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Metal Complexes As Catalysts for the Synthesis of Heterocycles

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Metal Complexes As Catalysts for the Synthesis of Heterocycles METAL COMPLEXES AS CATALYSTS FOR THE SYNTHESIS OF HETEROCYCLES Steven Lal Department of Chemistry, Imperial College London A thesis submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, Imperial College London May 2013 1 Declaration I certify that all the work in this thesis is solely my own, except where explicitly stated and appropriately referenced. No part of the thesis has been submitted previously for a degree at this, or any other, university. 2 Copyright Notice Imperial College of Science, Technology and Medicine Department Of Chemistry Metal Complexes as Catalysts for the Synthesis of Heterocycles © 2013 Steven Lal [email protected] The copyright of this thesis rests with the author and is made available under a Creative Commons Attribution Non-Commercial No Derivatives License. Researchers are free to copy, distribute or transmit the thesis on the condition that they attribute it, that they do not use it for commercial purposes and that they do not alter, transform or build upon it. For any reuse or redistribution, researchers must make clear to others the license terms of this work. Steven Lal Department of Chemistry Imperial College London Exhibition Road London SW7 2AZ UK www.imperial.ac.uk 3 Contents Abstract ...................................................................................................................................... 8 Acknowledgements .................................................................................................................. 10 List of abbreviations and acronyms ......................................................................................... 11 List of tables ............................................................................................................................. 16 List of figures ........................................................................................................................... 19 1. Introduction .......................................................................................................................... 21 1.1. History and reactivity of azides .................................................................................... 22 1.2. Click Chemistry ............................................................................................................ 26 1.3. The copper-catalysed azide-alkyne cycloaddition (CuAAC) reaction ......................... 27 1.3.1. Catalytic systems used for CuAAC reactions ........................................................ 30 1.3.1.1. Nitrogen-based ligands ................................................................................... 32 1.3.1.1.1. Amines ..................................................................................................... 32 1.3.1.1.2. Imine ligands ............................................................................................ 33 1.3.1.1.3. Pyridine ligands ....................................................................................... 34 1.3.1.1.4. Triazole ligands ........................................................................................ 35 1.3.1.1.5. Benzimidazole ligands ............................................................................. 38 1.3.1.2. Carbon-based ligands ...................................................................................... 38 1.3.1.2.1. NHC ligands............................................................................................. 38 1.3.1.2.2. Isocyanate ligands .................................................................................... 44 1.3.1.3. Phosphorus-based ligands ............................................................................... 45 1.3.1.4. Sulfur-containing ligands ................................................................................ 47 1.3.2. Reactions of electron-deficient azides ................................................................... 49 1.3.3. CuAAC reactions with silver, aluminium and gold acetylides .............................. 53 1.4. Other metal-catalysed azide-alkyne cycloaddition reactions ........................................ 54 1.5. Project aims ................................................................................................................... 56 2. Copper(I) Complexes Bearing Phosphorous Ligands for Click Azide-Alkyne Cycloaddition Reactions .......................................................................................................... 58 4 2.1. Introduction ................................................................................................................... 59 2.2. Preparation of phosphorous ligands .............................................................................. 59 2.3. Preparation of copper(I) complexes .............................................................................. 63 2.3.1. Phosphine complexes ............................................................................................. 64 2.3.2. Phosphinite and phosphonite complexes ............................................................... 65 2.3.2.1. Literature precedents ....................................................................................... 65 2.3.2.2. Preparation of phosphinite and phosphonite complexes ................................. 66 2.3.3. Phosphite complexes .............................................................................................. 69 2.4. Characterisation of novel copper(I) complexes ............................................................ 70 2.5. Synthesis of azides ........................................................................................................ 74 2.6. Preparation of a glyco-alkyne ....................................................................................... 76 2.7. Catalytic studies – CuAAC reaction ............................................................................. 76 2.7.1. CuAAC with 1:1 metal/ligand complexes ............................................................. 79 2.7.1.1. {CuBr[PPh2(OPh-2-OMe)]}-catalysed three component reaction ................. 83 2.7.2. CuAAC with 3:1 ligand/copper complex [CuBr(PPh3)3] 2.17 .............................. 85 2.7.2.1. [CuBr(PPh3)3]-catalysed synthesis of triazoles at low catalyst loadings ........ 89 2.7.2.2. [CuBr(PPh3)3]-catalysed three-component reaction ....................................... 92 2.8. Comparison of catalytic systems for the CuAAC reaction ........................................... 94 2.9. Conclusions ................................................................................................................... 95 3. Ruthenium-Catalysed Azide-Alkyne Cycloaddition Reactions........................................... 97 3.1. Introduction ................................................................................................................... 98 3.2. Ruthenium(II)-catalysed cycloaddition reaction of azides and terminal alkynes ......... 98 3.2.1. Mechanism of the ruthenium(II)-catalysed formation of 1,5-disubstituted triazoles ........................................................................................................................................ 102 3.2. Project aims ................................................................................................................. 105 3.3. Preparation of water-soluble ruthenium(II) complexes .............................................. 105 3.4. Preparation of water-soluble azides ............................................................................ 106 3.5. Catalytic studies .......................................................................................................... 107 3.6. Conclusions ................................................................................................................. 111 4. Cycloaddition Reactions of Organic Azides and Internal Alkynes ................................... 113 5 4.1. Introduction ................................................................................................................. 114 4.2. Copper(I)- and ruthenium(II)-catalysed azide-internal alkyne cycloaddition reactions ............................................................................................................................................ 114 4.3. [3+2] Cycloadditions of organic azides and haloalkynes ........................................... 117 4.3.1. Halotriazoles as attractive synthetic intermediates .............................................. 123 4.4. Project aims ................................................................................................................. 126 4.5. Results and Discussion ............................................................................................... 127 4.5.1. Metal-catalysed cycloaddition of benzyl azide and 3-hexyne/4-octyne .............. 127 4.5.2. Preparation of iodoalkynes .................................................................................. 137 4.5.3. Catalytic studies - Azide-iodoalkyne cycloaddition reactions ............................. 141 4.5.3.1. Copper(I) complexes bearing phosphorous ligands ...................................... 141 4.5.3.2. Copper(I) complexes bearing N-heterocyclic carbene ligands ..................... 147 4.5.3.2.1. Synthesis of NHC complexes ................................................................ 147 4.5.3.2.2. [CuX(NHC)]-catalysed azide-iodoalkyne cycloaddition
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