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Hydride-Mediated Intramolecular Reductive Head-To-Tail Michael Reaction of Enones with Activated Alkene Tethers Moonki Seok

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Hydride-Mediated Intramolecular Reductive Head-To-Tail Michael Reaction of Enones with Activated Alkene Tethers Moonki Seok Florida State University Libraries Electronic Theses, Treatises and Dissertations The Graduate School 2006 Tin(IV) Hydride-Mediated Intramolecular Reductive Head-to-Tail Michael Reaction of Enones with Activated Alkene Tethers Moonki Seok Follow this and additional works at the FSU Digital Library. For more information, please contact [email protected] THE FLORIDA STATE UNIVERSITY COLLEGE OF ARTS AND SCIENCES TIN(IV) HYDRIDE-MEDIATED INTRAMOLECULAR REDUCTIVE HEAD-TO-TAIL MICHAEL REACTION OF ENONES WITH ACTIVATED ALKENE TETHERS By MOONKI SEOK A Thesis submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Master of Science Degree Awarded: Spring Semester, 2006 The members of the Committee approve the Thesis of Moonki Seok defended on April 5, 2006. __________________________________ Marie E. Krafft Professor Directing Thesis __________________________________ Gregory B. Dudley Committee Member __________________________________ Robert A. Holton Committee Member __________________________________ Albert E. Stiegman Committee Member The Office of Graduate Studies has verified and approved the above named committee members. ii To my parents, wife Hyunjung and daughter Minkyung (Jean) with love and gratitude iii ACKNOWLEDGMENTS I would like to express appreciation to my major professor, Dr. Marie E. Kraft, for her guidance and support. I also would like to thank the members of my committee, Dr. Dudley, Dr. Holton, Dr. Stiegman and Dr. Zakarian, for their comments. I need to thank all past and present members of the Krafft group, especially Dr. Yonghao Jin, Dr. Amin Wang and James Wright for their help and advice. Finally, I would like to thank all my Korean friends. iv TABLE OF CONTENTS List of Tables .................................................................................................................. vii List of Figures .................................................................................................................. viii Standard List of Abbreviations ............................................................................................. xii Abstract ........................................................................................................................ xix 1. INTRODUCTION ............................................................................................................ 1 1. Enones as Latent Enolates ........................................................................................ 1 2. Catalytic Hydrometallation Method ......................................................................... 2 2.1 Catalytic enolization via conjugate reduction of enones.................................... 2 2.2 Catalytic reductive coupling of enones .............................................................. 4 Aldol processes................................................................................................... 4 Michael processes............................................................................................... 7 3. Reductive Couplings of Enones via Tin Enolates (Hydride Reduction Methods) ... 10 3.1 1,4-hydrostannation of conjugated enones by a radical process ........................ 11 3.2 Ionic 1,4-hydrostannation................................................................................... 14 Summary .................................................................................................................. 16 2. RESULTS AND DISCUSSION ....................................................................................... 17 1. Enone to Enone Reductive Coupling Reaction......................................................... 18 2. Enone to Enoate Reductive Coupling Reaction........................................................ 21 3. Enone to Enenitrile Reductive Coupling Reaction................................................... 33 Summary .................................................................................................................. 34 3. EXPERIMENTAL............................................................................................................ 36 General Considerations................................................................................................. 36 Synthesis of Substrates ................................................................................................. 37 Cyclization of Substrates .............................................................................................. 47 v APPENDIX .................................................................................................................. 53 REFERENCES .................................................................................................................. 115 BIOGRAPHICAL SKETCH ................................................................................................ 119 vi LIST OF TABLES Table 1: Reductive Aldol Coupling Catalyzed by Phosphine Modified Rh4(CO)12.............. 5 Table 2: Radical Cyclization at the β-Carbons of Activated Alkenes................................... 12 Table 3: Optimization of Michael Cyclizations of Bisenones under Radical Conditions..... 20 Table 4: Activation of Tin enolates by the Addition of Additives ........................................ 23 Table 5: Michael Cyclization of α,β-Unsaturated Esters Catalyzed by Bu4NBr................... 26 Table 6: NOE Observations for Cyclization Products........................................................... 27 Table 7: Michael Cyclization of α,β-Unsaturated Ester 57 Using V-70 as a Radical Initiator 31 Table 8: Michael Cyclization of Additional Alkyl Enones ................................................... 32 vii LIST OF FIGURES Figure 1: 500 MHz 1H NMR Spectrum of Enone 58 ............................................................ 54 Figure 2: 75 MHz 13C Spectrum of Enone 58 ....................................................................... 55 Figure 3: IR Spectrum of Enone 58 ...................................................................................... 56 Figure 4: 500 MHz 1H NMR Spectrum of Enone 69 ............................................................ 57 Figure 5: 75 MHz 13C Spectrum of Enone 69 ....................................................................... 58 Figure 6: IR Spectrum of Enone 69 ...................................................................................... 59 Figure 7: 500 MHz 1H NMR Spectrum of Enone 71 ............................................................ 60 Figure 8: 75 MHz 13C Spectrum of Enone 71 ....................................................................... 61 Figure 9: IR Spectrum of Enone 71 ...................................................................................... 62 Figure 10: 500 MHz 1H NMR Spectrum of Alcohol 87 ....................................................... 63 Figure 11: 75 MHz 13C Spectrum of Alcohol 87 .................................................................. 64 Figure 12: IR Spectrum of Alcohol 87 ................................................................................. 65 Figure 13: 500 MHz 1H NMR Spectrum of Enone 73 .......................................................... 66 Figure 14: IR Spectrum of Enone 73 .................................................................................... 67 Figure 15: 500 MHz 1H NMR Spectrum of Enone 76 .......................................................... 68 Figure 16: IR Spectrum of Enone 76 .................................................................................... 69 Figure 17: 500 MHz 1H NMR Spectrum of Enone 77 .......................................................... 70 Figure 18: IR Spectrum of Enone 77 .................................................................................... 71 viii Figure 19: 500 MHz 1H NMR Spectrum of syn-49 .............................................................. 72 Figure 20: 75 MHz 13C Spectrum of syn-49 ......................................................................... 73 Figure 21: IR Spectrum of syn-49 ........................................................................................ 74 Figure 22: 500 MHz 1H NMR Spectrum of anti-49 ............................................................. 75 Figure 23: 75 MHz 13C Spectrum of anti-49 ........................................................................ 76 Figure 24: IR Spectrum of anti-49 ........................................................................................ 77 Figure 25: 500 MHz 1H NMR Spectrum of syn-51 .............................................................. 78 Figure 26: 75 MHz 13C Spectrum of syn-51 ......................................................................... 79 Figure 37: IR Spectrum of syn-51 ........................................................................................ 80 Figure 28: 500 MHz 1H NMR Spectrum of anti-51 ............................................................. 81 Figure 29: 75 MHz 13C Spectrum of anti-51 ........................................................................ 82 Figure 30: IR Spectrum of anti-51 ........................................................................................ 83 Figure 31: 500 MHz 1H NMR Spectrum of syn-59 .............................................................. 84 Figure 32: 75 MHz 13C Spectrum of syn-59 ......................................................................... 85 Figure 33: IR Spectrum of syn-59 .......................................................................................
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