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Metal-Free Transfer Hydrogenation of Polar Unsaturated Compounds with Polar Hydrogen Donors – Scope, Limitations and Reaction Mechanism

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Metal-Free Transfer Hydrogenation of Polar Unsaturated Compounds with Polar Hydrogen Donors – Scope, Limitations and Reaction Mechanism Zurich Open Repository and Archive University of Zurich Main Library Strickhofstrasse 39 CH-8057 Zurich www.zora.uzh.ch Year: 2011 Metal-free transfer hydrogenation of polar unsaturated compounds with polar hydrogen donors – Scope, limitations and reaction mechanism Yang, X Posted at the Zurich Open Repository and Archive, University of Zurich ZORA URL: https://doi.org/10.5167/uzh-60420 Dissertation Published Version Originally published at: Yang, X. Metal-free transfer hydrogenation of polar unsaturated compounds with polar hydrogen donors – Scope, limitations and reaction mechanism. 2011, University of Zurich, Faculty of Science. Metal-Free Transfer Hydrogenation of Polar Unsaturated Compounds with Polar Hydrogen Donors－Scope, Limitations and Reaction Mechanism DISSERTATION zur Erlangung der naturwissenschaftlichen Doktorwürde (Dr. sc. nat.) vorgelegt der Mathematisch-naturwissenschaftlichen Fakultät der Universität Zürich von XIANGHUA YANG aus der V. R. China Promotionskomitee Prof. Dr. Heinz Berke (Vorsitz und Leitung) Prof. Dr. Roger Alberto Zürich, 2011 Xianghua Yang Contents 2011 CONTENTS Acknowledgments.................................................................................................................................... III Abbreviations ............................................................................................................................................. V 1. Introduction (I): Ammonia Borane for Chemical Hydrogen Storage ........................................ 1 1.1 Fossil fuels ...................................................................................................................................... 2 1.2 Renewable energy sources .......................................................................................................... 4 1.3 Hydrogen economy ........................................................................................................................ 5 1.4 Chemical hydrogen storage ......................................................................................................... 9 1.4.1 Metal hydrides ..................................................................................................................... 9 1.4.2 Chemical hydrides ............................................................................................................ 10 1.5 Ammonia borane .......................................................................................................................... 14 1.5.1 Hydrogen release from ammonia borane ..................................................................... 17 1.5.1.1 Thermal decomposition of ammonia borane in the solid state ......................... 17 1.5.1.2 Thermal decomposition of ammonia borane in solution .................................... 23 1.5.1.3 Metal catalyzed dehydrocoupling of ammonia borane ...................................... 28 1.5.1.4 Metal catalyzed solvolysis of ammonia borane .................................................. 31 1.5.1.5 Acid-catalyzed dehydrocoupling of ammonia borane ........................................ 35 1.5.2 Regeneration of ammonia borane .................................................................................. 37 1.6 Final remarks ................................................................................................................................ 41 1.7 References .................................................................................................................................... 42 2. Introduction (II): Transfer Hydrogenation Reactions .................................................................. 47 2.1 Catalytic hydrogenation .............................................................................................................. 47 2.2 Transfer hydrogenation ............................................................................................................... 49 2.2.1 Metallocatalytic transfer hydrogenations ....................................................................... 49 2.2.2 Organocatalytic transfer hydrogenations ...................................................................... 50 2.3 Goals and strategies .................................................................................................................... 54 2. 4 References ................................................................................................................................... 55 3. Transfer Hydrogenation of Imines with Ammonia-Borane: A Concerted Double-H Transfer Reaction? ................................................................................................................................................... 57 3.1 Introduction ................................................................................................................................... 57 3.2 Results and discussions ............................................................................................................. 58 3.3 Conclusions .................................................................................................................................. 66 3.4 References .................................................................................................................................... 67 3.5 Supporting information ................................................................................................................ 69 4. Facile Metal-Free Regioselective Transfer Hydrogenation of Polarized Olefins with Ammonia Borane ...................................................................................................................................... 87 4.1 Introduction ................................................................................................................................... 87 4.2 Results and discussion ............................................................................................................... 88 4.3 Conclusions................................................................................................................................... 94 4.4 References .................................................................................................................................... 95 4.5 Supplementary material .............................................................................................................. 96 I Xianghua Yang Contents 2011 5. Synthetic and Mechanistic Studies of Metal-Free Transfer Hydrogenations Applying Polarized Olefins as Hydrogen Acceptors and Amine Borane Adducts as Hydrogen Donors ..................................................................................................................................................................... 107 5.1 Introduction ................................................................................................................................. 107 5.2 Results and discussion ............................................................................................................. 108 5.3 Conclusions................................................................................................................................. 119 5.4 Experimental ............................................................................................................................... 120 5.5 References .................................................................................................................................. 127 6. Ammonia Borane as a Metal-Free Reductant for Ketones and Aldehydes: A Mechanistic Study .......................................................................................................................................................... 129 6.1 Introduction ................................................................................................................................. 129 6.2 Results and discussion ............................................................................................................. 130 6.3 Mechanistic studies of the hydroboration process ................................................................ 135 6.4 Conclusions................................................................................................................................. 141 6.5 Experimental section ................................................................................................................. 142 6.6 References ................................................................................................................................ 148 7. Theoretical Study and Metal-Free Transfer Hydrogenation and Dehydrogenation Reactions Applying Polarized Olefins .............................................................................................. 151 7.1 DFT calculations of hydrogenation/dehydrogenation energies ........................................... 151 7.2 Attempts of metal-free dehydrocoupling of AB using push-pull olefins .............................. 156 7.3 Metal-free transfer-hydrogenations using hydrogenated olefins as hydrogen donors .... 159 7.4 Outlook ........................................................................................................................................ 162 7.5 Experimental ............................................................................................................................... 163 7.6 References ...............................................................................................................................
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