.2.2.1.1.1 Method 1: Suzuki–Miyaura Coupling of Benzo[b]quinoliziniumboronic Acids 118
15.7.5.2.2.1.1.2 Method 2: Replacement of Halogen Atoms by Nucleophilic Substitution 119
15.7.5.3 Benzo[c]quinolizinium Salts 121
15.7.5.3.1 Synthesis by Ring-Closure Reactions 121
15.7.5.3.1.1 By Annulation to an Arene 121
15.7.5.3.1.1.1 By Formation of One N--C Bond 121
15.7.5.3.1.1.1.1 Method 1: Cyclization of 2-[2-(2-Halophenyl)vinyl]pyridine Derivatives 121
15.7.5.4 Benzo[a]quinolizinium Salts 123
15.7.5.4.1 Synthesis by Ring-Closure Reactions 123
15.7.5.4.1.1 By Annulation to an Arene 123
15.7.5.4.1.1.1 By Formation of One C--C Bond 123
15.7.5.4.1.1.1.1 Method 1: Ring-Closing Metathesis of 1-Vinyl-2-(2-vinylphenyl)pyridinium Derivatives 123
Volume 16: Six-Membered Hetarenes with Two Identical Heteroatoms 126
16.5 Product Class 5: 1,2-Diselenins 126
16.5.2 1,2-Diselenins 126
16.5.2.1 Synthesis by Ring-Closure Reactions 127
16.5.2.1.1 By Formation of One Se--Se and Two Se--C Bonds 127
16.5.2.1.1.1 Fragment C--C--C--C and Two Se Fragments 127
16.5.2.1.1.1.1 Method 1: Selenation of an Organolithium Compound with Elemental Selenium 127
16.5.2.1.1.1.2 Method 2: Selenium Transfer from Selenous Acid to Benzyl Halides Using Tin(II) Chloride and Copper(II) Chloride 127
16.5.2.1.1.1.3 Method 3: Synthesis from 1,4-Bis(2-haloaryl)- or 1,4-Bis(2-halohetaryl)buta-1,3-diynes via Triple Cyclization 128
16.6 Product Class 6: 1,4-Diselenins 132
16.6.4 1,4-Diselenins 132
16.6.4.1 Synthesis by Ring-Closure Reactions 132
16.6.4.1.1 By Formation of Two Se--C Bonds 132
16.6.4.1.1.1 Fragments Se--C--C--Se and C--C 132
16.6.4.1.1.1.1 Method 1: Thermolysis of (Z)-1,2-Bis(benzylselanyl)ethene 132
16.6.4.1.1.1.2 Method 2: Cyclization of 3,4-Disubstituted Cyclobutene-1,2-diones 133
16.6.4.1.1.2 Fragments C--C--Se and C--C--Se 133
16.6.4.1.1.2.1 Method 1: Thermolysis of Selenadiazoles 133
16.6.4.1.1.2.2 Method 2: Photolysis of Dibenzo[c,g][1,2,5,6]tetraselenocins 134
16.12 Product Class 12: Pyrimidines 136
16.12.1 Synthesis by Ring-Closure Reactions 144
16.12.1.1 By Formation of Four N--C Bonds and One C--C Bond 144
16.12.1.1.1 Fragments C--C, N, N, C, and C 144
16.12.1.1.1.1 Method 1: Reaction of Alkyl Ketones with Orthoformates and Ammonia 144
16.12.1.1.1.2 Method 2: Reaction of 1-(2-Oxoethyl)pyridinium Bromides with 4-Nitrobenzaldehyde and Ammonia 145
16.12.1.2 By Formation of Four N--C Bonds 145
16.12.1.2.1 Fragments C--C--C, N, N, and C 145
16.12.1.2.1.1 Method 1: Reaction of ß-Dicarbonyl Derivatives with Aldehydes and Ammonia 145
16.12.1.2.1.2 Method 2: Reaction of (Perfluoroalkyl)acetaldehydes with Ammonia and Aldehydes 146
16.12.1.2.1.3 Method 3: Reaction of ß-Dicarbonyl Derivatives with Ortho Esters 147
16.12.1.3 By Formation of Three N--C Bonds and One C--C Bond 148
16.12.1.3.1 Fragments N--C--C, N, C, C 148
16.12.1.3.1.1 Method 1: Reaction of Vinylamines with Orthoformates and Ammonia 148
16.12.1.3.2 Fragments N--C, C--C, N, and C 150
16.12.1.3.2.1 Method 1: Reaction of Aryl Methyl Ketones with Aryl Aldehydes, Aryl Cyanides, and Hydroxylamine 150
16.12.1.4 By Formation of Two N--C Bonds and Two C--C Bonds 150
16.12.1.4.1 Fragments N--C--N, C, C, and C 150
16.12.1.4.1.1 Method 1: One-Pot Reaction of Aryl Cyanides with Alkylphosphonates, Aromatic Aldehydes, and Amidines 150
16.12.1.5 By Formation of Three N--C Bonds 151
16.12.1.5.1 Fragments N--C--C--C, N, and C 151
16.12.1.5.1.1 Method 1: Reaction of 2-(Aminomethyl)acrylates with Formamide 151
16.12.1.5.2 Fragments C--C--C, N--C, and N 152
16.12.1.5.2.1 Method 1: Reaction of ß-Dicarbonyl Derivatives with Formamide 152
16.12.1.5.2.1.1 Variation 1: Reaction of 1,3-Diketones 152
16.12.1.5.2.1.2 Variation 2: Reaction of 4,4-Dimethoxybutan-2-one 153
16.12.1.5.2.1.3 Variation 3: Reaction of Malonaldehyde Diacetals 153
16.12.1.5.2.1.4 Variation 4: Reaction of 3-Heterosubstituted Propenals or Propenones 154
16.12.1.5.2.2 Method 2: Reaction of Malonyl Chlorides with Nitriles 155
16.12.1.5.2.3 Method 3: Reaction of ß-Diketones with Cyanamide 156
16.12.1.6 By Formation of Two N--C Bonds and One C--C Bond 157
16.12.1.6.1 Fragments N--C, N--C, and C--C 157
16.12.1.6.1.1 Method 1: Trimerization of Nitriles 157
16.12.1.6.1.2 Method 2: Reaction of Alkynes with Nitriles 158
16.12.1.6.1.3 Method 3: Reaction of Alkyne Precursors with Nitriles 160
16.12.1.6.1.3.1 Variation 1: Reaction of Carbonyl Compounds Activated with Trifluoromethanesulfonic Anhydride 160
16.12.1.6.1.3.2 Variation 2: Reaction of Ketimines 162
16.12.1.6.1.3.3 Variation 3: Reaction of Enol Trifluoromethanesulfonates 163
16.12.1.6.1.3.4 Variation 4: Reaction of Heterosubstituted Alkenes 163
16.12.1.6.1.3.5 Variation 5: Reaction of 1,1-Diethoxybut-2-ene 164
16.12.1.6.1.4 Method 4: Reaction of Diethyl Malonate with Trifluoroacetonitrile 165
16.12.1.6.1.5 Method 5: Reaction of C--H Acidic Compounds with Formamide and Equivalents 165
16.12.1.6.1.5.1 Variation 1: Reaction of Phenylacetonitrile 166
16.12.1.6.1.5.2 Variation 2: Reaction of Malononitrile and Dimethyl Malonate 166
16.12.1.6.1.5.3 Variation 3: Reaction of Ketones 167
16.12.1.6.1.6 Method 6: Reaction of Acetonitriles with Aryl Cyanates 168
16.12.1.6.2 Fragments N--C--C, N--C, and C 169
16.12.1.6.2.1 Method 1: Reaction of Acetonitriles with Phosgene 169
16.12.1.6.2.2 Method 2: Reaction of Acetonitriles with (Trichloromethyl)benzene 170
16.12.1.6.3 Fragments C--N--C, C--C, and N 170
16.12.1.6.3.1 Method 1: Reaction of Vinylamines with Benzoyl Isocyanate 170
16.12.1.6.4 Fragments N--C--N, C--C, and C 171
16.12.1.6.4.1 Method 1: Reaction of Cyanoacetates and Aromatic Aldehydes with Amidine Derivatives 171
16.12.1.6.4.1.1 Variation 1: Reaction with Guanidine 171
16.12.1.6.4.1.2 Variation 2: Reaction with a Polymer-Bound Thiouronium Salt 172
16.12.1.6.4.2 Method 2: Reaction of Malononitrile and Aromatic Aldehydes with Amidine Derivatives 173
16.12.1.6.4.3 Method 3: Reaction of Malononitrile with Carbon Disulfide, an S-Alkylisothiouronium Salt, and an Alkylating Agent 174
16.12.1.6.4.4 Method 4: Reaction of a Substituted Acetate with Ethyl Formate and Guanidine 174
16.12.1.6.4.5 Method 5: Reaction of Aryl Methyl Ketones with Benzaldehydes and Acetimidamide 175
16.12.1.6.4.6 Method 6: Reaction of Aroylacetonitriles with Guanidines and Activated Formates 176
16.12.1.6.4.7 Method 7: Reaction of Amidines with Alkynes and a One-Carbon Fragment 177
16.12.1.6.4.7.1 Variation 1: Reaction of tert-Butyl Isocyanide with Alkynes and Amidines 177
16.12.1.6.4.7.2 Variation 2: Reaction of Acid Chlorides with Alkynes and Amidines 178
16.12.1.6.4.7.3 Variation 3: Reaction of Hexacarbonylmolybdenum(0) with Alkynes, Amidines, and Iodobenzene 179
16.12.1.7 By Formation of Two N--C Bonds 179
16.12.1.7.1 Fragments N--C--C--C--N and C 179
16.12.1.7.1.1 Method 1: Reaction of Malonamides with Ethyl Formate 180
16.12.1.7.1.2 Method 2: Reaction of Amidinoacetamides with Formamide 180
16.12.1.7.1.3 Method 3: Reaction of Malonimidic Acid Esters with Acid Chlorides 181
16.12.1.7.1.4 Method 4: Reaction of Malonimidamides with Esters 182
16.12.1.7.1.5 Method 5: Reaction of 3-Aminoacrylamides with Acid Derivatives 182
16.12.1.7.1.6 Method 6: Reaction of 3-Amino-2-cyanoacrylamides with Anhydrides 183
16.12.1.7.1.7 Method 7: Reaction of 4-Amino-1-azabutadiene and Dimethylformamide 184
16.12.1.7.2 Fragments C--C--C--N--C and N 184
16.12.1.7.2.1 Method 1: Reaction of N-Acylacrylamides with Ammonia 184
16.12.1.7.2.2 Method 2: Reaction of N,2-Diacylvinylamines with Ammonia and Derivatives 185
16.12.1.7.2.2.1 Variation 1: Reaction with Ammonium Salts 186
16.12.1.7.2.2.2 Variation 2: Reaction with Formamide 186
16.12.1.7.2.2.3 Variation 3: Reaction with Urea 187
16.12.1.7.3 Fragments C--C--C--N and N--C 188
16.12.1.7.3.1 Method 1: Reaction of 3-Chloroacrylonitriles with Nitriles 188
16.12.1.7.3.2 Method 2: Reaction of 3,3-Bis(methylsulfanyl)acrylonitrile with Amides 189
16.12.1.7.3.3 Method 3: Reaction of 3-Aminoacrylates 190
16.12.1.7.3.3.1 Variation 1: With Amides 190
16.12.1.7.3.3.2 Variation 2: With Benzimidates 191
16.12.1.7.3.3.3 Variation 3: With Nitriles 191
16.12.1.7.3.4 Method 4: Reaction of 3-Aminoprop-2-en-1-ones with Nitriles 191
16.12.1.7.3.5 Method 5: Reaction of 1,3-Diketimines with Benzonitrile 192
16.12.1.7.3.6 Method 6: Reaction of 3-Aminopropenals with Formamide 193
16.12.1.7.3.7 Method 7: Reaction of 3-Aminoacrylonitriles with Nitriles 194
16.12.1.7.4 Fragments N--C--N and C--C--C 194
16.12.1.7.4.1 Method 1: Reaction of Vinamidinium Salts with Amidine Derivatives 194
16.12.1.7.4.2 Method 2: Reaction of Malonates with Amidine Derivatives 196
16.12.1.7.4.3 Method 3: Reaction of Cyanoacetates (a-Cyanocarboxylates) with Amidine Derivatives 197
16.12.1.7.4.4 Method 4: Reaction of 3,3-Diheterosubstituted Acrylates with Amidine Derivatives 198
16.12.1.7.4.4.1 Variation 1: Reaction of 3,3-Dialkoxyacrylates with Amidine Derivatives 198
16.12.1.7.4.4.2 Variation 2: Reaction of 3,3-Bis(methylsulfanyl)acrylates with Amidine Derivatives 198
16.12.1.7.4.4.3 Variation 3: Reaction of 3-Amino-3-(methylsulfanyl)acrylates with Guanidine or Thiourea 199
16.12.1.7.4.5 Method 5: Reaction of a-Formyl Esters or Equivalents with Amidine Derivatives 199
16.12.1.7.4.6 Method 6: Reaction of ß-Oxo Esters with Amidine Derivatives 201
16.12.1.7.4.7 Method 7: Reaction of 3-Heterosubstituted Acrylates with Amidine Derivatives 204
16.12.1.7.4.8 Method 8: Reaction of Alkynyl or Allenyl Esters with Amidine Derivatives 207
16.12.1.7.4.9 Method 9: Reaction of 3-Unsubstituted, 3-Alkyl-, and 3-Arylacrylates with Amidine Derivatives 208
16.12.1.7.4.10 Method 10: Reaction of Malononitriles with Amidine Derivatives 209
16.12.1.7.4.11 Method 11: Reaction of 3,3-Diheterosubstituted Acrylonitriles with Amidine Derivatives 210
16.12.1.7.4.11.1 Variation 1: Reaction of 3,3-Dialkoxyacrylonitriles 210
16.12.1.7.4.11.2 Variation 2: Reaction of 3,3-Bis(methylsulfanyl)acrylonitriles 211
16.12.1.7.4.12 Method 12: Reaction of 3-Heterosubstituted Acrylonitriles with Amidine Derivatives 212
16.12.1.7.4.12.1 Variation 1: Reaction of 3-Haloacrylonitriles 213
16.12.1.7.4.12.2 Variation 2: Reaction of 3-Alkoxyacrylonitriles 213
16.12.1.7.4.12.3 Variation 3: Reaction of 3-(Methylsulfanyl)acrylonitriles 215
16.12.1.7.4.12.4 Variation 4: Reaction of 3-Aminoacrylonitriles 216
16.12.1.7.4.13 Method 13: Reaction of Propynenitriles or Buta-2,3-dienenitriles with Amidine Derivatives 217
16.12.1.7.4.14 Method 14: Reaction of 3-Arylacrylonitriles with Amidine Derivatives 218
16.12.1.7.4.15 Method 15: Reaction of ß-Dialdehydes or Equivalents with Amidine Derivatives 220
16.12.1.7.4.15.1 Variation 1: Reaction of Malonaldehydes 220
16.12.1.7.4.15.2 Variation 2: Reaction of Sodium 3,3-Dimethoxy-2-(methoxycarbonyl)prop-1-en-1-olate 221
16.12.1.7.4.15.3 Variation 3: Reaction of Malonaldehyde Diacetals 221
16.12.1.7.4.15.4 Variation 4: Reaction of 3-Heterosubstituted Propenals 223
16.12.1.7.4.16 Method 16: Reaction of ß-Diketones with Amidine Derivatives 226
16.12.1.7.4.16.1 Variation 1: Reaction with Guanidines 226
16.12.1.7.4.16.2 Variation 2: Reaction with O-Methyluronium Salts 228
16.12.1.7.4.16.3 Variation 3: Reaction with Urea or Thiourea 228
16.12.1.7.4.16.4 Variation 4: Reaction with Arylamidines 229
16.12.1.7.4.17 Method 17: Reaction of 3,3-Dialkoxypropan-1-ones with Amidine Derivatives 230
16.12.1.7.4.18 Method 18: Reaction of 3,3-Diheterosubstituted Prop-2-en-1-ones with Amidine Derivatives 231
16.12.1.7.4.18.1 Variation 1: Reaction of 3,3-Dialkoxyprop-2-en-1-ones 231
16.12.1.7.4.18.2 Variation 2: Reaction of 3,3-Disulfanylprop-2-en-1-ones or 3-Amino-3-sulfanylprop-2-en-1-ones 231
16.12.1.7.4.18.3 Variation 3: Reaction of 3,3-Diaminoprop-2-en-1-ones 234
16.12.1.7.4.19 Method 19: Reaction of 3-Heterosubstituted Prop-2-en-1-ones with Amidine Derivatives 234
16.12.1.7.4.19.1 Variation 1: Reaction of 3-Haloprop-2-en-1-ones 234
16.12.1.7.4.19.2 Variation 2: Reaction of 3-Alkoxyprop-2-en-1-ones 235
16.12.1.7.4.19.3 Variation 3: Reaction of 3-Sulfanylprop-2-en-1-ones 238
16.12.1.7.4.19.4 Variation 4: Reaction of 3-Aminoprop-2-en-1-ones 238
16.12.1.7.4.20 Method 20: Reaction of Prop-2-yn-1-ones with Amidine Derivatives 240
16.12.1.7.4.21 Method 21: Reaction of 3-Arylprop-2-en-1-ones with Amidine Derivatives 243
16.12.1.7.4.22 Method 22: Reaction of 1-Amino-1-(benzotriazol-1-yl)-3,4,4-trichloro-2-nitrobuta-1,3-dienes with Amidine Derivatives 246
16.12.1.7.4.23 Method 23: Pyrimidines by Solid-Phase Synthesis 246
16.12.1.7.4.23.1 Variation 1: Reactions of Polymer-Supported Three-Carbon Fragments 246
16.12.1.7.4.23.2 Variation 2: Reactions of Polymer-Supported Amidine Derivatives 252
16.12.1.8 By Formation of One N--C and One C--C Bond 254
16.12.1.8.1 Fragments N--C--N--C--C and C 254
16.12.1.8.1.1 Method 1: Reaction of N-[2-(3-Methylisoxazol-5-yl)vinyl]amidines with Dimethylformamide Acetals 254
16.12.1.8.2 Fragments N--C--N--C and C--C 255
16.12.1.8.2.1 Method 1: Reaction of 3-Cyano-2-methylisothiourea or 2-Cyanoguanidines with Ketones 255
16.12.1.8.2.2 Method 2: Reaction of 1,3-Diazabuta-1,3-dienes with Alkynes 255
16.12.1.8.2.2.1 Variation 1: Reaction of 4,4-Bis(methylsulfanyl)-2-phenyl-1,3-diazabuta-1,3-diene 256
16.12.1.8.2.2.2 Variation 2: Reaction of 4-(Dimethylamino)-1,3-diazabuta-1,3-dienes 256
16.12.1.8.2.3 Method 3: Reaction of 4-(Dimethylamino)-2-(methylsulfanyl)-1,3-diazabuta-1,3-diene with Ketenes 257
16.12.1.8.3 Fragments C--C--N--C and N--C 258
16.12.1.8.3.1 Method 1: Reaction of Azapropenylium Perchlorates with 1,1,3,3-Tetramethylguanidine 258
16.12.1.8.3.2 Method 2: Reaction of 2-Azabuta-1,3-dienes with Nitriles 259
16.12.1.8.3.3 Method 3: Reaction of N-Vinylamides with Nitriles 261
16.12.1.8.3.4 Method 4: Reaction of Ethyl (Cyanoacetyl)carbamate with Trifluoroacetonitrile 262
16.12.1.8.3.5 Method 5: Dimerization of N-Cyanothioacetimidates 263
16.12.1.8.4 Fragments N--C--C and C--N--C 263
16.12.1.8.4.1 Method 1: Reaction of Acetonitriles with N-(Dichloromethylene)trichloromethanamine 263
16.12.1.8.4.2 Method 2: Reaction of Cyanothioacetamide with Benzoyl Isothiocyanate 264
16.12.1.8.4.3 Method 3: Reaction of Acetamides with N-Cyanoimidates or N-Acylimidates 264
16.12.1.8.4.4 Method 4: Reaction of Enamines with N-(Dichloromethylene)trichloromethanamine 266
16.12.1.8.4.5 Method 5: Reaction of Enamines with Acyl Isothiocyanates 267
16.12.1.8.4.6 Method 6: Reaction of Enamines with N-[Bis(methylsulfanyl)methylene]cyanamide 268
16.12.1.8.4.7 Method 7: Reaction of a-Halo Oxime Derivatives with Grignard Reagents 268
16.12.1.9 By Formation of One N--C Bond 270
16.12.1.9.1 Fragment N--C--C--C--N--C 270
16.12.1.9.1.1 Method 1: Cyclization of 3-(Acylamino)but-2-enamides 270
16.12.1.9.1.2 Method 2: Cyclization of 3-Amino-N-acylthioacrylamides 270
16.12.1.9.1.3 Method 3: Cyclization of 3-Amino-N-cyano-3-methoxyacrylimidate 271
16.12.1.9.1.4 Method 4: Cyclization of 3-(Acylamino)-2-cyanoacrylates and 2-Cyano-3-(thioacylamino)acrylates 272
16.12.1.9.1.5 Method 5: Cyclization of N-(2-Cyanovinyl)amidines 275
16.12.1.9.1.6 Method 6: Cyclization of 1-(Dimethylamino)-5-(dimethylimino)-2-azapenta-1,3-dienes 275
16.12.1.9.1.7 Method 7: Cyclization of 3-(Vinylamino)but-2-enamides 276
16.12.1.9.2 Fragment N--C--N--C--C--C 276
16.12.1.9.2.1 Method 1: Cyclization of N-(3-Substituted Acryloyl)ureas 276
16.12.1.9.2.2 Method 2: Cyclization of 3-Ureidoacrylates 278
16.12.1.9.2.3 Method 3: Cyclization of N-[2-(Methoxycarbonyl)ethylidene]ureas 280
16.12.1.9.2.4 Method 4: Cyclization of 3-Ureidoacrylonitriles 281
16.12.1.9.2.5 Method 5: Cyclization of N-(2-Cyanovinyl)imidamides 282
16.12.1.9.2.6 Method 6: Cyclization of 1-(Cyanoacetyl)-2-methylisoureas 283
16.12.1.9.2.7 Method 7: Cyclization of 3-(Cyanoamino)acrylonitriles 284
16.12.1.9.2.8 Method 8: Cyclization of (Cyanoacetyl)cyanamides and Equivalents 284
16.12.1.10 By Formation of One C--C Bond 287
16.12.1.10.1 Fragment C--C--N--C--N--C 287
16.12.1.10.1.1 Method 1: Cyclization of 1-Acetyl-3-cyanourea 288
16.12.1.10.1.2 Method 2: Cyclization of N2-Carbamoyl-N1-vinylbenzimidamides 288
16.12.2 Synthesis by Ring Transformation 289
16.12.2.1 By Ring Enlargement 289
16.12.2.1.1 Of Three-Membered Carbocycles 289
16.12.2.1.1.1 Method 1: Reaction of Cyclopropenones with Amidoximes 289
16.12.2.1.2 Of Four-Membered Heterocycles 290
16.12.2.1.2.1 Method 1: Reaction of Azetes with Nitriles 290
16.12.2.1.2.2 Method 2: Reaction of Azetidinones with Imidates 290
16.12.2.1.3 Of Five-Membered Heterocycles 291
16.12.2.1.3.1 Method 1: Reaction of Furans 291
16.12.2.1.3.2 Method 2: Reaction of 3-Acyl-2-oxotetrahydrothiophene with Amidine Derivatives 293
16.12.2.1.3.3 Method 3: Reaction of 2,3,4,5-Tetraphenylpyrrole with Sulfenamides 294
16.12.2.1.3.4 Method 4: Reaction of Isoxazoles 295
16.12.2.1.3.4.1 Variation 1: Rearrangement of 5-(Acylamino)isoxazoles 295
16.12.2.1.3.4.2 Variation 2: Rearrangement of N-(Isoxazol-4-ylcarbonyl)ureas and N1-(Isoxazol-4-ylcarbonyl)benzimidamides 296
16.12.2.1.3.5 Method 5: Reaction of Oxazoles 297
16.12.2.1.3.6 Method 6: Reaction of Pyrazoles 298
16.12.2.1.3.7 Method 7: Reaction of Imidazoles 299
16.12.2.1.3.7.1 Variation 1: Reaction with Chloroform 299
16.12.2.1.3.7.2 Variation 2: Rearrangement of 1-Benzoyldihydroimidazoles 300
16.12.2.1.3.7.3 Variation 3: Rearrangement of 4-(Chloromethyl)dihydroimidazoles 300
16.12.2.1.3.7.4 Variation 4: Rearrangement of Methyleneimidazolidin-4-ones 302
16.12.2.1.3.7.5 Variation 5: Reaction with Acetylenes 302
16.12.2.1.3.7.6 Variation 6: Reaction with Phenylmalonaldehyde 303
16.12.2.1.3.8 Method 8: Reaction of 1,2,4-Oxadiazoles 304
16.12.2.1.3.8.1 Variation 1: Hydrogenation of 3-[(3-Oxoprop-1-enyl)amino)]-1,2,4-oxadiazoles 304
16.12.2.1.3.8.2 Variation 2: Reaction of 3-Amino-5-methyl-1,2,4-oxadiazole with ß-Diketones 304
16.12.2.1.3.9 Method 9: Reaction of 1,2,4-Dithiazolium Salts with Nitrogen-Containing Derivatives of Carboxylic Acids 305
16.12.2.2 Formal Exchange of Ring Members with Retention of the Ring Size 306
16.12.2.2.1 Method 1: Reaction of Pyran-2-ones with Amidine Derivatives 307
16.12.2.2.1.1 Variation 1: Use of Two-Carbon Ring Fragments 307
16.12.2.2.1.2 Variation 2: Use of Three-Carbon Ring Fragments 309
16.12.2.2.2 Method 2: Reaction of Pyran-4-ones with Amidine Derivatives 310
16.12.2.2.3 Method 3: Reaction of 1,3-Oxazines 314
16.12.2.2.3.1 Variation 1: Reaction of 1,3-Oxazin-4-ones with Ammonia 314
16.12.2.2.3.2 Variation 2: Rearrangement of 2-Amino-1,3-oxazin-4-ones 315
16.12.2.2.3.3 Variation 3: Reaction of 1,3-Oxazin-4-ones with Thioamides 315
16.12.2.2.3.4 Variation 4: Reaction of 1,3-Oxazin-6-ones with Ammonia 316
16.12.2.2.3.5 Variation 5: Rearrangement of 1,3-Oxazine-5-carboxamides 317
16.12.2.2.3.6 Variation 6: Reaction of 1,3-Oxazinium Perchlorates with Ammonia 317
16.12.2.2.4 Method 4: Reaction of 1,3-Thiazinones or 1,4-Benzothiazines 318
16.12.2.2.5 Method 5: Reaction of Pyrimidinones and Pyrimidinecarboxylates 320
16.12.2.2.6 Method 6: Ring Opening of Polycycles with Retention of the Pyrimidine Ring 321
16.12.2.2.7 Method 7: Rearrangement of 1,2,4-Oxadiazines 323
16.12.2.2.8 Method 8: Reaction of 1,3,5-Oxadiazinium or 1,3,5-Thiadiazinium Salts with Active Methylene Compounds 323
16.12.2.2.9 Method 9: Reaction of 1,2,4-Triazines with N,N-Diethylprop-1-ynamine 325
16.12.2.2.10 Method 10: Reaction of 1,3,5-Triazines 326
16.12.2.2.10.1 Variation 1: Reaction of 1,3,5-Triazines with Dienophiles 326
16.12.2.2.10.2 Variation 2: Reaction of 1,3,5-Triazines with Active Methylene Compounds 329
16.12.2.2.10.3 Variation 3: Rearrangement of 2-(Acylmethyl)-1,3,5-triazines 330
16.12.2.2.10.4 Variation 4: Thermolysis of 2-Alkyl-1,2-dihydro-1,3,5-triazines 331
16.12.2.2.10.5 Variation 5: Reaction of 1,3,5-Triazinediones 331
16.12.2.2.11 Method 11: Reaction of 1,2,3,5-Oxathiadiazine 2,2-Dioxides with Active Methylene Compounds 332
16.12.2.3 By Ring Contraction 333
16.12.2.3.1 Method 1: Ring Contraction of 1,4-Diazepines 333
16.12.3 Aromatization 333
16.12.3.1 By Oxidation 333
16.12.3.1.1 Method 1: Dehydrogenation of Dihydropyrimidines 333
16.12.3.1.2 Method 2: Dehydrogenation of Tetrahydropyrimidines 335
16.12.3.1.3 Method 3: Pyrimidinones by Dehydrogenation 336
16.12.3.1.4 Method 4: Oxidation of 6-Methyl-3,4-dihydropyrimidin-2(1H)-ones 339
16.12.3.2 By Elimination 340
16.12.3.2.1 Method 1: Acid-Catalyzed Elimination of Water 340
16.12.3.2.2 Method 2: Base-Catalyzed Elimination of HX 341
16.12.4 Synthesis by Substituent Modification 343
16.12.4.1 Substitution of Existing Substituents 343
16.12.4.1.1 Of Hydrogen 343
16.12.4.1.1.1 Method 1: Hydrogen/Deuterium Exchange 343
16.12.4.1.1.2 Method 2: Metalation 344
16.12.4.1.1.3 Method 3: Silylation 349
16.12.4.1.1.4 Method 4: C-Acylation 350
16.12.4.1.1.4.1 Variation 1: Formylation 350
16.12.4.1.1.4.2 Variation 2: Acylation by Radicals 351
16.12.4.1.1.4.3 Variation 3: Carboxylation 352
16.12.4.1.1.4.4 Variation 4: Carbamoylation 353
16.12.4.1.1.5 Method 5: Cyanation 354
16.12.4.1.1.6 Method 6: Hydroxyalkylation and Related Reactions 355
16.12.4.1.1.7 Method 7: C-Alkylation 356
16.12.4.1.1.8 Method 8: C-Arylation 360
16.12.4.1.1.9 Method 9: Halogenation 364
16.12.4.1.1.10 Method 10: Hydroxylation 367
16.12.4.1.1.11 Method 11: Nitration 368
16.12.4.1.1.12 Method 12: Nitrosation 369
16.12.4.1.1.13 Method 13: Amination 370
16.12.4.1.2 Of Metals 373
16.12.4.1.2.1 Method 1: Reaction of (Trialkylstannyl)pyrimidines with Aryl Halides or Acid Chlorides 373
16.12.4.1.2.2 Method 2: Reaction of Pyrimidin-5-ylboronic Acids or (Pyrimidin-5-yl)trifluoroborates with Hetaryl Halides 376
16.12.4.1.3 Of Carbon Functionalities 380
16.12.4.1.3.1 Method 1: Decarboxylation 380
16.12.4.1.3.2 Method 2: N-Deacylation 381
16.12.4.1.3.3 Method 3: N-Dealkylation 382
16.12.4.1.3.4 Method 4: Removal of Protecting Groups 382
16.12.4.1.3.4.1 Variation 1: Benzyloxymethyl Group 382
16.12.4.1.3.4.2 Variation 2: Cyanoethyl Group 383
16.12.4.1.3.4.3 Variation 3: Benzyl Group 384
16.12.4.1.3.5 Method 5: Conversion of Pyrimidine-5-carbaldehydes into 5-Hydroxypyrimidines 385
16.12.4.1.4 Of Heteroatoms 385
16.12.4.1.4.1 Dehalogenation 385
16.12.4.1.4.1.1 Method 1: Dehalogenation with Palladium on Carbon 386
16.12.4.1.4.1.2 Method 2: Dechlorination by Zinc Dust 387
16.12.4.1.4.1.3 Method 3: Dechlorination of 3-Chloropyrimidines with Tosylhydrazine 389
16.12.4.1.4.2 Halogen–Metal Exchange Reactions 389
16.12.4.1.4.2.1 Method 1: Formation of Stannylpyrimidines 389
16.12.4.1.4.2.2 Method 2: Formation of Pyrimidinylboronic Acids 391
16.12.4.1.4.2.3 Method 3: Formation of Pyrimidinylzinc Halides 391
16.12.4.1.4.2.4 Method 4: Formation of Pyrimidinylmagnesium Halides 393
16.12.4.1.4.3 Substitution of Halogens by Carbofunctional Groups 393
16.12.4.1.4.3.1 Method 1: Reaction with Carbonyl Compounds via Lithiated Intermediates 394
16.12.4.1.4.3.2 Method 2: Palladium-Catalyzed Cross Coupling with Alkenes or Alkynes (Heck-Type Reactions) 396
16.12.4.1.4.3.2.1 Variation 1: Coupling with Alkenes 396
16.12.4.1.4.3.2.2 Variation 2: Coupling with Alkynes (Sonogashira Coupling) 399
16.12.4.1.4.3.3 Method 3: Palladium-Catalyzed Cross Coupling with Organostannanes (Stille Reaction) 404
16.12.4.1.4.3.4 Method 4: Palladium-Catalyzed Cross Coupling with Organozinc Reagents (Negishi Coupling) 406
16.12.4.1.4.3.5 Method 5: Reaction with Arylboronic Acids (Suzuki and Suzuki–Miyaura Coupling) 409
16.12.4.1.4.3.6 Method 6: Reaction with Aryl- or Alkyltrifluoroborates 414
16.12.4.1.4.3.7 Method 7: Reaction with Triaryl- or Trialkynylindiums 416
16.12.4.1.4.3.8 Method 8: Reaction with Grignard Reagents (Kumada Cross Coupling) 417
16.12.4.1.4.3.9 Method 9: Reaction with Active Methylene Compounds 419
16.12.4.1.4.3.10 Method 10: Cyanation 421
16.12.4.1.4.3.11 Method 11: Other Substitution Reactions 423
16.12.4.1.4.4 Halogen-Exchange Reactions 425
16.12.4.1.4.4.1 Method 1: Exchange of Chlorine for Fluorine 425
16.12.4.1.4.4.2 Method 2: Exchange of Chlorine for Iodine 427
16.12.4.1.4.5 Substitution of Halogen by Oxygen Functions 429
16.12.4.1.4.5.1 Method 1: Hydrolysis of Halopyrimidines 429
16.12.4.1.4.5.2 Method 2: Exchange of Halogen for Alkoxides 430
16.12.4.1.4.6 Substitution of Halogen by Sulfur Functionalities 434
16.12.4.1.4.6.1 Method 1: Conversion of Halopyrimidines into Thiols 434
16.12.4.1.4.6.2 Method 2: Reaction of Halopyrimidines with Thiolates 436
16.12.4.1.4.7 Substitution of Halogens by Nitrogen Functionalities 439
16.12.4.1.4.7.1 Method 1: Substitution of Halogens by Ammonia 439
16.12.4.1.4.7.2 Method 2: Substitution of Halogens by Aliphatic Amines 441
16.12.4.1.4.7.3 Method 3: Substitution of Halogens by Aromatic Amines 445
16.12.4.1.4.7.4 Method 4: Substitution of Halogens by N-Heterocycles 449
16.12.4.1.4.7.5 Method 5: Substitution of Halogens by Sulfonamides 449
16.12.4.1.4.7.6 Method 6: Substitution of Halogens by Hydrazines 450
16.12.4.1.4.7.7 Method 7: Substitution of Halogens by Azide 451
16.12.4.1.4.8 Substitution of Oxygen Functions 452
16.12.4.1.4.8.1 Method 1: Exchange of Oxygen for a Carbofunctional Group 452
16.12.4.1.4.8.2 Method 2: Exchange of Hydroxy for Halogen 453
16.12.4.1.4.8.2.1 Variation 1: Introduction of Chlorine 453
16.12.4.1.4.8.2.2 Variation 2: Introduction of Bromine 456
16.12.4.1.4.8.3 Method 3: Exchange of Hydroxy for Alkoxy and Aryloxy 458
16.12.4.1.4.8.4 Method 4: Exchange of Oxygen for Sulfur 459
16.12.4.1.4.8.5 Method 5: Exchange of Hydroxy for Amino 460
16.12.4.1.4.9 Substitution of Sulfur Functions 462
16.12.4.1.4.9.1 Method 1: Desulfurization 463
16.12.4.1.4.9.1.1 Variation 1: Reduction with Raney Nickel 463
16.12.4.1.4.9.1.2 Variation 2: Detosylation 463
16.12.4.1.4.9.2 Method 2: Exchange for Carbofunctional Groups 464
16.12.4.1.4.9.3 Method 3: Exchange for Hydroxy and Alkoxy Groups 466
16.12.4.1.4.9.4 Method 4: Exchange for Amino Groups 468
16.12.4.1.4.10 Substitution of Amino Groups 470
16.12.4.1.4.10.1 Method 1: Conversion of Pyrimidin-2-amines into 2-Phenylpyrimidines 471
16.12.4.1.5 Solid-Phase Synthesis Based on Substitution Reactions 471
16.12.4.2 Addition Reactions 478
16.12.4.2.1 Addition of Organic Groups 478
16.12.4.2.1.1 Method 1: N-Alkylations 478
16.12.4.2.1.2 Method 2: C-Alkylations 479
16.12.4.2.2 Addition of Heteroatoms 480
16.12.4.2.2.1 Method 1: Generation of N-Oxides 480
16.12.4.3 Rearrangement of Substituents 483
16.12.4.3.1 Method 1: Dimroth Rearrangement 483
16.12.4.3.2 Method 2: Conversion of 3-Phenyl-2H-isoxazolo[2,3-a]pyrimidin-2-ones into 2-Benzoylpyrimidines 484
16.12.4.3.3 Method 3: Conversion of 3H-[1,2,4]Thiadiazolo[4,3-c]pyrimidin-3-ones into Pyrimidin-4-ylcarbamates 485
16.12.4.4 Modification of Substituents 486
16.12.4.4.1 Modification of Carbon Functions 486
16.12.4.4.1.1 Method 1: Modification of 5-(Ethoxymethyl)pyrimidines 486
16.12.4.4.1.2 Method 2: Conversion of Methyl into Pyrazol-4-yl 487
16.12.4.4.1.3 Method 3: Conversion of Ethynyl into Indol-3-yl 488
16.12.4.4.2 Modification of Oxygen Functions 488
16.12.4.4.2.1 Method 1: O-Alkylation and O-Arylation 488
16.12.4.4.2.2 Method 2: O-Acylation 490
16.12.4.4.2.3 Method 3: O-Silylation 492
16.12.4.4.2.4 Method 4: O-Sulfonation 492
16.12.4.4.3 Modification of Sulfur Functions 493
16.12.4.4.3.1 Method 1: S-Alkylation and S-Dealkylation 493
16.12.4.4.3.2 Method 2: S-Oxidation 494
16.12.4.4.4 Modification of Nitrogen Functions 496
16.12.4.4.4.1 Method 1: Reduction of Nitro and Nitroso Groups 496
16.12.4.4.4.2 Method 2: Arylation of Primary Amino Groups 497
Volume 39: Sulfur, Selenium, and Tellurium 526
39.17 Product Class 17: Acyclic Dialkyl Selenoxides and Derivatives 526
39.17.3 Acyclic Dialkyl Selenoxides and Derivatives 526
39.17.3.1 Applications of Acyclic Dialkylselenium Dihalides in Organic Synthesis 526
39.17.3.1.1 Utilization of Dialkylselenium Dihalides as Reagents 526
39.17.3.1.1.1 Method 1: Reduction of Tertiary Amides 526
39.17.3.1.1.2 Method 2: Reduction of Nitriles 527
39.17.3.1.1.3 Method 3: Transformation of Alcohols into the Corresponding Halides 528
39.17.3.1.1.4 Method 4: Transformation of Alcohols into Alkyl Chlorides 529
39.17.3.1.1.5 Method 5: Selenation of Metallocene-1,1'-dichalcogenols 530
39.17.3.1.2 Transformation of Dialkylselenium Dihalides 531
39.17.3.1.2.1 Method 1: Transformation into Dialkylselenium Diazides 531
39.17.3.1.2.2 Method 2: Dehalogenation into Selenides 531
39.17.3.1.2.3 Method 3: Migration of Chlorine 533
39.17.3.1.2.4 Method 4: Addition with Ring Opening of Tetrahydrofuran 534
Author Index 536
Abbreviations 570
List of All Volumes 576

Produkt-Details

• Erscheint lt. Verlag: 14.5.2014
• Reihe/Serie: Science of Synthesis
• Verlagsort: Stuttgart
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Organische Chemie
• Themenwelt: Technik
• Schlagworte: 1 • 1H-Indazoles • 1H-INDAZOLE S • 2-Diselenins • 2H-Indazoles • 4-Diselenins • Acyclic Dialkyl Selenoxides • Benzo Analogues • Chemie • Chemische Synthese • chemistry of organic compound • chemistry organic reaction • chemistry reference work • chemistry synthetic methods • compound functional group • compound organic synthesis • Dialkylmagnesiums • Diarylmagnesiums • Functional Group • Mechanism • Method • methods in organic synthesis • methods peptide synthesis • 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 • Peptide synthesis • Practical • practical organic chemistry • Pyrimidines • quinolizinium salts • Reaction • reference work • Review • review organic synthesis • review synthetic methods • REVIEW SYNTHE TIC METHODS • selenoxdies • Selenoxides • Synthese • Synthetic chemistry • Synthetic Methods • Synthetic Organic Chemistry • synthetic transformation
• ISBN-10: 3-13-178711-2 / 3131787112
• ISBN-13: 978-3-13-178711-8 / 9783131787118