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Transfer Hydrogenation: Employing a Simple, in Situ Prepared Catalytic System

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Transfer Hydrogenation: Employing a Simple, in Situ Prepared Catalytic System Transfer Hydrogenation: Employing a Simple, in situ Prepared Catalytic System Thesis by Eleanor Pei Ling Ang In Partial Fulfillment of the Requirements For the Degree of Master of Science King Abdullah University of Science and Technology Thuwal, Kingdom of Saudi Arabia © April, 2017 Eleanor Ang Pei Ling All Rights Reserved 2 EXAMINATION COMMITTEE PAGE The thesis of Eleanor Pei Ling Ang is approved by the examination committee. Committee Chairperson: Prof. Kuo-Wei Huang Committee Members: Prof. Jörg Eppinger Prof. Zhiping Lai 3 ABSTRACT Transfer hydrogenation has been recognized to be an important synthetic method in both academic and industrial research to obtain valuable products including alcohols. Transition metal catalysts based on precious metals, such as Ru, Rh and Ir, are typically employed for this process. In recent years, iron-based catalysts have attracted considerable attention as a greener and more sustainable alternative since iron is earth abundant, inexpensive and non-toxic. In this work, a combination of iron disulfide with chelating bipyridine ligand was found to be effective for the transfer hydrogenation of a variety of ketones to the corresponding alcohols in the presence of a simple base. It provided a convenient and economical way to conduct transfer hydrogenation. A plausible role of sulfide next to the metal center in facilitating the catalytic reaction is demonstrated. 4 ACKNOWLEDGEMENTS I would like to express my gratitude to my supervisor, Professor Kuo-Wei Huang, for his guidance, support, valuable insights and advice throughout the course of this research. I would also like to acknowledge Prof. Jörg Eppinger and Prof. Zhiping Lai for their kind agreement to be part of my examination committee. My appreciation also goes to all members in Pofesso Huag’s goup and KAUST Catalysis Center (KCC) who have helped me in one way or another and for making my time at King Abdullah University of Science and Technology a great experience. Finally, my heartfelt gratitude is extended to my husband for his patience, care and encouragement. 5 TABLE OF CONTENTS Page EXAMINATION COMMITTEE PAGE .................................................................... 2 ABSTRACT ........................................................................................................ 3 ACKNOWLEDGEMENTS ..................................................................................... 4 TABLE OF CONTENTS ........................................................................................ 5 LIST OF ABBREVIATIONS ................................................................................... 7 LIST OF ILLUSTRATIONS .................................................................................... 8 LIST OF TABLES ................................................................................................. 10 Chapter 1: Reduction of C=O ……………………………………….………………………..…………... 11 1.1 General Background on Transfer Hydrogenation .………………………………… 13 1.2 Developments in Transfer Hydrogenation ……..………..………….….…..………. 14 1.3 Ru-, Rh- and Ir- Catalyzed Transfer Hydrogenation …..………….………...….. 18 1.4 Iron-Catalyzed Transfer Hydrogenation ……..………..………….…..………….….. 24 Chapter 2: Iron-Based Catalytic System in Transfer Hydrogenation …….…..…….……. 31 2.1 Introduction .………………………………………..……………………………….….………….. 31 2.2 Results and Discussion …………………………………………………………………………… 33 2.2.1 Optimization of reaction conditions .…………….……………………….………….. 34 6 2.2.2 Control reactions ……….…….………..……………………………………………………... 37 2.2.3 Plausible role of sulfides ……….……………..…….………….………………….……... 38 2.3 Conclusion ………………………….………..……………………………………………………... 39 2.4 Experimental Section …………………..…………………………………………………….... 40 Chapter 3: Molybdenum-Based Catalytic System in Transfer Hydrogenation .……… 41 3.1 Introduction .………………………………………..………………………………….……….….. 41 3.2 Results and Discussion …………………………………………………………….….……….. 42 3.3 Using a Different Hydrogen Donor …….………………………………………….…….. 45 3.4 Scope of the Catalytic Transfer Hydrogenation ……………………….…….……… 45 3.5 Experimental Section …………………..…………………………………………………….... 47 Chapter 4: Mechanistic insights .…………………………………………………………………….…… 49 4.1 Introduction .………………………………………..……………………………….….………….. 49 4.2 Results and Discussion …………………………………………………………………………… 49 4.2.1 ReactIR .…………….…………………………………………….…………………….………….. 50 4.2.2 APCI-MS ……….…….………..…………………………………………………………………... 53 4.2.3 Proposed Mechanism ……….…….………..….…………………………………………... 58 4.3 Conclusion ………………………….………..……………………………………………………... 64 4.4 Experimental Section …………………..…………………………………………………….... 65 REFERENCES ..................................................................................................... 66 APPENDIX ......................................................................................................... 72 7 LIST OF ABBREVIATIONS APCI Atmospheric Pressure Chemical Ionization ATR Attenuated Total Reflection DPEN 1,2-diphenyl-1,2-ethylenediamine FeS iron sulfide FeS2 iron disulfide GC Gas Chromatography h hour IR Infrared KOH potassium hydroxide m/z mass/charge Mes mesityl group MPV Meerwein-Ponndorf-Verley MS Mass Spectrometry MoS2 molybdenum disulfide NHC N-heterocyclic carbene NMR Nuclear Magnetic Resonance R organic substituent 8 LIST OF ILLUSTRATIONS Scheme 1. A typical metal hydride reduction ................................................................. 11 Scheme 2. A typical catalytic hydrogenation .................................................................. 12 Scheme 3. Catalytic transfer hydrogenation using isopropanol as hydrogen source ..... 13 Scheme 4. Hydrogen transfer in Meerwein-Ponndorf-Verley reduction ........................ 15 Figure 1. Catalytic cycle of ruthenium dihyride mediated transfer hydrogenation ........ 16 Figure 2. Tasfe hdogeatio ediated Sho’s atalst ………………………………..... 19 Figure 3. Selected examples of ruthenium-ased tasfe hdogeatio atalsts …... 21 Figure 4. Selected examples of rhodium-based transfer hydrogenation catalysts ......... 22 Figure 5. Selected examples of iridium-based transfer hydrogenation catalysts ........... 24 Figure 6. Ketone hydrogenation catalysts of Casey and Guan and Shvo with hydridic M-H and protonic O-H groups. ……………………………………………………………………………………........ 26 Figure 7. Repesetatie eaples of Gao’s goup PNNP ligads ad thei io complexes ....................................................................................................................... 27 Scheme 5. Partial PNNP ligand reduction in the iron comple ……………………………......... 28 Figure 8. Aieiiediphosphie io oplees ……………………………………………........ 29 Figure 9. Iron-NHC complexes for transfer hydrogenation …………….………………….…....... Figure 10. Proposed mechanism for transfer hydrogenation of ketones catalyzed by Ru12 ………………………………………..………………………………………………………………………………... 32 Scheme 6. Formation of dearomatized iron complex in the pesee of a ase …......... 33 Scheme 7. Iron-catalyzed transfer hydrogen of cyclohexanone ..................................... 34 Figure 11. Kinetics of the transfer hydrogenation of cyclohexanone using the combination of iron disulfide with 6-amino-,’-bipyridie …………….………………….……... Scheme 8. Transfer hydrogenation of cyclohexanone using the combination of iron disulfide ith ,’-bipyridine .......................................................................................... 38 Scheme 9. Transfer hydrogenation of cyclohexanone using the combination of molybdenum disulfide with 6-amino-,’-bipyridine ..................................................... 42 9 Figure 12. Kinetics of the transfer hydrogenation of cyclohexanone using the combination of molybdenum disulfide with 6-amino-,’-bipidie .…………..…………... 43 Scheme 10. Transfer hydrogenation of cyclohexanone using the metal chloride salt ... 44 Figure 13. (a-d) Reaction spectra recorded at different time intervals for the: a) & b) iron-catalyzed transfer hydrogenation of cyclohexanone using 6-amino-,′-bipyridine ad ,′-bipyridine, respectively as the ligand, c) & d) reaction involving iron disulfide with 6-amino-,′-bipyridine and just 6-amino-,′-bipyridine, respectively without the substrate cyclohexanone. (e) Reference spectra for the solvent isopropanol and the ligand 6-amino-,′-ipidie dissoled i isopopaol. …………………………………………... Figure 14. APCI-MS analysis after the transfer hydrogenation using an in situ combination of 6-amino-,’-bipyridine with iron disulfide ………………………….…….……... 53 Figure 15. Possible iron species formed from aminobipyridine binding to the iron sulfide …………………………………………………………………………………………………………………………………… 54 Figure 16. Possile io die speies ……………………………………………………………………….. 54 Figure 17. Isotopic distribution centered around m/z = 259 in a) experimental and 2+ simulated mass spectra of b) the doubly charged dimeric species [M2+Fe2S2] and c) its corresponding monomeric species [M+FeS]+ ………………..…………………………….…………….. 56 Figure 18. Possible corresponding monomeric iron species from homolytic cleavage of the S-S bond during the ionization process ………………….……..……………………….…………….. 57 Figure 19. APCI-MS analysis after the reaction between iron disulfide with 6-amino-,′- bipyridine in the presence of the base, without the sustate ….……………………………….. 58 Figure 20. Proposed mechanism for catalytic transfer hydrogenation of ketone via the direct hydrogen transfer route .………………………………..…………………………………..…………... 60 Figure 21. Proposed mechanism for catalytic transfer hydrogenation of ketone via the hydridic route .……………………………………………………………………….……………………..…………... 62 Figure 22. A plausible
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