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		350
10.3.1 Nucleophilic Additions and Substitutions		351
10.3.1.1 Alkylations		351
10.3.1.2 Mitsunobu Reactions		352
10.3.1.3 Lactonization and Lactamization		354
10.3.2 Base- or Acid-Promoted Condensations		355
10.3.3 Nucleophilic Aromatic Substitutions		355
10.3.4 Palladium-Mediated Reactions		356
10.3.5 Ring-Closing Metatheses		358
10.3.6 Staudinger–aza-Wittig Reactions		358
10.3.7 Cycloadditions		359
10.4 The Bifunctional Approach (BIFA)		361
10.4.1 Applications of Amino Acids		363
10.4.2 Applications of Cyclic Imines		365
10.4.3 Applications of Tethered Aldehyde and Keto Acids		366
10.4.4 Heterocyclic Amidines as a Tethered Ugi Input		371
10.4.5 Combined Bifunctional and Post-Condensation Modifi cations		372
Acknowledgments		375
Abbreviations		375
References		376
X Contents
11 Synthesis of Pyrroles and Their Derivatives from Isocyanides		385
Noboru Ono and Tetsuo Okujima
11.1 Introduction		385
11.2 Synthesis of Pyrroles Using TosMIC		386
11.3 Synthesis of Pyrroles Using Isocyanoacetates		391
11.3.1 Synthesis from Nitroalkenes		391
11.3.2 Synthesis from α,β-Unsaturated Sulfones		396
11.3.3 Synthesis from Alkynes		401
11.3.4 Synthesis from Aromatic Nitro Compounds: Isoindole Derivatives		402
11.4 Synthesis of Porphyrins and Related Compounds		407
11.4.1 Tetramerization		407
11.4.2 Meso-Tetraarylporphyrins via the Lindsey Procedure		412
11.4.3 [3+2] and [2+2] Methods		414
11.4.4 Expanded, Contracted, and Isomeric Porphyrins		414
11.4.5 Functional Dyes from Pyrroles		420
11.5 Conclusion		423
References		424
12 Isocyanide-Based Multicomponent Reactions towards Benzodiazepines		431
Yijun Huang and Alexander Dцmling
12.1 Introduction		431
12.2 1,4-Benzodiazepine Scaffolds Assembled via IMCR Chemistry		433
12.2.1 Two-Ring Systems		433
12.2.2 Fused-Ring Systems		440
12.3 1,5-Benzodiazepine Scaffolds Assembled via IMCR Chemistry		443
12.4 Outlook		446
References		446
13 Applications of Isocyanides in the Synthesis of Heterocycles		451
Irini Akritopoulou-Zanze
13.1 Introduction		451
13.2 Furans		451
13.3 Pyrroles		453
13.4 Oxazoles		459
13.5 Isoxazoles		461
13.6 Thiazoles		464
13.7 Imidazoles		466
13.8 Pyrazoles		466
13.9 Oxadiazoles and Triazoles		470
13.10 Tetrazoles		471
13.11 Benzofurans and Benzimidazoles		473
13.12 Indoles		473
13.13 Quinolines		477
Contents XI
13.14 Quinoxaline		479
Abbreviations		480
References		480
14 Renaissance of Isocyanoarenes as Ligands in Low-Valent Organometallics		493
Mikhail V. Barybin, John J. Meyers, Jr, and Brad M. Neal
14.1 Historical Perspective		493
14.2 Isocyanidemetalates and Related Low-Valent Complexes		497
14.2.1 Introduction		497
14.2.2 Four-Coordinate Isocyanidemetalates and Redox-Related Complexes		497
14.2.3 Five-Coordinate Isocyanidemetalates		502
14.2.4 Six-Coordinate Isocyanidemetalates and Redox-Related Complexes		504
14.3 Coordination and Surface Chemistry of Nonbenzenoid Isocyanoarenes		508
14.3.1 Isocyanoazulenes		508
14.3.2 Organometallic η5-Isocyanocyclopentadienides		509
14.3.3 Homoleptic Complexes of Nonbenzenoid Isocyanoarenes		510
14.3.4 Bridging Nonbenzenoid Isocyanoarenes		514
14.3.5 Self-Assembled Monolayer Films of Nonbenzenoid Isocyano- and Diisocyanoarenes on Gold Surfaces		517
14.4 Conclusions and Outlook		521
Acknowledgments		522
References		523
15 Carbene Complexes Derived from Metal-Bound Isocyanides: Recent Advances		531
Konstantin V. Luzyanin and Armando J.L. Pombeiro
15.1 Introduction		531
15.2 Coupling of the Isocyanide Ligand with Simple Amines or Alcohols		532
15.3 Coupling of the Isocyanide Ligand with Functionalized Amines or Alcohols		537
15.4 Coupling of the Isocyanide Ligand with a Hydrazine or Hydrazone		537
15.5 Coupling of the Isocyanide Ligand with an Imine or Amidine		538
15.6 Intramolecular Cyclizations of Functionalized Isocyanide Ligands		540
15.7 Coupling of Isocyanides with Dipoles		543
15.8 Other Reactions		544
15.9 Final Remarks		546
Acknowledgments		546
References		547
XII Contents
16 Polyisocyanides		551
Niels Akeroyd, Roeland J.M. Nolte, and Alan E. Rowan
16.1 Introduction		551
16.1.1 Chiral Polymers		551
16.1.2 Polyisocyanides and Their Monomers		553
16.2 The Polymerization Mechanism		553
16.3 Conformation of the Polymeric Backbone		556
16.4 Polyisocyanopeptides		561
16.5 Polyisocyanides as Scaffolds for the Anchoring of Chromophoric Molecules		563
16.6 Functional Polyisocyanides		570
16.7 Conclusions and Outlook		575
References		576
Index		587

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Isocyanide ChemistryApplications in Synthesis and Material Science

Contents

Isocyanide Chemistry
Applications in Synthesis and Material Science