CATENANES, ROTAXANES, AND KNOTS
CONTENTS PART 1: SYNTHESIS AND SAFETY 1 LAB-SCALE SYNTHESIS OF AZIDO COMPOUNDS: SAFETY MEASURES AND ANALYSIS INTRODUCTION PROPERTIES THAT IMPOSE RESTRICTIONS ON LAB-SCALE HANDLING OF AZIDES HYDRAZOIC ACID AND ITS METAL SALTS ORGANIC AZIDES LABORATORY SAFETY INSTRUCTIONS FOR THE SMALL-SCALE SYNTHESIS OF AZIDO COMPOUNDS ANALYZING SAFETY-RELATED PROPERTIES OF AZIDES IMPACT SENSITIVITY TESTING FRICTION SENSITIVITY TESTING ESD TESTING THERMOANALYTICAL MEASUREMENTS CALORIMETRIC AND GRAVIMETRIC STABILITY TESTS KOENEN TEST REFERENCES 2 LARGE-SCALE PREPARATION AND USAGE OF AZIDES PRECURSOR AZIDES, TECHNICAL PRODUCTION AND PROPERTIES SODIUM AZIDE (NAN3) TRIMETHYLSILYL AZIDE (TMSA) DIPHENYLPHOSPHORYL AZIDE (DPPA) TRIBUTYLTIN AZIDE (TBSNA) AZIDOACETIC ACID ETHYL ESTER (AAE) TETRABUTYLAMMONIUM AZIDE (TBAA) OTHERS EXAMPLES FOR THE USE OF AZIDES ON A TECHNICAL SCALE ADDITION OF NAN3 TO MULTIPLE CC- OR CN-BONDS ADDITION OF ALK-N3 AND AR-N3 TO MULTIPLE CC- AND/OR CN-BONDS CARBOXYLIC ACID AZIDES: PRECURSORS FOR ISOCYANATES ORGANIC AZIDES: RING OPENING REACTION ON OXIRANES AND AZIRIDINES: PACLITAXEL, TAMI? U® ORGANIC AZIDES: PROTECTIVE GROUP, MASKED AMINES ORGANIC AZIDES: CROSS-LINKING AGENTS FOR POLYMERS THE FUTURE OF COMMERCIAL-SCALE AZIDE CHEMISTRY 3 SYNTHESIS OF AZIDES SYNTHESIS OF ALKYL AZIDES CLASSIC NUCLEOPHILIC SUBSTITUTIONS: AZIDES FROM HALIDES, SULFONATES, SUL? TES, CARBONATES, THIOCARBONATES AND SULFONIUM SALTS AZIDES BY RING OPENING OF EPOXIDES AND AZIRIDINES AZIDES BY THE MITSUNOBU REACTION ALKYL AZIDES FROM AMINES ALKYL AZIDES FROM CARBON NUCLEOPHILES AND ELECTRON-POOR SULFONYL AZIDES SYNTHESIS OF ARYL AZIDES NUCLEOPHILIC AROMATIC SUBSTITUTION: SNAR REACTIONS ARYL AZIDES FROM DIAZONIUM COMPOUNDS ARYL AZIDES FROM ORGANOMETALLIC REAGENTS ARYL AZIDES BY DIAZO TRANSFER ARYL AZIDES FROM HYDRAZINES AND FROM NITROSOARENES SYNTHESIS OF ACYL AZIDES ACYL AZIDES FROM MIXED ACID CHLORIDES ACYL AZIDES FROM MIXED ANHYDRIDES ACYL AZIDES BY DIRECT CONVERSION OF CARBOXYLIC ACIDS ACYL AZIDES BY DIRECT CONVERSION OF ALDEHYDES ACYL AZIDES BY DIRECT CONVERSION OF ACYLHYDRAZINES ACYL AZIDES FROM N-ACYLBENZOTRIAZOLES 4 AZIDES BY OLE? N HYDROAZIDATION REACTIONS CONJUGATE ADDITION OF HYDRAZOIC ACID AND ITS DERIVATIVES ADDITION OF HYDRAZOIC ACID AND ITS DERIVATIVES TO NON-ACTIVATED OLE? NS COBALT-CATALYZED HYDROAZIDATION OPTIMIZATION OF THE COBALT-CATALYZED HYDROAZIDATION REACTION SCOPE OF THE HYDROAZIDATION OF OLE? NS FURTHER PROCESS OPTIMIZATION ONE-POT FUNCTIONALIZATION OF THE AZIDE PRODUCTS MECHANISTIC INVESTIGATIONS CONCLUSION PART 2: REACTIONS 5 THE CHEMISTRY OF VINYL, ALLENYL, AND ETHYNYL AZIDES INTRODUCTION AND EARLY SYNTHETIC METHODS FOR VINYL AZIDES NEW METHODS TO PREPARE VINYL AZIDES REACTIONS OF VINYL AZIDES THE CHEMISTRY OF ALLENYL AZIDES GENERATION OF ETHYNYL AZIDES ACKNOWLEDGMENT 6 SMALL RINGS BY AZIDE CHEMISTRY 2H-AZIRINES AZIRIDINES AZIRIDINES VIA NITRENE INTERMEDIATES AZIRIDINES VIA TRIAZOLINES AZIRIDINES FROM EPOXIDES OR 1,2-DIOLS AZIRIDINES FROM VINYL AZIDES VIA 2H-AZIRINES TRIAZIRIDINES AZETIDINONES 7 SCHMIDT REARRANGEMENT REACTIONS WITH ALKYL AZIDES INTRODUCTION AND EARLY ATTEMPTS (1940–60) SCHMIDT REACTIONS OF ALKYL AZIDES WITH CARBONYL COMPOUNDS INTRAMOLECULAR REACTIONS INTERMOLECULAR REACTIONS REACTIONS OF HYDROXYALKYL AZIDES SCHMIDT REACTIONS OF ALKYL AZIDES WITH CARBOCATIONS METAL-MEDIATED SCHMIDT REACTIONS OF ALKYL AZIDES WITH ALKENES AND ALKYNES REACTIONS OF ALKYL AZIDES WITH ?,?-UNSATURATED KETONES REACTIONS OF ALKYL AZIDES WITH EPOXIDES COMBINED SCHMIDT REARRANGEMENT CASCADE REACTIONS SCHMIDT REARRANGEMENTS IN THE TOTAL SYNTHESIS OF NATURAL PRODUCTS SCHMIDT REARRANGEMENTS OF ALKYL AZIDES IN THE SYNTHESIS OF INTERESTING NON-NATURAL PRODUCTS 7 10 SCHMIDT REARRANGEMENTS OF HYDROXYALKYL AZIDES TOWARD BIOLOGICALLY RELEVANT COMPOUNDS 7 11 FINAL COMMENTS ACKNOWLEDGMENTS 8 RADICAL CHEMISTRY WITH AZIDES ADDITION OF THE AZIDYL RADICAL ONTO ALKENES METAL GENERATED AZIDYL RADICALS AZIDATION USING HYPERVALENT IODINE COMPOUNDS HALOGEN AZIDES AS A SOURCE OF AZIDYL RADICALS ELECTROCHEMICALLY GENERATED AZIDYL RADICALS AZIDATION OF CARBON CENTERED RADICALS RADICAL AZIDATION RADICAL ADDITIONS TO ALKYL AND ARYL AZIDES AMINYL AND AMIDYL RADICALS VIA REDUCTION OF AZIDES PHOTO- AND ELECTROCHEMICAL REDUCTIONS OF ORGANIC AZIDES TO AMINES REDUCTION OF ORGANIC AZIDES WITH METALS RADICAL REACTIONS OF ORGANIC AZIDES WITH TRIBUTYLTIN HYDRIDE RADICAL REDUCTIONS OF ORGANIC AZIDES WITH SILANES FRAGMENTATION REACTION OF ?-AZIDOALKYL RADICALS CONCLUSIONS 9 CYCLOADDITION REACTIONS WITH AZIDES: AN OVERVIEW HUISGEN 1,3-DIPOLAR CYCLOADDITION COPPER-CATALYZED AZIDE-ALKYNE CYCLOADDITION (CUAAC) GENERAL ASPECTS OF THE CUAAC REACTION MECHANISM OF THE CUAAC REACTION ACCELERATION OF THE CLICK REACTION ADDITION OF LIGANDS ADDITION OF BASE COPPER-FREE CLICK CHEMISTRY RUTHENIUM-CATALYZED AZIDE-ALKYNE CYCLOADDITION (RUAAC) USE OF OTHER METALS FOR THE CYCLOADDITION OF AZIDES AND ALKYNES: NI(II), PT(II), PD(II) CYCLOADDITION REACTIONS WITH AZIDES FOR THE SYNTHESIS OF TETRAZOLES INTERMOLECULAR APPROACHES CLICK CHEMISTRY FOR THE SYNTHESIS OF DIHYDROTRIAZOLES CYCLOADDITION REACTIONS WITH AZIDES TO GIVE THIATRIAZOLES 10 DIPOLAR CYCLOADDITION REACTIONS IN PEPTIDE CHEMISTRY 10 1 INTRODUCTION 10 2 AMINO ACID DERIVATIVES BY DCR 10 3 PEPTIDE BACKBONE MODI? CATIONS BY DCR 10 4 OTHER PEPTIDE MODI? CATIONS BY DCR 10 5 MACROCYCLIZATION BY DCR 10 6 DENDRIMERS AND POLYMERS 10 7 ISOTOPIC LABELING BY DCR 10 8 PERSPECTIVE PHOTOCHEMISTRY OF AZIDES: THE AZIDE/NITRENE INTERFACE 11 1 INTRODUCTION 11 2 PHOTOCHEMISTRY OF HYDRAZOIC ACID (HN3) 11 3 PHOTOCHEMISTRY OF ALKYL AZIDES 11 4 PHOTOCHEMISTRY OF VINYL AZIDES 11 5 PHOTOCHEMISTRY OF CARBONYL AZIDES AND AZIDE ESTERS 11 5 1 PHOTOCHEMISTRY OF AZIDE ESTERS 11 6 PHOTOCHEMISTRY OF PHENYL AZIDE AND ITS SIMPLE DERIVATIVES 11 6 1 PHOTOCHEMISTRY OF PHENYL AZIDE 11 6 2 PHOTOCHEMISTRY OF SIMPLE DERIVATIVES OF PHENYL AZIDE 11 6 3 PHOTOCHEMISTRY OF POLYNUCLEAR AROMATIC AZIDES 11 7 CONCLUSION 12 ORGANOAZIDES AND TRANSITION METALS 12 1 INTRODUCTION 12 2 METAL COMPLEXES CO-CRYSTALLIZED WITH AN ORGANOAZIDE 12 3 CATIONIC METAL COMPLEXES WITH ORGANOAZIDE CONTAINING ANIONS 12 4 METAL COMPLEXES WITH LIGANDS BEARING A NON-COORDINATING ORGANOAZIDE UNIT 12 5 METAL COMPLEXES WITH AN INTACT, COORDINATING AND LINEAR ORGANOAZIDE LIGAND 12 6 METAL COMPLEXES WITH AN INTACT, COORDINATING BUT BENT ORGANOAZIDE LIGAND 12 7 ORGANOAZIDES REACTING WITH OTHER METAL BOUND LIGANDS PART 3: MATERIAL SCIENCES 13 AZIDE-CONTAINING HIGH ENERGY MATERIALS 13 1 INTRODUCTION 13 2 ORGANIC AZIDES 13 2 1 ALKYL AND ALKENYL SUBSTITUTED AZIDES 13 2 2 ARYL SUBSTITUTED AZIDES 13 2 3 HETEROCYCLES CONTAINING AZIDE GROUPS 14 AZIDE CHEMISTRY IN ROTAXANE AND CATENANE SYNTHESIS 14 1 INTRODUCTION 14 2 PURELY ORGANIC ROTAXANES AND CATENANES 14 2 1 WITH CUCURBITURILS (CB) AND CYCLODEXTRINS (CD) AS CYCLIC COMPONENTS 14 2 2 BASED ON HYDROGEN BONDING OR ON ORGANIC DONOR-ACCEPTOR COMPLEXES 14 3 TRANSITION METAL TEMPLATED APPROACHES 14 3 1 CU(I) ASSEMBLED ROTAXANES 14 3 2 CU(I) AS BOTH A TEMPLATE AND A CATALYST 14 4 CONCLUSION PART 4: APPLICATION IN BIOORGANIC CHEMISTRY 15 AZA-WITTIG REACTION IN NATURAL PRODUCT SYNTHESES 15 1 INTRODUCTION 15 2 INTERMOLECULAR AZA-WITTIG REACTION 15 2 1 REACTION WITH CARBONYL COMPOUNDS 15 2 2 REACTION WITH HETEROCUMULENE DERIVATIVES 15 3 INTRAMOLECULAR AZA-WITTIG REACTION 15 3 1 FUNCTIONALIZED PHOSPHAZENES CONTAINING AN ALDEHYDE GROUP 15 3 2 FUNCTIONALIZED PHOSPHAZENES CONTAINING A KETONE GROUP 15 3 3 FUNCTIONALIZED PHOSPHAZENES CONTAINING AN ESTER GROUP 15 3 4 FUNCTIONALIZED PHOSPHAZENES CONTAINING AN AMIDE GROUP 15 4 CONCLUSIONS 16 AZIDES IN CARBOHYDRATE CHEMISTRY 16 1 INTRODUCTION 16 2 SYNTHESIS OF AZIDE-CONTAINING CARBOHYDRATES 16 3 AZIDES AS PROTECTING GROUPS DURING AMINOGLYCOSIDE SYNTHESIS 16 4 AZIDES AS NON-PARTICIPATING NEIGHBORING GROUPS IN GLYCOSYLATIONS 16 5 GLYCOSYL AZIDES AS PRECURSORS FOR GLYCOSYL AMIDES 16 6 SYNTHESIS OF GLYCOCONJUGATES VIA AZIDE-ALKYNE [3+2] CYCLOADDITION 16 7 METABOLIC OLIGOSACCHARIDE ENGINEERING