Nenajdenko, V. (ed.) - Isocyanide Chemistry. Applications in Synthesis and Material Science - 2012 - ISBN 978-3-527-33043-0

Nenajdenko, V. (ed.)

Isocyanide Chemistry
Applications in Synthesis and Material Science

Wiley-VCH, 2012, ISBN 978-3-527-33043-0

Filling a gap in the literature, the highly experienced and internationally renowned editor has brought together an equally distinguished author team to cover the topic in unrivaled depth, presenting all aspects of synthetic isocyanide chemistry.

Contents
Preface		XIII
List of Contributors		XV
1 Chiral Nonracemic Isocyanides		1
Luca Banfi, Andrea Basso, and Renata Riva
1.1 Introduction		1
1.2 Simple Unfunctionalized Isocyanides		1
1.3 Isocyanides Containing Carboxylic, Sulfonyl, or Phosphonyl Groups		4
1.3.1 α-Isocyano Esters		4
1.3.2 α-Isocyano Amides		7
1.3.3 Other Isocyano Esters or Amides		9
1.3.4 Chiral Sulfonylmethyl or Phosphonylmethyl Isocyanides		10
1.4 Isocyanides Containing Amino or Alcoholic Functionalities		11
1.4.1 Chiral Amino or Azido Isocyanides		11
1.4.2 Chiral Hydroxy Isocyanides		12
1.5 Natural Isocyanides		16
1.5.1 Isolation and Natural Sources		16
1.5.2 Synthesis of Naturally Occurring Isocyanides		17
1.6 Isocyanides Used in the Synthesis of Chiral Polyisocyanides		23
1.6.1 Properties		24
1.6.2 Synthesis		25
1.6.3 Applications		26
References		26
2 General Aspects of Isocyanide Reactivity		35
Maxim A. Mironov
2.1 Introduction		35
2.2 Isocyanide-Cyanide Rearrangement		37
2.3 Oxidation/Reduction of the Isocyano Group		41
2.3.1 Oxidation of the Isocyano Group		41
2.3.2 Reactions with Sulfur and Selenium		43
VI Contents
2.3.3 Reduction of the Isocyano Group		45
2.4 Reactions of Isocyanides with Electrophiles		47
2.4.1 Reaction with Acids		49
2.4.2 Reactions with Halogens and Acyl Halides		52
2.4.3 Reactions with Activated Alkenes and Alkynes		55
2.4.4 Reactions with Carbonyl Compounds and Imines		58
2.4.5 Reactions with Activated Heterocumulens		60
2.5 Reactions of Isocyanides with Nucleophiles		62
2.5.1 Reactions with Organometallic Compounds		62
2.5.2 Reactions with Hydroxide, Alcohols, and Amines		64
2.6 Conclusions		66
References		67
3 α-Acidic Isocyanides in Multicomponent Chemistry		75
Niels Elders, Eelco Ruijter, Valentine G. Nenajdenko, and Romano V.A. Orru
3.1 Introduction		75
3.2 Synthesis of α-Acidic Isocyanides		76
3.3 Reactivity of α-Acidic Isocyanides		78
3.4 MCRs Involving α-Acidic Isocyanides		80
3.4.1 van Leusen Imidazole MCR		81
3.4.2 2,6,7-Trisubstituted Quinoxaline MCR		82
3.4.3 4,5-Disubstituted Oxazole MCR		83
3.4.4 Nitropyrrole MCR		83
3.4.5 2,4,5-Trisubstituted Oxazole MCR		84
3.4.5.1 2,4,5-Trisubstituted Oxazoles		84
3.4.5.2 Variations on the 2,4,5-Trisubstituted Oxazole MCR		86
3.4.5.3 Oxazole MCR and In-Situ Domino Processes		88
3.4.6 2-Imidazoline MCR		91
3.4.6.1 2-Imidazoline MCR in the Union of MCRs		93
3.4.7 Dihydropyridone MCR		95
3.5 Conclusions		97
References		98
4 Synthetic Application of Isocyanoacetic Acid Derivatives		109
Anton V. Gulevich, Alexander G. Zhdanko, Romano V.A. Orru, and Valentine G. Nenajdenko
4.1 Introduction		109
4.2 Synthesis of α-Isocyanoacetate Derivatives		109
4.3 Alkylation of Isocyanoacetic Acid Derivatives		113
4.4 α-Isocyanoacetates as Michael Donors		115
4.5 Reaction of Isocyanoacetic Acids with Alkynes: Synthesis of Pyrroles		119
4.6 Reaction of Isocyanoacetic Acid Derivatives with Carbonyl Compounds and Imines		121
4.6.1 Aldol-Type Reaction of Isocyanoacetic Acids with Aldehydes: Synthesis of Oxazolines		122
Contents VII
4.6.2 Transition Metal-Catalyzed Aldol-Type Reactions		124
4.6.3 Reaction of Isocyanoacetic Acids with Imines: Imidazoline Formation		126
4.7 Reaction with Acylating Agents		129
4.8 Multicomponent Reactions of Isocyanoacetic Acid Derivatives		133
4.9 Chemistry of Isocyanoacetates Bearing an Additional Functional Group		134
4.10 Reactions of Isocyanoacetic Acids with Sulfur Electrophiles		138
4.11 Miscellaneous Reactions		139
4.12 Concluding Remarks		144
4.13 Notes Added in Proof		145
References		145
5 Ugi and Passerini Reactions with Carboxylic Acid Surrogates		159
Laurent El Kaпm and Laurence Grimaud
5.1 Introduction		159
5.2 Carboxylic Acid Surrogates		160
5.2.1 Thiocarboxylic Acids		160
5.2.2 Carbonic Acid and Derivatives		163
5.2.3 Selenide and Sulfi de		165
5.2.4 Silanol		165
5.2.5 Isocyanic Acid and Derivatives		166
5.2.6 Hydrazoic Acid		167
5.2.7 Phenols and Derivatives		171
5.2.8 Cyanamide		179
5.3 Use of Mineral and Lewis Acids		180
5.3.1 Ugi and Passerini Reactions Triggered by Mineral Acids		181
5.3.2 Ugi and Passerini Reactions Triggered by Lewis Acids		184
5.4 Conclusions		189
References		189
6 Amine (Imine) Component Surrogates in the Ugi Reaction and Related Isocyanide-Based Multicomponent Reactions		195
Mikhail Krasavin
6.1 Introduction		195
6.2 Hydroxylamine Components in the Ugi Reaction		196
6.3 Hydrazine Components in the Ugi Reaction		200
6.4 Miscellaneous Amine Surrogates for the Ugi Reaction		218
6.5 Activated Azines in Reactions with Isocyanides		220
6.6 Enamines, Masked Imines, and Cyclic Imines in the
Ugi Reaction		223
6.7 Concluding Remarks		227
Acknowledgments		227
References		227
VIII Contents
7 Multiple Multicomponent Reactions with Isocyanides		233
Ludger A. Wessjohann, Ricardo A.W. Neves Filho, and Daniel G. Rivera
7.1 Introduction		233
7.2 One-Pot Multiple IMCRs		234
7.2.1 Synthesis of Multivalent Glycoconjugates		236
7.2.2 Synthesis of Hybrid Peptide-Peptoid Podands		237
7.2.3 Covalent Modifi cation and Immobilization of Proteins		240
7.2.4 Assembly of Polysaccharide Networks as Synthetic Hydrogels		241
7.2.5 Synthesis of Macromolecules by Multicomponent Polymerization		243
7.3 Isocyanide-Based Multiple Multicomponent Macrocyclizations		243
7.3.1 Synthesis of Hybrid Macrocycles by Double Ugi-4CR-Based Macrocyclizations		244
7.3.2 Synthesis of Macrobicycles by Threefold Ugi-4CR-Based Macrocyclization		246
7.4 Sequential Isocyanide-Based MCRs		248
7.4.1 Sequential Approaches to Linear and Branched Scaffolds		248
7.4.2 Sequential Approaches to Macrocycles		254
7.4.3 Convergent Approach to Natural Product Mimics		256
7.5 Conclusions		257
References		258
8 Zwitterions and Zwitterion-Trapping Agents in Isocyanide Chemistry		263
Ahmad Shaabani, Afshin Sarvary, and Ali Maleki
8.1 Introduction		263
8.2 Generation of Zwitterionic Species by the Addition of Isocyanides to Alkynes		265
8.2.1 CH-Acids as Zwitterion-Trapping Agents		266
8.2.2 NH-Acids as Zwitterion-Trapping Agents		271
8.2.3 OH-Acids as Zwitterion-Trapping Agents		273
8.2.4 Carbonyl Compounds as Zwitterion-Trapping Agents		275
8.2.5 Imine Compounds as Zwitterion-Trapping Agents		278
8.2.6 Electron-Defi cient Olefi ns as Zwitterion-Trapping Agents		279
8.2.7 Miscellaneous Compounds as Zwitterion-Trapping Agents		280
8.3 Generation of Zwitterionic Species by the Addition of Isocyanides to Arynes		283
8.4 Generation of Zwitterionic Species by the Addition of Isocyanides to Electron-Deficient Olefins		284
8.5 Miscellaneous Reports for the Generation of Zwitterionic Species		286
8.6 Isocyanides as Zwitterion-Trapping Agents		287
8.7 Conclusions		289
Acknowledgments		289
References		289
Contents IX
9 Recent Progress in Nonclassical Isocyanide-Based MCRs		299
Rosario Ramуn, Nicola Kielland, and Rodolfo Lavilla
9.1 Introduction		299
9.2 Type I MCRs: Isocyanide Attack on Activated Species		300
9.3 Type II MCRs: Isocyanide Activation		308
9.4 Type III MCRs: Formal Isocyanide Insertion Processes		320
9.5 Conclusions		327
Acknowledgments		327
References		327
10 Applications of Isocyanides in IMCRs for the Rapid Generation of Molecular Diversity		335
Muhammad Ayaz, Fabio De Moliner, Justin Dietrich, and Christopher Hulme
10.1 Introduction		335
10.2 Ugi/Deprotect/Cyclize (UDC) Methodology		337
10.2.1 Ugi-4CC: One Internal Nucleophile		337
10.2.2 TMSN3-Modifi ed Ugi-4CC: One Internal Nucleophile		343
10.2.3 Ugi-4CC: Two Internal Nucleophiles		344
10.2.4 Ugi-4CC: Three Internal Nucleophiles		347
10.2.5 Ugi-5CC: One Internal Nucleophile		348
10.3 Secondary Reactions of Ugi Products

Isocyanide ChemistryApplications in Synthesis and Material Science

Contents

Isocyanide Chemistry
Applications in Synthesis and Material Science