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Rollover in the Synthesis of Polycyclic Indoles, and a One-Pot Zipper-Click Reaction

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Rollover in the Synthesis of Polycyclic Indoles, and a One-Pot Zipper-Click Reaction Rollover in the synthesis of polycyclic indoles, and a one-pot Zipper-Click reaction A thesis submitted to the University of Manchester for the degree of Doctor of Philosophy (PhD) in the Faculty of Engineering and Physical Science 2015 Sinead Balgobin School of Chemistry ii Contents 1. C–H activation for alkyne insertion ........................................................... 1 1.1. Introduction ........................................................................................ 1 1.1.1. C–H bond activation and functionalisation .................................... 1 1.1.2. Palladium in C–H bond activation and functionalisation ............... 5 1.1.3. Rhodium in C–H bond activation and functionalisation .............. 13 1.1.4. Ruthenium in C–H bond activation and functionalisation ............ 20 1.1.5. This work ................................................................................... 30 1.2. Results and Discussion ...................................................................... 31 1.2.1. Introduction ............................................................................... 31 1.2.2. Pd-catalysed alkyne insertion ...................................................... 36 1.2.3. Rh-catalysed alkyne insertion ...................................................... 48 1.2.4. Ru-catalysed alkyne insertion ...................................................... 65 1.3. Recent literature developments .......................................................... 69 1.4. Conclusion ....................................................................................... 72 2. A one-pot zipper-click reaction ................................................................ 73 2.1. Introduction ...................................................................................... 73 2.1.1. Migration of unsaturation ........................................................... 73 2.1.2. The acetylene zipper reaction ...................................................... 79 i 2.1.3. Azide-alkyne cycloadditions: click reactions ............................... 90 2.1.4. This work ................................................................................ 101 2.1. Results and discussion .................................................................... 102 2.1.1. One-pot zipper-click reaction .................................................... 102 2.1.2. Other one-pot zipper reactions .................................................. 114 2.1.3. Alternative zipper conditions .................................................... 120 2.1.4. Conclusions ............................................................................. 125 2.1.5. Future Work ............................................................................ 126 ii Abstract The University of Manchester School of Chemistry Sinead Balgobin Doctor of Philosophy 2015 Rollover in the synthesis of polycyclic indoles, and a one-pot Zipper-Click reaction This thesis contains two chapters, the first concerning the use of C–H activation in the synthesis of polyaromatic indoles, and the second concerning an investigation into the acetylene zipper reaction. C–H activation provides a convenient, atom efficient route for the construction of C–C bonds, without the prerequisite for stoichiometric organometallic precursors or pre-functionalisation of the substrates. In this research the use of C–H activation for the insertion of an alkyne into an N-(hetero)arylated indole system has been investigated; the transformation was achieved using Rh catalysis in moderate to good yields. The concept of rollover has also been discussed. This is where, after a metallation step, the molecule undergoes a bond rotation allowing further reaction at a different part of the molecule. The acetylene zipper reaction is a powerful contrathermodynamic reaction which allows the migration of an internal alkyne to the terminal position. The alkyne moiety is a useful handle for many reactions, not least the robust CuI-catalysed azide alkyne cycloaddition (CuAAC, also known as a click reaction), which can be used to synthesis useful triazole products. In this research a one-pot zipper-click reaction has been investigated to provide 1,4-disubstituted-1,2,3-triazoles. iii Declaration No portion of the work referred to in the thesis has been submitted in support of an application for another degree or qualification of this or any other university or other institute of learning. iv Copyright Statement i. The author of this thesis (including any appendices and/or schedules to this thesis) owns certain copyright or related rights in it (the “Copyright”) and she has given The University of Manchester certain rights to use such Copyright, including for administrative purposes. ii. Copies of this thesis, either in full or in extracts and whether in hard or electronic copy, may be made only in accordance with the Copyright, Designs and Patents Act 1988 (as amended) and regulations issued under it or, where appropriate, in accordance with licensing agreements which the University has from time to time. This page must form part of any such copies made. iii. The ownership of certain Copyright, patents, designs, trademarks and other intellectual property (the “Intellectual Property”) and any reproductions of copyright works in the thesis, for example graphs and tables (“Reproductions”), which may be described in this thesis, may not be owned by the author and may be owned by third parties. Such Intellectual Property and Reproductions cannot and must not be made available for use without the prior written permission of the owner(s) of the relevant Intellectual Property and/or Reproductions. iv. Further information on the conditions under which disclosure, publication and commercialisation of this thesis, the Copyright and any Intellectual Property and/or reproductions described in it may take place is available in the University IP Policy (see http://documents.manchester.ac.uk/DocuInfo.aspx?DocID=487), in any relevant thesis restriction declarations deposited in the University Library, The University Library’s regulations (see http://www.manchester.ac.uk/library/aboutus/regulations) and in The University’s policy on Presentation of Theses v Just like moons and like suns, With the certainty of tides, Just like hopes springing high, Still I’ll rise. Maya Angelou, 1928-2014 vi Acknowledgments Thanks must of course be extended to my supervisor Mike, for making this possible and for providing invaluable guidance, advice and support. Thank you as well to the staff of the School of Chemistry, past and present, technical and administrative. To The Girls, Sam and Rachel, for being fantastic housemates and chemistry buddies, and making my time in Manchester a pleasure. Thanks also to Matt, for giving me a place to stay in my final few months and being a generally brilliant Post-Doc (brilliant Post-Doc thanks also go to Smith and Storr). The Holy Trinity and attendees of GCB: you have been amazing, and continue to be. I can always count on you to brighten up my day. Sarah, Sarah, Sam, Rachel, Chris, Gabri, Boris, Tom, Craig, James and Catherine; you will probably never know just how much your friendship has meant to me in the time we have known each other. You, knowingly and unknowingly, have helped me through some incredibly difficult and challenging times, and for this I will be forever grateful. To everyone who proof read or edited this, I apologise for it being a hot mess. I have not good English. Thanks for making it readable. Thanks also go to the rest of the Greaney and Procter group members, past and present: thank you for making the lab a fun and distracting place to work (OK, maybe I will take responsibility for the distracting part). I am grateful we helped each other make it through the long lab days. Also the demonstrating gang, for pretty much the same reason: Debbie, Rachel, Maddie, Rob, Catherine, Sarah, Sarah and Boris. Thank you to my friends outside of the department, who were always there for me. You have kept me sane and stopped me from losing myself into the PhD. Laura, Scott and John; Reiss, Marcus and Liam: sorry I’m rubbish at replying to messages, but know that you all mean so much to me. To my family, who always stand by and support me. vii Abbreviations Ac - acetyl Acac - acetylacetone AcOH - acetic acid tAmOH - tert-amyl alcohol Ar - aryl ArF - 4-(CF)3C6F4 AP - affinity-purification APCI - atmospheric pressure chemical ionization Asc - ascorbate atm - atmosphere Boc - tert-butoxycarbonyl b.p. - boiling point nBuLi - n-butyl lithium sBuLi - sec-butyl lithium tBuLi - tert-butyl lithium tBu - tert-butyl tBuOH - tert-butanol Bz - benzoyl CAL-B - Candida antarctica lipase B cat. - catalytic/catalyst CMD - concerted-metalation-deprotonation Cp - cyclopentyldienyl Cp* - pentamethylcyclopentadienyl viii cod - cyclooctadiene CuAAC - Copper-Catalysed Azide-Alkyne Cycloaddition Cy - cyclohexyl DAP - diaminopropane dba - dibenzylideneacetone DCM - dichloromethane DEPT - distortionless enhancement by polarization transfer DFT - density functional theory DG - directing group DIPEA - N,N-diisopropylethylamine DMA - N,N-dimethylacetamide DCE - 1,2-dichloroethane DMAD - dimethylacetylene dicarboxylate DME - dimethoxyethane DMF - N,N,-dimethylformamide DMSO - dimethylsulfoxide EDA - ethylene diamine EDG - electron donating group equiv. - equivalent Et - ethyl EtOAc - ethyl acetate EtOH - ethanol EI - electron impact ES - electrospray ESI - electrospray ionisation ix EWG - electron withdrawing
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